U.S. patent application number 17/201150 was filed with the patent office on 2022-09-15 for dental adhesive composition excellent in storage stability.
This patent application is currently assigned to SHOFU INC.. The applicant listed for this patent is SHOFU INC.. Invention is credited to Daisuke HARA, Shunsuke MIYATA, Kenzo YAMAMOTO.
Application Number | 20220287918 17/201150 |
Document ID | / |
Family ID | 1000005855439 |
Filed Date | 2022-09-15 |
United States Patent
Application |
20220287918 |
Kind Code |
A1 |
YAMAMOTO; Kenzo ; et
al. |
September 15, 2022 |
DENTAL ADHESIVE COMPOSITION EXCELLENT IN STORAGE STABILITY
Abstract
[Problem] To provide a dental adhesive composition having
excellent storage stability and adhesive strength. [Solution] To
provide a dental adhesive composition, comprising (A) polymerizable
monomer, (D) photopolymerization accelerator, and (F) volatile
organic solvent, wherein, the dental adhesive composition comprises
(A-1) polymerizable monomer having an acidic group as the (A)
polymerizable monomer, and the dental adhesive composition
comprises (D-1) aliphatic tertiary amine compound represented by
formula (1) as the (D) photopolymerization accelerator.
##STR00001## (wherein R.sub.1 represents a substituent consisting
of three or more carbons having an electron-withdrawing group at
.alpha.-carbon and/or .beta.-carbon of an amine starting from N,
R.sub.2 represents a substituent consisting of three or more
carbons which may have an electron-withdrawing group, R.sub.3
represents a substituent consisting of one or more carbons which
may have an electron-withdrawing group, and .alpha.-carbon of N in
the formula (1) is not an electron-withdrawing group.)
Inventors: |
YAMAMOTO; Kenzo; (Kyoto,
JP) ; HARA; Daisuke; (Kyoto, JP) ; MIYATA;
Shunsuke; (Kyoto, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SHOFU INC. |
Kyoto |
|
JP |
|
|
Assignee: |
SHOFU INC.
Kyoto
JP
|
Family ID: |
1000005855439 |
Appl. No.: |
17/201150 |
Filed: |
March 15, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K 6/30 20200101; A61K
6/62 20200101; A61K 6/831 20200101 |
International
Class: |
A61K 6/30 20060101
A61K006/30; A61K 6/62 20060101 A61K006/62; A61K 6/831 20060101
A61K006/831 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 12, 2021 |
JP |
2021-40033 |
Mar 12, 2021 |
JP |
2021-40037 |
Mar 12, 2021 |
JP |
2021-40039 |
Mar 12, 2021 |
JP |
2021-40040 |
Claims
1. A dental adhesive composition, comprising (A) polymerizable
monomer, (D) photopolymerization accelerator, and (F) volatile
organic solvent, wherein, the dental adhesive composition comprises
(A-1) polymerizable monomer having an acidic group as the (A)
polymerizable monomer, and the dental adhesive composition
comprises (D-1) aliphatic tertiary amine compound represented by
formula (1) as the (D) photopolymerization accelerator.
##STR00035## (wherein R.sub.1 represents a substituent consisting
of three or more carbons having an electron-withdrawing group at
.alpha.-carbon and/or .beta.-carbon of an amine starting from N,
R.sub.2 represents a substituent consisting of three or more
carbons which may have an electron-withdrawing group, R.sub.3
represents a substituent consisting of one or more carbons which
may have an electron-withdrawing group, and .alpha.-carbon of N in
the formula (1) is not an electron-withdrawing group.)
2. The dental adhesive composition according to claim 1, wherein
the electron-withdrawing group in R.sub.1 is a substituent selected
from a functional group selected from the group consisting of a
hydroxyl group, a carboxyl group, a vinyl group, an aryl group and
a halogen, and, an organic group which is bonded via an ether bond,
an ester bond, a urethane bond or a urea bond and may have --OH
group, --O-group, --C(O)-group, --S-group, --NH--C(O)--NH-group,
--C(O)--O-group, --O--C(O)-group, --OC(O)--NH-group,
--NH--C(O)--O-group, an aromatic hydrocarbon group, or a
polymerizable functional group capable of radical
polymerization.
3. The dental adhesive composition according to claim 1, wherein
the (D-1) aliphatic tertiary amine compound represented by formula
(1) is an aliphatic tertiary amine compound in which R.sub.1 and
R.sub.2 have an aliphatic substituent consisting of three or more
carbons having an electron-withdrawing group at .alpha.-carbon
and/or .beta.-carbon.
4. The dental adhesive composition according to claim 1, wherein
the (D-1) aliphatic tertiary amine compound represented by formula
(1) is an aliphatic tertiary amine compound in which R.sub.1 and
R.sub.2 have an aryl group which may have a substituent, at
.alpha.-carbon and/or .beta.-carbon.
5. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition further comprises (G) water.
6. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition further comprises (B)
photosensitizer.
7. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition further comprises (C) photoacid
generator.
8. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition comprises an aryl iodonium salt as
the (C) photoacid generator, and the aryl iodonium salt is a salt
of an anion having an organic group and one or more atoms of P, B,
Al, S and Ga, and an aryl iodonium cation.
9. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition comprises an aryl iodonium salt as
the (C) photoacid generator, and the aryl iodonium salt is a salt
of an anion having an organic group in which at least one H is
substituted with F and one or more atoms of P, B, Al, S and Ga, and
an aryl iodonium cation.
10. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition is one pack type dental adhesive
composition comprising, with respect to 100 parts by mass of total
of the (A) polymerizable monomer and the (F) volatile organic
solvent or with respect to 100 parts by mass of total of the (A)
polymerizable monomer, the (F) volatile organic solvent and (G)
water in the case of containing the (G) water, 0.1 to 20 parts by
mass of the (A-1) polymerizable monomer having an acidic group, 1
to 99.9 parts by mass of the (F) volatile organic solvent, and 0.01
to 20 parts by mass of the (D-1) aliphatic tertiary amine compound
represented by formula (1).
11. The dental adhesive composition according to claim 1, wherein
the dental adhesive composition is two packs type dental adhesive
composition consisting of a first pack and a second pack, wherein a
mass ratio of the first pack and the second pack is 0.8:1 to 1.2:1,
the first pack comprises the (A-1) polymerizable monomer having an
acidic group, the (F) volatile organic solvent and the (D-1)
aliphatic tertiary amine compound represented by formula (1), the
first pack comprises, with respect to 100 parts by mass of total of
the (A) polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water
contained in the first pack, 0.2 to 20 parts by mass of the (A-1)
polymerizable monomer having an acidic group, 1 to 99.9 parts by
mass of the (F) volatile organic solvent, and 0.02 to 20 parts by
mass of the (D-1) aliphatic tertiary amine compound represented by
formula (1).
12. A dental adhesive kit comprising a dental photocurable
composition and the dental adhesive composition according to claim
1, wherein the dental photocurable composition comprises, with
respect to 100 parts by mass of the (A) polymerizable monomer
contained in the dental photocurable composition, 0.001 to 2 parts
by mass of (B) photosensitizer, and 0.01 to 10 parts by mass of the
(C) photoacid generator.
13. The dental adhesive composition according to claim 4, wherein
the dental adhesive composition further comprises (G) water.
14. The dental adhesive composition according to claim 13, wherein
the dental adhesive composition further comprises (B)
photosensitizer.
15. The dental adhesive composition according to claim 14, wherein
the dental adhesive composition further comprises (C) photoacid
generator.
16. The dental adhesive composition according to claim 15, wherein
the dental adhesive composition comprises an aryl iodonium salt as
the (C) photoacid generator, and the aryl iodonium salt is a salt
of an anion having an organic group and one or more atoms of P, B,
Al, S and Ga, and an aryl iodonium cation.
17. The dental adhesive composition according to claim 16, wherein
the dental adhesive composition comprises an aryl iodonium salt as
the (C) photoacid generator, and the aryl iodonium salt is a salt
of an anion having an organic group in which at least one H is
substituted with F and one or more atoms of P, B, Al, S and Ga, and
an aryl iodonium cation.
18. The dental adhesive composition according to claim 16, wherein
the dental adhesive composition is one pack type dental adhesive
composition comprising, with respect to 100 parts by mass of total
of the (A) polymerizable monomer and the (F) volatile organic
solvent or with respect to 100 parts by mass of total of the (A)
polymerizable monomer, the (F) volatile organic solvent and (G)
water in the case of containing the (G) water, 0.1 to 20 parts by
mass of the (A-1) polymerizable monomer having an acidic group, 1
to 99.9 parts by mass of the (F) volatile organic solvent, and 0.01
to 20 parts by mass of the (D-1) aliphatic tertiary amine compound
represented by formula (1).
19. The dental adhesive composition according to claim 17, wherein
the dental adhesive composition is two packs type dental adhesive
composition consisting of a first pack and a second pack, wherein a
mass ratio of the first pack and the second pack is 0.8:1 to 1.2:1,
the first pack comprises the (A-1) polymerizable monomer having an
acidic group, the (F) volatile organic solvent and the (D-1)
aliphatic tertiary amine compound represented by formula (1), the
first pack comprises, with respect to 100 parts by mass of total of
the (A) polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water
contained in the first pack, 0.2 to 20 parts by mass of the (A-1)
polymerizable monomer having an acidic group, 1 to 99.9 parts by
mass of the (F) volatile organic solvent, and 0.02 to 20 parts by
mass of the (D-1) aliphatic tertiary amine compound represented by
formula (1).
20. A dental adhesive kit comprising a dental photocurable
composition and the dental adhesive composition according to claim
18, wherein the dental photocurable composition comprises, with
respect to 100 parts by mass of the (A) polymerizable monomer
contained in the dental photocurable composition, 0.001 to 2 parts
by mass of (B) photosensitizer, and 0.01 to 10 parts by mass of the
(C) photoacid generator.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on and claims the benefit of
priorities from Japanese Patent Application Serial No. 2021-40033
(filed on Mar. 12, 2021), Japanese Patent Application Serial No.
2021-40037 (filed on Mar. 12, 2021), Japanese Patent Application
Serial No. 2021-40039 (filed on Mar. 12, 2021), and Japanese Patent
Application Serial No. 2021-40040 (filed on Mar. 12, 2021), the
contents of which are hereby incorporated by reference in their
entirety.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present disclosure relates to a dental adhesive
composition.
Description of the Related Art
[0003] A dental adhesive composition has been used in the dental
field, and applied to a dental adhesive material, a dental
composite resin, a dental core build-up material, a dental resin
cement, a dental coating material, a dental sealant material, a
dental manicure material, a dental splinting material and a dental
glass ionomer cement.
[0004] In Japanese Unexamined Patent Publication No. 2006-225350
and Japanese Patent No. 4783151, an adhesive composition containing
a basic compound containing an acidic group polymerizable monomer
and an aliphatic tertiary amine is proposed.
[0005] In Japanese Unexamined Patent Publication No. 2006-76973, an
adhesive composition containing an acidic group polymerizable
monomer, an aromatic tertiary amine and a triazine compound is
proposed.
SUMMARY OF THE INVENTION
Technical Problem
[0006] However, conventional dental adhesive compositions have room
for improvement in terms of storage stability and adhesive
strength.
[0007] An object of the present disclosure is to provide a dental
adhesive composition having excellent storage stability and
adhesive strength.
Solution to Problem
[0008] A dental adhesive composition of the present disclosure
comprises (A) polymerizable monomer, (D) photopolymerization
accelerator, and (F) volatile organic solvent, wherein, the dental
adhesive composition comprises (A-1) polymerizable monomer having
an acidic group as the (A) polymerizable monomer, and the dental
adhesive composition comprises (D-1) aliphatic tertiary amine
compound represented by formula (1) as the (D) photopolymerization
accelerator.
##STR00002##
(wherein R.sub.1 represents a substituent consisting of three or
more carbons having an electron-withdrawing group at .alpha.-carbon
and/or .beta.-carbon of an amine starting from N, R.sub.2
represents a substituent consisting of three or more carbons which
may have an electron-withdrawing group, R.sub.3 represents a
substituent consisting of one or more carbons which may have an
electron-withdrawing group, and .alpha.-carbon of N in the formula
(1) is not an electron-withdrawing group.)
Advantageous Effects of Invention
[0009] The dental adhesive composition of the present disclosure is
excellent in storage stability and adhesive strength.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] In the present disclosure, the electron-withdrawing group in
R.sub.1 may be a substituent selected from a functional group
selected from the group consisting of a hydroxyl group, a carboxyl
group, a vinyl group, an aryl group and a halogen, and, an organic
group which is bonded via an ether bond, an ester bond, a urethane
bond or a urea bond and may have --OH group, --O-group,
--C(O)-group, --S-group, --NH--C(O)--NH-group, --C(O)--O-group,
--O--C(O)-group, --OC(O)--NH-group, --NH--C(O)--O-group, an
aromatic hydrocarbon group, or a polymerizable functional group
capable of radical polymerization.
[0011] In the present disclosure, the (D-1) aliphatic tertiary
amine compound represented by formula (1) may be an aliphatic
tertiary amine compound in which R.sub.1 and R.sub.2 have an
aliphatic substituent consisting of three or more carbons having an
electron-withdrawing group at .alpha.-carbon and/or
.beta.-carbon.
[0012] In the present disclosure, the (D-1) aliphatic tertiary
amine compound represented by formula (1) may be an aliphatic
tertiary amine compound in which R.sub.1 and R.sub.2 have an aryl
group which may have a substituent, at .alpha.-carbon and/or
.beta.-carbon.
[0013] In the present disclosure, the dental adhesive composition
may further comprise (G) water.
[0014] In the present disclosure, the dental adhesive composition
may further comprise (B) photosensitizer.
[0015] In the present disclosure, the dental adhesive composition
may further comprise (C) photoacid generator.
[0016] In the present disclosure, the dental adhesive composition
may comprise an aryl iodonium salt as the (C) photoacid generator,
and the aryl iodonium salt may be a salt of an anion having an
organic group and one or more atoms of P, B, Al, S and Ga, and an
aryl iodonium cation.
[0017] In the present disclosure, the dental adhesive composition
may comprise an aryl iodonium salt as the (C) photoacid generator,
and the aryl iodonium salt may be a salt of an anion having an
organic group in which at least one H is substituted with F and one
or more atoms of P, B, Al, S and Ga, and an aryl iodonium
cation.
[0018] In the present disclosure, the dental adhesive composition
may be one pack type dental adhesive composition comprising, with
respect to 100 parts by mass of total of the (A) polymerizable
monomer and the (F) volatile organic solvent or with respect to 100
parts by mass of total of the (A) polymerizable monomer, the (F)
volatile organic solvent and (G) water in the case of containing
the (G) water, 0.1 to 20 parts by mass of the (A-1) polymerizable
monomer having an acidic group, 1 to 99.9 parts by mass of the (F)
volatile organic solvent, and 0.01 to 20 parts by mass of the (D-1)
aliphatic tertiary amine compound represented by formula (1).
[0019] In the present disclosure, the dental adhesive composition
may be two packs type dental adhesive composition consisting of a
first pack and a second pack, wherein a mass ratio of the first
pack and the second pack is 0.8:1 to 1.2:1, the first pack
comprises the (A-1) polymerizable monomer having an acidic group,
the (F) volatile organic solvent and the (D-1) aliphatic tertiary
amine compound represented by formula (1), the first pack
comprises, with respect to 100 parts by mass of total of the (A)
polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water
contained in the first pack, 0.2 to 20 parts by mass of the (A-1)
polymerizable monomer having an acidic group, 1 to 99.9 parts by
mass of the (F) volatile organic solvent, and 0.02 to 20 parts by
mass of the (D-1) aliphatic tertiary amine compound represented by
formula (1).
[0020] The present disclosure provides a dental adhesive kit
comprising a dental photocurable composition and the dental
adhesive composition according to any one of claims 1 to 11,
wherein the dental photocurable composition comprises, with respect
to 100 parts by mass of the (A) polymerizable monomer contained in
the dental photocurable composition, 0.001 to 2 parts by mass of
(B) photosensitizer, and 0.01 to 10 parts by mass of the (C)
photoacid generator.
[0021] Hereinafter, each component in the dental adhesive
composition of the present disclosure is described in detail. A
dental adhesive composition of the present disclosure can be
applied to a dental adhesive material, a dental composite resin, a
dental core build-up material, a dental resin cement, a dental
coating material, a dental sealant material, a dental manicure
material, a dental splinting material and a dental glass ionomer
cement.
[0022] In a dental practice, in order to restore aesthetically and
functionally a lost portion of a tooth by caries, breakages and the
like, a direct restoration by a dental composite resin and an
indirect restoration by a prosthetic device consisting of ceramics
or hard resin by using a dental resin cement have been performed as
treatment. A dental adhesive material has been used for adhering a
dental composite resin to various dental materials and natural
tooth. In addition, a dental adhesive material has been used for
adhering a dental splinting material for fixing a mobile tooth, a
dental coating material for protect a vital tooth after forming,
against a hyperesthesia, an external stimulation and secondary
caries, a dental sealant material for preventing caries by filling
complex grooves such as especially a deciduous tooth, a dental
manicure material for temporary recovering aesthetic property by
masking discoloration of a tooth, a dental core build-up material
for forming an abutment tooth in the case of collapsing of a dental
crown due to caries, and the like.
[0023] As a dental adhesive, a self-etching primer containing water
and an acidic group-containing polymerizable monomer has been
proposed in order to achieve both an enamel decalcification
function and a dentin penetration promoting function. Such a
composition has an advantage that the operation is simplified
because the etching operation before applying the primer is not
required. On the other hand, when the acidic group-containing
polymerizable monomer and water coexist in the same package, the
acidic group-containing polymerizable monomer is hydrolyzed when
stored for a long period of time, therefore there has been a
disadvantage that the adhesive strength to the adherend
decreases.
[0024] Therefore, a composition in which an acidic group-containing
polymerizable monomer, water and a basic compound coexist has been
proposed. In such a composition, the acidity is neutralized by
forming a salt between the acidic group-containing polymerizable
monomer and the basic compound, so that the storage stability is
improved. However, since basic inorganic compounds and tertiary
aliphatic amine compounds that are usually used form strong salts
with acidic group-containing polymerizable monomers, there is a
problem in that the adhesive strength is lowered.
[0025] In order to solve the above problem, the present inventors
have been found that the dental adhesive composition of the present
disclosure realizes both excellent storage stability and excellent
adhesive strength when an aliphatic tertiary amine having a
specific structure is used, and have completed the present
disclosure.
[0026] Further, the present inventors have been found that when the
dental adhesive composition of the present disclosure and the
dental photocurable composition containing a photoacid generator
are adhered, further excellent adhesive strength is exhibited.
[0027] The dental adhesive composition of the present disclosure
can be applied as a dental adhesive material, a dental coating
material and a dental manicure material, and further can be used as
a kit in combination with a dental adhesive material, a dental
composite resin, a dental core build-up material, a dental resin
cement, a dental coating material, a dental sealant material, a
dental manicure material, a dental splinting material, a dental
hard resin, a dental cutting and machining material or a dental 3D
printer material which are dental curable compositions.
[(A) Polymerizable Monomer]
[0028] As the (A) polymerizable monomer of the present disclosure,
any polymerizable monomers can be used without limitation as long
as it is known. In the polymerizable monomer or the compound having
a polymerizable group described in the present disclosure, the
polymerizable group preferably exhibits radical polymerizability,
and specifically, from the viewpoint of easy radical
polymerization, the polymerizable group is preferably (meth)
acrylic group and/or (meth) acrylamide group. In the present
specification, "(meth) acrylic" means acrylic and/or methacrylic,
"(meth) acryloyl" means acryloyl and/or methacryloyl, "(meth)
acrylate" means acrylate and/or methacrylate, and, "(meth)
acrylamide" means acrylamide and/or methacrylamide. A polymerizable
monomer having a substituent at the .alpha.-position of an acrylic
group and/or an acrylamide group can also be preferably used.
Specific examples include one having one radical polymerizable
group, one having two radical polymerizable groups, one having
three or more radical polymerizable groups, one having an acidic
group, one having an alkoxysilyl group, and one having a sulfur
atom.
[0029] Specific examples of a polymerizable monomer having one
radical polymerizable group and not containing acidic group include
2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
4-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate,
10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth)
acrylate, glycerol mono (meth) acrylate, erythritol mono (meth)
acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth)
acrylamide, N,N-(dihydroxyethyl) (meth) acrylamide, methyl (meth)
acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl
(meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
benzyl (meth) acrylate, lauryl (meth) acrylate, 2,3-dibromopropyl
(meth) acrylate, 3-(meth) acryloyloxypropyl trimethoxysilane,
11-(meth) acryloyloxyundecyl trimethoxysilane, (meth) acrylamide
and the like.
[0030] Specific Examples of the polymerizable monomer having two
radical polymerizable groups and not containing acidic group
include 2,2-bis ((meth) acryloyloxy phenyl) propane, 2,2-bis
[4-(3-(meth) acryloyloxy)-2-hydroxy propoxyphenyl]propane
(generally called "Bis-GMA"), 2,2-bis (4-(meth) acryloyloxy phenyl)
propane, 2,2-bis (4-(meth) acryloyloxy polyethoxyphenyl) propane,
2,2-bis (4-(meth) acryloyloxy diethoxyphenyl) propane, 2,2-bis
(4-(meth) acryloyloxy tetraethoxyphenyl) propane, 2,2-bis
(4-(meth)) acryloyloxy pentaethoxyphenyl) propane, 2,2-bis
(4-(meth) acryloyloxy dipropoxyphenyl) propane, 2-(4-(meth)
acryloyloxy diethoxyphenyl)-2-(4-(meth) acryloyloxy diethoxyphenyl)
propane, 2-(4-(meth) acryloyloxy diethoxyphenyl)-2-(4-(meth)
acryloyloxy ditriethoxyphenyl) propane, 2-(4-(meth) acryloyloxy
dipropoxyphenyl)-2-(4-(meth) acryloyloxy triethoxyphenyl) propane,
2,2-bis (4-(meth) acryloyloxy propoxyphenyl) propane, 2,2-bis
(4-(meth) acryloyloxy isopropoxyphenyl) propane, 1,4-bis (2-(meth)
acryloyloxyethyl) pyromellitate, glycerol di (meth) acrylate,
1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethyleneglycol di
(meth) acrylate, diethyleneglycol di (meth) acrylate, triethylene
glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
butylene glycol di (meth) acrylate, neopentyl glycol di (meth)
acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di
(meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol
di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis
(3-methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethyl
hexamethylene bis (2-carbamoyloxy ethyl) dimethacrylate (generally
called "UDMA"), 1,2-bis (3-methacryloyloxy-2-hydroxy propoxy)
ethane and the like.
[0031] Specific Examples of the polymerizable monomer having three
or more radical polymerizable groups and not containing acidic
group include trimethylolpropane tri (meth) acrylate,
trimethylolethane tri (meth) acrylate, trimethylolmethane tri
(meth) acrylate, pentaerythritol tri (meth) acrylate,
pentaerythritol tetra (meth) acrylate, dipentaerythritol penta
(meth) acrylate, N,N-(2,2,4-trimethyl hexamethylene) bis
[2-(aminocarboxy) propane-1,3-diol] tetra methacrylate,
1,7-diacryloyloxy-2,2,6,6-tetra acryloyloxymethyl-4-oxyheptane and
the like.
[0032] For the (A-1) polymerizable monomer having an acidic group,
any polymerizable monomer can be used without any limitation as
long as it has one or more polymerizable group and at least one
acidic group such as a phosphoric acid group, a pyrophosphoric acid
group, a thiophosphoric acid group, a phosphonic acid group, a
sulfonic acid group and a carboxylic acid group and the like.
[0033] Specific examples of a phosphoric acid group-containing
polymerizable monomer include 2-(meth) acryloyloxyethyl dihydrogen
phosphate, 3-(meth) acryloyloxypropyl dihydrogen phosphate,
4-(meth) acryloyloxybutyl dihydrogen phosphate, 5-(meth)
acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl
dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen
phosphate, 8-(meth) acryloyloxyoctyl dihydrogen phosphate, 9-(meth)
acryloyloxynonyl dihydrogen phosphate, 10-(meth) acryloyloxydecyl
dihydrogen phosphate, 11-(meth) acryloyloxyundecyl dihydrogen
phosphate, 12-(meth) acryloyloxydodecyl dihydrogen phosphate,
16-(meth) acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)
acryloyloxyicosyl dihydrogen phosphate, bis [2-(meth) acryloyl
oxyethyl]hydrogensphosphate, bis [4-(meth) acryloyl oxybutyl]
hydrogen phosphate, bis [6-(meth) acryloyl oxyhexyl] hydrogen
phosphate, bis [8-(meth) acryloyl oxyoctyl] hydrogen phosphate, bis
[9-(meth) acryloyl oxynonyl] hydrogen phosphate, bis [10-(meth)
acryloyl oxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyl
oxypropyl dihydrogenphosphate, 2-(meth) acryloyl oxyethylphenyl
hydrogen phosphate, 2-(meth) acryloyloxyethyl-2-bromoethyl hydrogen
phosphate and bis [2-(meth) acryloyloxy-(1-hydroxymethyl) ethyl]
hydrogen phosphate; acyl chloride, alkali metal salt and ammonium
salt thereof; and (meth) acrylamide compound in which the ester
bond of these compounds is substituted with an amide bond, and the
like.
[0034] Specific examples of a pyrophosphoric acid group-containing
polymerizable monomer include bis [2-(meth) acryloyl oxyethyl]
pyrophosphate, bis [4-(meth) acryloyl oxybutyl] pyrophosphate, bis
[6-(meth) acryloyl oxyhexyl] pyrophosphate, bis [8-(meth) acryloyl
oxyoctyl] pyrophosphate, bis [10-(meth) acryloyl oxydecyl]
pyrophosphate; acyl chloride, alkali metal salt and ammonium salt
thereof; and (meth) acrylamide compound in which the ester bond of
these compounds is substituted with an amide bond, and the
like.
[0035] Specific examples of a thiophosphate group-containing
polymerizable monomer include 2-(meth) acryloyloxyethyl dihydrogen
thiophosphate, 3-(meth) acryloyloxypropyl dihydrogen thiophosphate,
4-(meth) acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)
acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)
acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)
acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)
acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)
acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)
acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)
acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)
acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)
acryloyloxyhexadecyl dihydrogen thiophosphate, 20-(meth)
acryloyloxyicosyl dihydrogen thiophosphate; acyl chloride, alkali
metal salt and ammonium salt thereof; and (meth) acrylamide
compound in which the ester bond of these compounds is substituted
with an amide bond, and the like. The polymerizable monomer having
a thiophosphate group is also classified as a polymerizable monomer
having a sulfur atom.
[0036] Specific examples of a phosphonic acid group-containing
polymerizable monomer include 2-(meth) acryloyloxy ethylphenyl
phosphonate, 5-(meth) acryloyloxy pentyl-3-phosphonopropionate,
6-(meth) acryloyloxy hexyl-3-phosphonopropionate, 10-(meth)
acryloyloxy decyl-3-phosphonopropionate, 6-(meth) acryloyloxy
hexyl-3-phosphonoacetate, 10-(meth) acryloyloxy
decyl-3-phosphonoacetate; acyl chloride, alkali metal salt and
ammonium salt thereof; and (meth)acrylamide compound in which the
ester bond of these compounds is substituted with an amide bond,
and the like.
[0037] Specific examples of a sulfonic acid group-containing
polymerizable monomer include 2-(meth) acrylamide-2-methyl
propanesulfonic acid and 2-sulfoethyl (meth) acrylate and the
like.
[0038] The carboxylic acid group-containing polymerizable monomers
are classified into a (meth) acrylic-based compound having one
carboxyl group in the molecule and a (meth) acrylic-based compound
having a plurality of carboxyl groups in the molecule. Examples of
the (meth) acrylic-based compound having one carboxyl group in the
molecule include (meth) acrylic acid, N-(meth) acryloyl glycine,
N-(meth) acryloyl aspartic acid, O-(meth) acryloyl tyrosine,
N-(meth) acryloyl tyrosine, N-(meth) acryloyl phenylalanine,
N-(meth) acryloyl-p-aminobenzoic acid, N-(meth)
acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)
acryloyloxybenzoic acid, 3-(meth) acryloyloxybenzoic acid, 4-(meth)
acryloyloxybenzoic acid, N-(meth) acryloyl-5-aminosalicylic acid,
N-(meth) acryloyl-4-aminosalicylic acid, 2-(meth) acryloyloxyethyl
hydrogen succinate, 2-(meth) acryloyloxyethyl hydrogen phthalate,
2-(meth) acryloyloxyethyl hydrogenmalate; acyl chloride thereof;
and (meth)acrylamide compound in which the ester bond of these
compounds is substituted with an amide bond, and the like. Examples
of the (meth) acrylic-based compound having a plurality of carboxyl
groups in the molecule include 6-(meth) acryloyl
oxyhexane-1,1-dicarboxylic acid, 9-(meth) acryloyl
oxynonane-1,1-dicarboxylic acid, 10-(meth) acryloyl
oxydecane-1,1-dicarboxylic acid, 11-(meth) acryloyloxy
undecane-1,1-dicarboxylic acid, 12-(meth) acryloyl
oxydodecane-1,1-dicarboxylic acid, 13-(meth) acryloyloxy
tridecane-1,1-dicarboxylic acid, 4-(meth) acryloyloxyethyl
trimeritate, 4-(meth) acryloyloxybutyl trimeritate, 4-(meth)
acryloyloxyhexyl trimeritate, 4-(meth) acryloyloxydecyl
trimeritate, 2-(meth) acryloyl oxyethyl-3'-(meth)
acryloyloxy-2'-(3,4-dicarboxy benzoyloxy) propylsuccinate; acid
anhydrides and acid halides thereof; and (meth) acrylamide compound
in which the ester bond of these compounds is substituted with an
amide bond, and the like.
[0039] Specific examples of the polymerizable monomer having an
alkoxysilyl group include a (meth) acrylic compound having one
alkoxysilyl group in the molecule and a (meth) acrylic compound
having a plurality of alkoxysilyl groups in the molecule. Specific
examples include 2-(meth) acryloxyethyl trimethoxysilane, 3-(meth)
acryloxypropyl trimethoxysilane, 3-(meth) acryloxypropyl
triethoxysilane, 3-(meth) acryloxypropyl methyldimethoxysilane,
4-(meth) acryloxybutyl trimethoxysilane, 5-(meth) acryloxypentyl
trimethoxysilane, 6-(meth) acryloxyhexyl trimethoxysilane, 7-(meth)
acryloxyheptyl trimethoxysilane, 8-(meth) acryloxyoctyl
trimethoxysilane, 9-(meth) acryloxynonyl trimethoxysilane,
10-(meth) acryloxydecyl trimethoxysilane, 11-(meth) acryloxyundecyl
trimethoxysilane.
[0040] As the polymerizable monomer having a sulfur atom, any known
compound can be used without any limitation as long as it is a
polymerizable monomer having one or more sulfur atoms and a
polymerizable group. Specifically, it refers to a compound having a
partial structure such as --SH, --S--S--, >C.dbd.S,
>C--S--C<, >P.dbd.S, or a compound prepared by
tautomerism. Specific examples include 10-methacryloxy
decyl-6,8-dithiooctanate, 6-methacryloxy hexyl-6,8-dithiooctanate,
6-methacryloxy hexyl-2-thiouracil-5-carboxylate, 2-(11-methacryloxy
undecylthio)-5-mercapto-1,3,4-thiadiazole, 10-(meth) acryloxy decyl
dihydrogenthiophosphate.
[0041] An oligomer or a prepolymer having at least one
polymerizable group in its molecule may be used other than such a
polymerizable monomer, without any limitation. There is no problem
even if a substituent such as a fluoro group is contained in the
same molecule. The polymerizable monomers described above can be
used not only singly but also in combinations of a plurality
thereof.
[0042] The dental adhesive composition of the present disclosure
contains (A-1) polymerizable monomer having an acidic group in
order to impart adhesive property with respect to a tooth substance
and a prosthetic device. Among them, 10-methacryloyloxydecyl
dihydrogenphosphate, 6-methacryloxyhexyl phosphonoacetate,
10-methacryloyloxydecyl dihydrogenthiophosphate, 4-(meth)
acryloyloxyethyl trimeritate and 4-(meth) acryloyloxyethyl
trimeritate anhydride are preferable.
[0043] The compounding amount of the (A-1) polymerizable monomer
having an acidic group in the case that the dental adhesive
composition is one pack type dental adhesive composition is
preferably 0.1 to 20 parts by mass, more preferably 1 to 20 parts
by mass, with respect to 100 parts by mass of total of the (A)
polymerizable monomer containing the (A-1) polymerizable monomer
having an acidic group and the (F) volatile organic solvent or with
respect to 100 parts by mass of total of the (A) polymerizable
monomer, the (F) volatile organic solvent and (G) water in the case
of containing the (G) water. When the compounding amount is less
than 0.1 parts by mass, there is a case that adhesive property to
the tooth substance and the prosthetic device is not imparted, and
when the compounding amount exceeds 20 parts by mass, there is a
case that the storage stability deteriorates.
[0044] The compounding amount of the (A-1) polymerizable monomer
having an acidic group in the case that the dental adhesive
composition is two packs type dental adhesive composition
consisting of a first pack and a second pack is preferably 0.2 to
20 parts by mass, more preferably 1 to 20 parts by mass in the
first pack, with respect to 100 parts by mass of total of the (A)
polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water
contained in the first pack. When the compounding amount is less
than 0.2 parts by mass, there is a case that adhesive property to
the tooth substance and the prosthetic device is not imparted, and
when the compounding amount exceeds 20 parts by mass, there is a
case that the storage stability deteriorates.
[0045] The dental adhesive composition of the present disclosure
may contain a silane coupling agent having a polymerizable group as
the (A) polymerizable monomer in order to impart adhesive property
with respect to glass ceramics and a resin material consisting of a
matrix of an inorganic component and a polymerizable monomer. Any
known silane coupling agent can be used without any limitation, but
3-(meth) acryloxypropyl trimethoxysilane, 8-(meth) acryloxyoctyl
trimethoxysilane, 11-(meth) acryloxyundecyl trimethoxysilane,
4,4-diethoxy-17-oxo-3,16-dioxa-18-aza-4-cilaicosan-20-yl (meth)
acrylate and
4,4-diethoxy-17-oxo-3,16,21-trioxa-18-aza-4-silatricosan-23-yl
(meth) acrylate are preferable. From the view point of imparting
adhesive property, the compounding amount is preferably 0.01 to 10
parts by mass, more preferably 0.01 to 5 parts by mass, with
respect to 100 parts by mass of total of the (A) polymerizable
monomer and the (F) volatile organic solvent or with respect to 100
parts by mass of total of the (A) polymerizable monomer, the (F)
volatile organic solvent and (G) water in the case of containing
the (G) water. Since the purpose of the silane coupling agent as a
polymerizable monomer is to impart adhesive property with respect
to glass ceramics or a resin material containing a filler
consisting of glass ceramics, the silane coupling agent is
compounded separately from the surface treatment agent of the
filler.
[0046] The dental adhesive composition of the present disclosure
may contain a polymerizable monomer having a sulfur atom as the (A)
polymerizable monomer in order to impart adhesive property with in
which respect to a noble metal. From the view point of imparting
adhesive property, the compounding amount of the polymerizable
monomer having a sulfur atom is preferably 0.01 to 10 parts by
mass, more preferably 0.1 to 5 parts by mass, with respect to 100
parts by mass of total of the (A) polymerizable monomer and the (F)
volatile organic solvent or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water.
<Photopolymerization Initiator>
[0047] The dental adhesive composition of the present disclosure
contains (D-1) aliphatic tertiary amine compound represented by
formula (1). The dental adhesive composition of the present
disclosure may contain (B) photosensitizer, (C) photoacid generator
and (D) photopolymerization accelerator other than the (D-1)
aliphatic tertiary amine compound represented by formula (1), as a
photopolymerization initiator, in addition to the (D-1) aliphatic
tertiary amine compound represented by formula (1). These may be
compounded alone and are not particularly limited, and any known
compounds commonly used may be used without any limitation in the
case of containing these.
[(B) Photosensitizer]
[0048] Specific examples of the (B) photosensitizer which can be
used in the present disclosure include .alpha.-diketones such as
benzil, camphorquinone, camphorquinone carboxylic acid,
camphorquinone sulfonic acid, .alpha.-naphthyl, acetonaphthone,
p,p'-dimethoxybenzyl, p,p'-dichlorobenzylacetyl, pentanedion,
1,2-phenanthrenequinone, 1,4-phenanthrenequinone,
3,4-phenanthrenequinone, 9,10-phenanthrenequinone and
naphthoquinone; benzoin alkyl ethers such as benzoin, benzoin
methyl ether and benzoin ethyl ether; thioxanthones such as
thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone,
2-isopropylthioxanthone, 2-methoxythioxanthone,
2-hydroxythioxanthone, 2,4-diethylthioxanthone and
2,4-diisopropylthioxanthone; benzophenones such as benzophenone,
p-chlorobenzophenone and p-methoxybenzophenone; acylphosphine
oxides such as bis (2,6-dimethoxy benzoyl) phenylphosphine oxide,
bis (2,6-dimethoxy benzoyl) (2,4,4-trimethyl pentyl) phosphine
oxide, bis (2,6-dimethoxy benzoyl)-n-butylphosphine oxide, bis
(2,6-dimethoxy benzoyl)-(2-methylprop-1-yl) phosphine oxide, bis
(2,6-dimethoxy benzoyl)-(1-methylprop-1-yl) phosphine oxide, bis
(2,6-dimethoxy benzoyl)-t-butyl phosphine oxide, bis (2,6-dimethoxy
benzoyl) cyclohexyl phosphine oxide, bis (2,6-dimethoxy benzoyl)
octyl phosphine oxide, bis (2-methoxy benzoyl) (2-methylprop-1-yl)
phosphine oxide, bis (2-methoxy benzoyl) (1-methylprop-1-yl)
phosphine oxide, bis (2,6-diethoxy benzoyl) (2-methylprop-1-yl)
phosphine oxide, bis (2,6-diethoxy benzoyl) (1-methylprop-1-yl)
phosphine oxide, bis (2,6-dibutoxy benzoyl) (2-methylprop-1-yl)
phosphine oxide, bis (2,4-dimethoxy benzoyl) (2-methylprop-1-yl)
phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine
oxide, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis
(2,4,6-trimethyl benzoyl) (2,4-dipentoxy phenyl) phosphine oxide,
bis (2,6-dimethoxy benzoyl) benzyl phosphine oxide, bis
(2,6-dimethoxy benzoyl)-2-phenylpropyl phosphine oxide, bis
(2,6-dimethoxy benzoyl)-2-phenylethyl phosphine oxide, bis
(2,6-dimethoxy benzoyl) benzyl phosphine oxide, bis (2,6-dimethoxy
benzoyl)-2-phenylpropyl phosphine oxide, bis (2,6-dimethoxy
benzoyl)-2-phenylethyl phosphine oxide, 2,6-dimethoxy benzoyl
benzyl butyl phosphine oxide, 2,6-dimethoxy benzoyl benzyl octyl
phosphine oxide, bis (2,4,6-trimethyl benzoyl) isobutyl phosphine
oxide and 2,6-dimethoxy benzoyl-2,4,6-trimethyl benzoyl-n-butyl
phosphine oxide; acylgermanium compounds such as bisbenzoyl
diethylgermanium, bisbenzoyl dimethylgermanium, bisbenzoyl
dibutylgermanium, bis (4-methoxybenzoyl) dimethylgermanium and bis
(4-methoxybenzoyl) diethylgermanium; .alpha.-aminoacetophenones
such as 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1,
and 2-benzyl-diethylamino-1-(4-morpholinopheny)-propanone-1; ketals
such as benzyl dimethyl ketal, benzyl diethyl ketal and benzyl
(2-methoxyethyl ketal); and titanocenes such as bis
(cyclopentadienyl)-bis [2,6-difluoro-3-(1-pyrrolyl)
phenyl]-titanium, bis (cyclopentadienyl)-bis
(pentanefluorophenyl)-titanium and bis (cyclopentadienyl)-bis
(2,3,5,6-tetrafluoro-4-disiloxyphenyl)-titanium.
[0049] The photosensitizer (B) may be appropriately selected
according to the wavelength, the intensity and the irradiation time
of light used for polymerization, and the type and the compounding
amount of other components to be combined. In addition, the
photosensitizer may be used not only singly but also in
combinations of two or more. Among them, .alpha.-diketone compounds
having a maximum absorption wavelength in the visible light region
are preferably used, and camphorquinone compounds such as
camphorquinone, camphorquinone carboxylic acid and camphorquinone
sulfonic acid are more preferable. Camphorquinone is particularly
preferred because it is easily available.
[0050] In the case that the dental adhesive composition of the
present disclosure contains (B) a photosensitizer, the compounding
amount of the (B) photosensitizer is preferably 0.001 to 5 parts by
mass, more preferably 0.1 to 1 parts by mass, with respect to 100
parts by mass of total of the (A) polymerizable monomer and the (F)
volatile organic solvent or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water. When
the compounding amount of the photosensitizer is less than 0.001
parts by mass, there is a case that the polymerization activity
with respect to the irradiation light is poor and the curing
becomes insufficient. When the compounding amount is more than 5
parts by mass, there is a case that although sufficient curability
is exhibited, the sensitivity to light is shortened, and yellowness
is increased.
[(C) Photoacid Generator]
[0051] The dental adhesive composition of the present disclosure
may contain (C) photoacid generator. As the (C) photoacid
generator, known compound can be used without limitation. Specific
examples include triazine compounds, iodonium salt compounds,
sulfonium salt compounds, and sulfonic acid ester compounds. Among
these, triazine compounds and iodonium salt-based compounds are
preferable because of having high polymerizability in the case of
using in combination with a sensitizer. Iodonium salt-based
compounds are more preferable. Iodonium-based salt compounds are
susceptible to sensitization by photosensitizers that have
absorption in the visible light region.
[0052] Specific examples of the triazine compound include
2,4,6-tris (trichloro methyl)-s-triazine, 2,4,6-tris (tribromo
methyl)-s-triazine, 2-methyl-4,6-bis (trichloro methyl)-s-triazine,
2-methyl-4,6-bis (tribromo methyl)-s-triazine, 2-phenyl-4,6-bis
(trichloro methyl)-s-triazine, 2-(p-methoxy phenyl)-4,6-bis
(trichloro methyl)-s-triazine, 2-(p-methyl thiophenyl)-4,6-bis
(trichloro methyl)-s-triazine, 2-(p-chloro phenyl)-4,6-bis
(trichloro methyl)-s-triazine, 2-(2,4-dichloro phenyl)-4,6-bis
(trichloro methyl)-s-triazine, 2-(p-bromo phenyl)-4,6-bis
(trichloro methyl)-s-triazine, 2-(p-tolyl)-4,6-bis (trichloro
methyl)-s-triazine, 2-n-propyl-4,6-bis (trichloro
methyl)-s-triazine, 2-(.alpha.,.alpha.,.beta.-trichloro
ethyl)-4,6-bis (trichloro methyl)-s-triazine, 2-styryl-4,6-bis
(trichloro methyl)-s-triazine, 2-[2-(p-methoxy phenyl)
ethenyl]-4,6-bis (trichloro methyl)-s-triazine, 2-[2-(o-methoxy
phenyl) ethenyl]-4,6-bis (trichloro methyl)-s-triazine,
2-[2-(p-butoxy phenyl) ethenyl]-4,6-bis (trichloro
methyl)-s-triazine, 2-[2-(3,4-dimethoxy phenyl) ethenyl]-4,6-bis
(trichloro methyl)-s-triazine, 2-[2-(3,4,5-trimethoxy phenyl)
ethenyl]-4,6-bis (trichloro methyl)-s-triazine,
2-(1-naphthyl)-4,6-bis(trichloro methyl)-s-triazine,
2-(4-biphenylyl)-4,6-bis(trichloro methyl)-s-triazine,
2-[2-{N,N-bis(2-hydroxy ethyl) amino} ethoxy]-4,6-bis (trichloro
methyl)-s-triazine, 2-[2-{N-hydroxy ethyl-N-ethylamino}
ethoxy]-4,6-bis (trichloro methyl)-s-triazine, 2-[2-{N-hydroxy
ethyl-N-methylamino} ethoxy]-4,6-bis (trichloro methyl)-s-triazine,
2-[2-{N,N-diallyl amino} ethoxy]-4,6-bis (trichloro
methyl)-s-triazine and the like. Among them, 2,4,6-tris (trichloro
methyl)-s-triazine is preferable.
[0053] Any iodonium salt-based compound can be used as long as it
is known. For the specific examples, the structural formula of the
iodonium salt-based compound can be represented by the following
formula (2).
[(R1).sub.2I].sup.+[A].sup.- [Formula (2)]
(In the formula, [(R1).sub.2I].sup.+ is a cation part, [A].sup.- is
an anion part, R1 shown in the formula (2) represents an organic
group bonded to I, and R1s may be the same or different. R1
represents, for example, an aryl group having 6 to 30 carbon atoms,
a heterocyclic group having 4 to 30 carbon atoms, an alkyl group
having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon
atoms, or an alkynyl group having 2 to 30 carbon atoms, which may
have at least one substituted group selected from the group
consisting of groups such as alkyl, hydroxy, alkoxy, alkylcarbonyl,
arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl,
acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy,
alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl,
alkyleneoxy, amino, cyano, nitro groups and halogens.)
[0054] In the above, examples of the aryl group having 6 to 30
carbon atoms include a monocyclic aryl group such as a phenyl group
and a condensed polycyclic aryl group such as a naphthyl,
anthrasenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl,
benzanthrasenyl, anthraquinolyl, fluorenyl, naphthoquinone and
anthraquinone.
[0055] Examples of the heterocyclic group having 4 to 30 carbon
atoms include cyclic groups containing 1 to 3 heteroatoms such as
oxygen, nitrogen, and sulfur, which may be the same or different.
Specific examples include a monocyclic heterocyclic group such as
thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl,
pyrimidyl and pyrazinyl, and a condensed polycyclic heterocyclic
group such as indolyl, benzofuranyl, isobenzofuranyl, benzothienyl,
isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl,
carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl,
thianthrenyl, phenoxazinyl, phenoxathiinyl, chromanyl,
isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl and
dibenzofuran.
[0056] Specific examples of alkyl groups having 1 to 30 carbon
atoms include a linear alkyl group such as methyl, ethyl, propyl,
butyl, hexadecyl and octadecyl, a branched alkyl group such as
isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl,
tert-pentyl, isohexyl and a cycloalkyl groups such as cyclopropyl,
cyclobutyl, cyclopentyl and cyclohexyl.
[0057] In addition, specific examples of the alkenyl group having 2
to 30 carbon atoms include a linear chain or branched group such as
vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl,
3-butenyl and 1-methyl-1-propenyl.
[0058] Further, specific examples of the alkynyl group having 2 to
30 carbon atoms include a linear chain or branched group such as
ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl,
1-methyl-1-propynyl and 1-methyl-2-propynyl.
[0059] The above-described aryl group having 6 to 30 carbon atoms,
heterocyclic group having 4 to 30 carbon atoms, alkyl group having
1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms and
alkynyl group having 2 to 30 carbon atoms may have at least one
substituted group. Specific examples of the substituted group
include a linear alkyl group having 1 to 18 carbon atoms such as
methyl, ethyl, propyl, butyl and octadecyl; a branched alkyl group
having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl
and tert-butyl; a cycloalkyl group having 3 to 18 carbon atoms such
as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a hydroxy
group; a linear chain or branched alkoxy group having 1 to 18
carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy,
isobutoxy, sec-butoxy, tert-butoxy and dodecyloxy; a linear chain
or branched alkylcarbonyl group having 2 to 18 carbon atoms such as
acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl,
2-methylbutanoyl, 3-methylbutanoyl and octanoyl; an arylcarbonyl
group having 7 to 11 carbon atoms such as benzoyl and naphthoyl; a
linear chain or branched alkoxycarbonyl group having 2 to 19 carbon
atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,
isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,
sec-butoxycarbonyl and tert-butoxycarbonyl; an aryloxycarbonyl
group having 7 to 11 carbon atoms such as phenoxycarbonyl and
naphthoxycarbonyl; an arylthiocarbonyl group having 7 to 11 carbon
atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl; a
linear chain or branched acyloxy group having 2 to 19 carbon atoms
such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy,
isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy
and octadecylcarbonyloxy; an arylthio group having 6 to 20 carbon
atoms such as phenylthio, biphenylthio, methylphenylthio,
chlorophenylthio, bromophenylthio, fluorophenylthio,
hydroxyphenylthio, methoxyphenylthio, naphthylthio,
4-[4-(phenylthio) benzoyl] phenylthio, 4-[4-(phenylthio) phenoxy]
phenylthio, 4-[4-(phenylthio) phenyl] phenylthio, 4-(phenylthio)
phenylthio, 4-benzoyl phenylthio, 4-benzoyl-chlorophenylthio,
4-benzoyl-methylthio phenylthio, 4-(methylthiobenzoyl) phenylthio
and 4-(p-tert-butylbenzoyl) phenylthio; a linear chain or branched
alkylthio group having 1 to 18 carbon atoms such as methylthio,
ethylthio, propylthio, tert-butylthio, neopentylthio and
dodecylthio; an aryl group having 6 to 10 carbon atoms such as
phenyl, tolyl, dimethylphenyl and naphthyl; a heterocycle group
having 4 to 20 carbon atoms such as thienyl, furanyl, pyranyl,
xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl and
dibenzofuranyl; an aryloxy group having 6 to 10 carbon atoms such
as phenoxy and naphthyloxy; a linear chain or branched
alkylsulfinyl group having 1 to 18 carbon atoms such as
methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl
and octylsulfinyl; an arylsulfinyl group having 6 to 10 carbon
atoms such as phenylsulfinyl, tolylsulfinyl and naphthylsulfinyl; a
linear chain or branched alkylsulfonyl group having 1 to 18 carbon
atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl,
isopropylsulfonyl, butylsulfonyl and octylsulfonyl; an arylsulfonyl
group having 6 to 10 carbon atoms such as phenylsulfonyl,
tolylsulfonyl (tosyl), naphthylsulfonyl; an alkyleneoxy groups; a
cyano groups; a nitro groups; and halogens such as fluorine,
chlorine, bromine and iodine.
[0060] Among the iodonium salt-based compounds, the aryl iodonium
salt is preferable because of having high stability. Further, it is
preferable that the aryl group has a substituent in order to
improve the solubility to the dental adhesive composition.
Specifically, a linear alkyl group such as methyl, propyl, octyl,
decyl, undecyl, dodecyl and tridecyl, a branched alkyl group such
as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl,
neopentyl, tert-pentyl and isohexyl, a functional group in which
one or more of H of these is substituted with F, a perfluoroalkyl
group and halogen is suitable as the substituent.
[0061] The structure of an anion portion of the iodonium salt-based
compound is not particularly limited, and examples include those
having atoms such as P, S, B, Al and Ga. From the viewpoint of
safety, anions having As or Sb can be used, but they are not
preferable in dental applications. Further, the anion preferably
has an organic group such as an alkyl group and/or an alkoxy group
and/or an aryl group, and further, most preferably has an organic
group such as an alkyl group and/or an alkoxy group and/or an aryl
group, in which at least one H is substituted with F. Since the
iodonium salt-based compound having such an anion has high
solubility in the dental adhesive composition, it is expected to
preventing precipitation during low-temperature storage or
long-term storage and to shorten the time for preparing due to
dissolving in the composition in a short time.
[0062] Further, an iodonium salt-based compound of an anion having
an organic group such as an alkyl group and/or an alkoxy group
and/or an aryl group, in which at least one H is substituted with F
can be expected to have higher solubility. When the photoacid
generator is precipitated, there is a case that it may cause a
decrease in color stability after irradiation and a decrease in
flexural strength, and therefore it is not preferable. As the anion
having an organic group such as an alkyl group and/or an alkoxy
group and/or an aryl group, in which at least one H is substituted
with F, an anion having any atom can be used. However, from the
viewpoint of versatility and safety, those having one or more of P,
S, B, Al and Ga are preferable.
[0063] Examples of the anion having no alkyl group and/or alkoxy
group and/or aryl group include halogens such as chloride and
bromide, perhalonic acids such as perchloric acid, aromatic
sulfonic acids such as p-toluenesulfonate, camphorsulfonnic acids,
nitrates, acetates, chloroacetates, carboxylates, phenolates,
tetrafluoroborates, hexafluorophosphates, hexafluoroantimonates,
hexafluoroarsenates and the like. Among these, p-toluenesulfonate,
camphorsulfonic acid and carboxylate are preferably used.
[0064] Since the anionic part of [A].sup.- of the iodonium
salt-based compound of the formula (1) improves the solubility to
the composition, it is preferable that the anion has an alkyl group
and/or alkoxy group and/or aryl group, in which at least one H is
substituted with F. Specifically, the number of carbon atoms of the
alkyl group in the anion part of [A].sup.- of the iodonium
salt-based compound of the formula (2) is 1 to 8, and preferably 1
to 4. Specific examples include a linear alkyl group such as
methyl, ethyl, propyl, butyl, pentyl and octyl, a branched alkyl
group such as isopropyl, isobutyl, sec-butyl and tert-butyl, and a
cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl and
cyclohexyl. The ratio (F/H) of the number of hydrogen atoms to
fluorine atoms in the alkyl group is 4 or more, and the ratio (F/H)
of the number of hydrogen atoms to fluorine atoms in the alkyl
group is preferably 9 or more. More preferably, all hydrogen atoms
of the hydrocarbon are substituted with fluorine. An iodonium salt
consisting of an anion having an alkyl group having a different
ratio of a hydrogen atom and a fluorine atom may be compounded in
the dental adhesive composition.
[0065] Further, specific examples of the alkyl group include a
linear chain or branched perfluoroalkyl group such as CF.sub.3,
CF.sub.3CF.sub.2, (CF.sub.3).sub.2CF, CF.sub.3CF.sub.2CF.sub.2,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2, (CF.sub.3).sub.2CFCF.sub.2.
CF.sub.3CF.sub.2(CF.sub.3)CF and (CF.sub.3).sub.3C.
[0066] The number of carbon atoms of the alkyl group in the anion
part of [A].sup.- of the iodonium salt-based compound of the
formula (2) is 1 to 8, and preferably 1 to 4. Specific examples
include a linear alkoxy group such as methoxy, ethoxy, propoxy,
butoxy, pentoxy and octoxy, and a branched alkoxy group such as
isopropoxy, isobutoxy, sec-butoxy and tert-butoxy. The ratio (F/H)
of the number of hydrogen atoms to fluorine atoms in the alkyl
group is 4 or more, and the ratio (F/H) of the number of hydrogen
atoms to fluorine atoms in the alkyl group is preferably 9 or more.
More preferably, all hydrogen atoms of the hydrocarbon are
substituted with fluorine. An iodonium salt consisting of an anion
having an alkoxy group having a different ratio of a hydrogen atom
and a fluorine atom may be compounded in the dental adhesive
composition.
[0067] Further, specific examples of the alkoxy group include a
linear or branched perfluoroalkoxy group such as CF.sub.3O,
CF.sub.3CF.sub.2O, CF.sub.3CF.sub.2CF.sub.2O, (CF.sub.3).sub.2CFO,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2O, (CF.sub.3).sub.2CFCF.sub.2O,
CF.sub.3CF.sub.2(CF.sub.3)CFO,
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2O and
CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.su-
b.2O.
[0068] The phenyl group in the anion part of [A].sup.- of the
iodonium salt compound of the formula (2) may be a phenyl group, in
which at least one H is substituted with fluorine atom, an alkyl
group and/or an alkoxy group substituted with fluorine atom. The
alkyl group and/or alkoxy group substituted with fluorine atom are
preferably those described above. Specific examples of particularly
preferable phenyl group include perfluorophenyl group such as
pentafluorophenyl group (C.sub.6F.sub.5), trifluorophenyl group
(C.sub.6H.sub.2F.sub.3), tetrafluorophenyl group (C.sub.6HF.sub.4),
trifluoromethylphenyl group (CF.sub.3C.sub.6H.sub.4), bis
(trifluoromethyl) phenyl group ((CF.sub.3).sub.2C.sub.6H.sub.3),
pentafluoroethyl phenyl group (CF.sub.3CF.sub.2C.sub.6H.sub.4), bis
(pentafluoroethyl) phenyl group ((CF.sub.3).sub.2C.sub.6H.sub.3),
trifluoromethyl fluorophenyl group (CF.sub.3C.sub.6H.sub.3F),
bistrifluoromethyl fluorophenyl group
((CF.sub.3).sub.2C.sub.6H.sub.2F), pentafluoroethyl fluorophenyl
group (CF.sub.3CF.sub.2C.sub.6H.sub.3F), bispentafluoroethyl
fluorophenyl group (CF.sub.3CF.sub.2).sub.2C.sub.6H.sub.2F and the
like. An iodonium salt consisting of an anion having a phenyl group
having a different ratio of a hydrogen atom and a fluorine atom may
be compounded in the dental adhesive composition.
[0069] As specific examples of the anion portion of [A].sup.- of
the iodonium salt compound of the formula (3), examples of the
anion having P include [(CF.sub.3CF.sub.2).sub.3PF.sub.3].sup.-,
[(CF.sub.3CF.sub.2CF.sub.2).sub.3PF.sub.3].sup.-,
[((CF.sub.3).sub.2CF).sub.2PF.sub.4].sup.-,
[((CF.sub.3).sub.2CF).sub.3PF.sub.3].sup.-,
[((CF.sub.3).sub.2CF).sub.4PF.sub.2].sup.-,
[((CF.sub.3).sub.2CFCF.sub.2).sub.2PF.sub.4].sup.-,
[((CF.sub.3).sub.2CFCF.sub.2).sub.3PF.sub.3].sup.- and the like.
Examples of the anion having S include
[(CF.sub.3SO.sub.2).sub.3C].sup.-,
[(CF.sub.3CF.sub.2SO.sub.2).sub.3C].sup.-,
[(CF.sub.3CF.sub.2CF.sub.2SO.sub.2).sub.3C].sup.-,
[(CF.sub.3CF.sub.2CF.sub.2CF.sub.2SO.sub.2).sub.3C].sup.-,
[CF.sub.3CF.sub.2CF.sub.2CF.sub.2SO.sub.3].sup.-,
[CF.sub.3CF.sub.2CF.sub.2SO.sub.3],
[(CF.sub.3CF.sub.2SO.sub.2).sub.3C].sup.-,
[(SO.sub.2CF.sub.3).sub.3N].sup.-,
[(SO.sub.2CF.sub.2CF.sub.3).sub.2N].sup.-,
[((CF.sub.3)C.sub.6H.sub.4)SO.sub.3].sup.-,
[SO.sub.3(CF.sub.2CF.sub.2CF.sub.2CF.sub.2)SO.sub.3].sub.2.sup.-
and the like. Examples of the anion having B include
[B(CFs).sub.4].sup.-,
[(C.sub.6H.sub.5)B(C.sub.6F.sub.5).sub.3].sup.-,
[(C.sub.6H.sub.5)B((CF.sub.3).sub.2C.sub.6H.sub.3).sub.3].sup.- and
the like. Examples of an anion having Ga include
[((CF.sub.3).sub.4Ga)].sup.-, [Ga(C.sub.6F.sub.5).sub.4].sup.- and
the like. Examples of anions having Al include
[((CF.sub.3).sub.3CO).sub.4Al].sup.-,
[((CF.sub.3CF.sub.2).sub.3CO).sub.4Al].sup.-.
[0070] In the case that the dental adhesive composition of the
present disclosure contains the (C) photoacid generator, the
compounding amount of the (C) photoacid generator is preferably
0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass,
with respect to 100 parts by mass of total of the (A) polymerizable
monomer and the (F) volatile organic solvent or with respect to 100
parts by mass of total of the (A) polymerizable monomer, the (F)
volatile organic solvent and (G) water in the case of containing
the (G) water. When the compounding amount of the (C) photoacid
generator is less than 0.01 parts by mass, there is a case that the
polymerization promoting ability is poor and the curing becomes
insufficient. When the compounding amount is more than 10 parts by
mass, there is a case that storage stability decreases.
[0071] The photoacid generator that can be used in the dental
adhesive composition of the present disclosure is not limited to
the photoacid generator described in the specific example, and two
or more types can be used in combination.
[0072] The dental adhesive composition of the present disclosure
may comprise only an aryl iodonium salt which is a salt of an anion
having an organic group and one or more atoms of P, B, Al, S, and
Ga, and an aryl iodonium cation as the (C) photoacid generator. The
dental adhesive composition of the present disclosure may comprise
only an aryl iodonium salt which is a salt of an anion having an
organic group in which at least one H may be substituted with F and
one or more atoms of P, B, Al, S, and Ga, and an aryl iodonium
cation as the (C) photoacid generator.
[(D) Photopolymerization Accelerator]
[0073] The dental adhesive composition of the present disclosure
contains (D-1) aliphatic tertiary amine compound represented by
formula (1) as the (D) photopolymerization accelerator. The dental
adhesive composition of the present disclosure may contains (D)
photopolymerization accelerator other than (D-1) aliphatic tertiary
amine compound represented by formula (1). The (D)
photopolymerization accelerator other than (D-1) aliphatic tertiary
amine compound represented by formula (1) which is used for the
dental adhesive composition of the present disclosure is not
particularly limited as long as it has polymerization promoting
ability, and any known photopolymerization accelerator commonly
used in the dental field may be used without any limitation. As the
photopolymerization accelerator, a primary to tertiary amine
compound such as an aromatic amine compound and an aliphatic amine
compound, an organic metal compound, a phosphine compound and the
like can be used. Among these, an aromatic amine compound, a
tertiary aliphatic amine compound and an organic metal compound are
preferable because they are excellent in curability.
[0074] Aromatic amine compound refers to a compound in which one or
more H of ammonia (NH.sub.3) is replaced with an aromatic ring.
Aromatic amine compound in which one H of NH.sub.3 is substituted
with an aromatic ring is classified into an aromatic primary amine
compound, aromatic amine compound in which one H of NH.sub.3 is
substituted with an aromatic ring and one H of remaining two H is
substituted with an aromatic ring or an alkyl group is classified
into an aromatic secondary amine compound, and aromatic amine
compound in which one H of NH.sub.3 is substituted with an aromatic
ring and remaining two H are substituted with an aromatic ring or
an alkyl group is classified into an aromatic tertiary amine
compound.
[0075] Specific examples of the aromatic primary amine compound
include aniline. Specific examples of the aromatic secondary amine
compound include N-protected amino acid (ester) such as N-phenyl
benzylamine, N-benzyl-p-anisidine, N-benzyl-o-phenetidine,
N-phenylglycine ethyl and N-phenylglycine. Specific examples of the
aromatic tertiary amine compound include N,N-dimethylaniline,
N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline,
p-N,N-dimethyl-toluidine, m-N,N-dimethyl-toluidine,
p-N,N-diethyl-toluidine, p-bromo-N,N-dimethylaniline,
m-chloro-N,N-dimethylaniline, p-dimethylamino benzaldehyde,
p-dimethylamino acetophenone, p-dimethylamino benzoic acid,
p-dimethylamino benzoic acid ethyl ester, p-dimethylamino benzoic
acid isoamyl estel, p-dimethylamino benzoic acid 2-butoxyethyl,
p-dimethylamino benzoic acid 2-ethylhexyl, p-dimethylamino benzoic
acid amino ester, N,N-dimethyl anthranic acid methyl ester,
N,N-dihydroxyethyl aniline, N,N-diisopropanol aniline,
p-N,N-dihydroxyethyl-toluidine, p-N,N-diisopropanol-toluidine,
p-dimethylamino phenyl alcohol, p-dimethylamino styrene,
N,N-dimethyl-3,5-xylidine, 4-dimethylamino pyridine,
N,N-dimethyl-.alpha.-naphthylamine,
N,N-dimethyl-.beta.-naphthylamine and the like.
[0076] Specific examples of the above organic metal compound
include an organic metal compound containing scandium (Sc),
titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt
(Co), nickel (Ni), copper (Cu), tin (Sn), zinc (Zn) an/or zirconia
(Zr), and an organic metal compound containing tin (Sn), vanadium
(V) and/or copper (Cu) is preferable. Specific examples of the
organic metal compound containing tin (Sn) include
dibutyl-tin-diacetate, dibutyl-tin-dimaleate,
dioctyl-tin-dimaleate, dioctyl-tin-dilaurate,
dibutyl-tin-dilaurate, dioctyl-tin-diversate,
dioctyl-tin-S,S'-bis-isooctyl mercapto acetate,
tetramethyl-1,3-diacetoxy distanoxane and the like. Specific
examples of the organic metal compound containing vanadyl (V)
include acetylacetone vanadium, divanadium tetraoxide, vanadyl
acetylacetonate, vanadyl stearate oxide, vanadyl oxalate, vanadyl
sulphate, oxobis (1-phenyl-1,3-butandionate) vanadium, bis
(maltlate) oxovanadium, vanadium pentoxide and sodium metavanadate.
Specific examples of the organic metal compound containing copper
(Cu) include copper acetylacetone, copper naphthenate, copper
octylate, copper stearate and copper acetate.
[0077] The phosphine compound refers to a compound which is
trisubstituted on P atom with organic groups, and the aromatic
phosphine compound refers to a compound which is substituted on P
atom with a phenyl group which may have one or more substituents.
Specific examples of the phosphine compound include
trimethylphosphine, tributylphosphine, trihexylphosphine,
tri-n-octylphosphine, tricyclohexylphosphine, tri (2-thienyl)
phosphine, diphenylpropyl phosphine, di-tert-butyl
(3-methyl-2-butenyl) phosphine, methyldiphenyl phosphine, triphenyl
phosphine, 2-(diphenylphosphino) styrene, 3-(diphenylphosphino)
styrene, 4-(diphenylphosphino) styrene, allyldiphenyl phosphine,
2-(diphenylphosphino) benzaldehyde, 3-(diphenylphosphino)
benzaldehyde, 4-(diphenylphosphino) benzaldehyde,
2-(phenylphosphine) benzoic acid, 3-(phenylphosphino) benzoic acid,
4-(phenylphosphino) benzoic acid, tris (2-methoxyphenyl) phosphine,
tris (3-methoxyphenyl) phosphine, tris (4-methoxyphenyl) phosphine,
2-(diphenylphosphino) biphenyl, tris (4-fluorophenyl) phosphine,
tri (o-trill) phosphine, tri (m-trill) phosphine, tri (p-trill)
phosphine, 2-(dimethylamino) phenyldiphenyl phosphine,
3-(dimethylamino) phenyldiphenyl phosphine, 4-(dimethylamino)
phenyldiphenyl phosphine, 2,2'-bis (diphenylphosphino) biphenyl,
bis [2-(diphenylphosphino) phenyl] ether and the like. Among them,
triphenylphosphine, 4-(phenylphosphino) benzoic acid, tri (o-tolyl)
phosphine, tri (m-tolyl) phosphine and tri (p-tolyl) phosphine are
preferable.
[0078] Aliphatic amine compounds refer to compounds in which one or
more H of ammonia (NH.sub.3) are substituted with alkyl group. As
for the alkyl group, CH.sub.3-- and --CH.sub.2-- are classified as
a primary alkyl group, the one in which one H of --CH.sub.2-- is
substituted with a substituent is classified as a secondary alkyl
group, and the one in which two H of --CH.sub.2-- are substituted
with substituents is classified as a tertiary alkyl group.
Aliphatic amine in which one H of NH.sub.3 is substituted with an
alkyl group is classified into an aliphatic primary amine compound,
aliphatic amine compound in which two H of NH.sub.3 are substituted
with an alkyl group is classified into an aliphatic secondary amine
compound, and aliphatic amine compound in which three H of NH.sub.3
are substituted with an alkyl group is classified into an aliphatic
tertiary amine compound.
[0079] Specific examples of the aliphatic primary amine compound
include amino acid or amino acid ester such as benzhydrylamine,
triphenylmethylamine and glycine. Specific examples of the
aliphatic secondary amine compound include dibenzylamine,
N-benzyl-1-phenylethylamine, bis (1-phenylethyl) amine, bis
(4-cyanobenzyl) amine, N-benzyl protected amino acid and N-benzyl
protected amino acid ester. Specific examples of the aliphatic
tertiary amine compound include tributylamine, tripropylamine,
triethylamine, N,N-dimethyl hexylamine, N,N-dimethyl dodecylamine,
N,N-dimethyl stearylamine, N-[3-(dimethylamino) propyl] acrylamide,
N,N-dimethyl formamide dimethylacetal, N,N-dimethylacetamide
dimethylacetal, N,N-dimethylformamide diethylacetal,
N,N-dimethylformamide dipropylacetal, N,N-dimethylformamide
di-tert-butylacetal, 1-(2-hydroxyethyl) ethyleneimine, N,N-dimethyl
ethanolamine, N,N-dimethyl isopropanolamine, N,N-diisopropyl
ethanolamine, N-methyl diethanolamine, N-ethyl diethanolamine,
N-ethyl diethanolamine, N-butyl diethanolamine, N-lauryl
diethanolamine, N-stearyl diethanolamine, triethanolamine,
triisopropanolamine, tribenzylamine, dibenzylglycine ethylester,
N'-(2-hydroxyethyl)-N,N,N'-trimethylethylene diamine,
2-(dimethylamino)-2-methyl-1-propanol, N,N-dimethyl-2,3-dihydroxy
propylamine, N,N-diethylethanolamine, 1-methyl-3-pyrrolidinol,
1-(2-hydroxyethyl) pyrrolidine, 1-isopropyl-3-pyrrolidinol,
1-piperidin ethanol, 2-[2-(dimethylamino) ethoxy] ethanol,
N,N-dimethylglycine, N,N-dimethylglycine methyl, N,N-diethylglycine
methyl, N,N-dimethylglycine ethyl, N,N-diethylglycine sodium,
2-(dimethylamino) ethylacetate, N-methylimimino diacetic acid,
N,N-dimethylamino ethylacrylate, N,N-diethylamino
ethylmethacrylate, N,N-diisopropylamino ethylmethacrylate,
N,N-dibutylamino ethylmethacrylate, N,N-dibenzylamino
ethylmethacrylate, 3-dimethylamino propionitrile, tris
(2-cyanoethyl) amine, N,N-dimethyl allylamine, N,N-diethyl
allylamine and triallylamine.
[0080] The dental adhesive composition of the present disclosure
contains (D-1) aliphatic tertiary amine compound represented by
formula (1) as the (D) photopolymerization accelerator.
##STR00003##
[0081] In formula, R.sub.1 represents a substituent consisting of
three or more carbons having an electron-withdrawing group at
.alpha.-carbon and/or .beta.-carbon of an amine starting from N,
R.sub.2 represents a substituent consisting of three or more
carbons which may have an electron-withdrawing group, R.sub.3
represents a substituent consisting of one or more carbons which
may have an electron-withdrawing group, and .alpha.-carbon of N in
the formula (1) is not an electron-withdrawing group.
[0082] The electron-withdrawing group in R.sub.1 may be a
substituent selected from a functional group selected from the
group consisting of a hydroxyl group, a carboxyl group, a vinyl
group, an aryl group and a halogen, and, an organic group which is
bonded via an ether bond, an ester bond, a urethane bond or a urea
bond and may have --OH group, --O-group, --C(O)-group, --S-group,
--NH--C(O)--NH-group, --C(O)--O-group, --O--C(O)-group,
--OC(O)--NH-group, --NH--C(O)--O-group, an aromatic hydrocarbon
group, or a polymerizable functional group capable of radical
polymerization.
[0083] Conventionally, an aliphatic tertiary amine such as
dimethylaminoethyl methacrylate or triethanolamine have been
compounded to the dental adhesive composition for the purpose of
promoting photopolymerization, improving solubility and improving
storage stability. However, when the above-mentioned conventional
aliphatic tertiary amine and (A-1) polymerizable monomer having an
acidic group are compounded in a dental adhesive composition, there
is a case that it is confirmed that the adhesive property with
respect to a tooth substance and a prosthetic device is reduced
after long-term storage. As a result of study by the present
inventors, it has been found that good adhesive property with
respect to a tooth substance and a prosthetic device can be
maintained even when stored for a long period of time by using the
(D-1) aliphatic tertiary amine compound represented by formula (1)
having an electron-withdrawing group and steric hindrance as
compared with the conventionally used tertiary aliphatic amine
compound. Further, the present inventors have been found that there
is a case in which the (D-1) aliphatic tertiary amine compound
represented by formula (1) exhibits the curing accelerating ability
and therefore exhibits good adhesive property and mechanical
property in the case of containing (B) photosensitizer and/or (C)
photoacid generator in the dental adhesive composition or in the
case of using a dental adhesive composition in combination with a
dental curable composition containing (B) photosensitizer and/or
(C) photoacid generator, and have completed the present
disclosure.
[0084] In the (D-1) aliphatic tertiary amine compound represented
by formula (1), R.sub.1 represents a substituent consisting of
three or more carbons having an electron-withdrawing group at
.alpha.-carbon and/or .beta.-carbon of an amine starting from N,
R.sub.2 represents a substituent consisting of three or more
carbons which may have an electron-withdrawing group, R.sub.3
represents a substituent consisting of one or more carbons which
may have an electron-withdrawing group. Here, R.sub.2 and R.sub.3
may be a carbon alicyclic compound or a complex alicyclic compound
in which three or more carbons are cyclically bonded. For the
meaning of .alpha.-position and/or .beta.-position starting from N,
the carbon bonded to N is the .alpha.-position carbon and the
carbon bonded to the .alpha.-position carbon is the .beta.-position
carbon. The number of the carbon in the substituent consisting of
three or more carbons includes the carbon contained in the
electron-attracting functional group. Further, N represented by the
formula (1) does not bond with an electron-withdrawing group
without passing through a hydrocarbon group.
[0085] The electron-withdrawing group refers a substituent that
easily attracts an electron from the bonded atom side. Examples of
the electron-withdrawing group include a hydroxyl group, a thiol
group, a nitro group, a carbonyl group, a carboxyl group, a
sulfonyl group, a cyano group, an aryl group, an amino group, a
halogen, and an organic group bonded via an unsaturated bond such
as a vinyl group and a propargyl group, an ether bond, an ester
bond, a urethane bond or a urea bond.
[0086] Among the electron-withdrawing groups in the formula (1),
the electron-withdrawing group of the .alpha.-carbon and/or
.beta.-carbon of R.sub.1 may be a functional group selected from
the group consisting of a hydroxyl group, a carboxyl group, a vinyl
group, an aryl group and a halogen, and, an organic group which is
bonded via an ether bond, an ester bond, a urethane bond or a urea
bond. This organic group may have --OH group, --O-group,
--C(O)-group, --S-group, --NH--C(O)--NH-group, --C(O)--O-group,
--O--C(O)-group, --OC(O)--NH-group, --NH--C(O)--O-group, an
aromatic hydrocarbon group, or a polymerizable functional group
capable of radical polymerization. Preferable is a hydroxyl group,
a carboxyl group, an aryl group and an organic group having an
ether bond, an ester bond, a urethane bond or a urea bond. More
preferable is an aryl group, a carboxyl group and an organic group
having an ester bond or a urethane bond because steric hindrance is
large or high electron attraction is expected. Furthermore
preferable is a tertiary aliphatic amine compound in which the
amino group is disubstituted or more with an aryl group which may
have a substituent.
[0087] When R.sub.2 and R.sub.3 have an electron-withdrawing group,
the electron-withdrawing group may be a functional group selected
from the group consisting of a hydroxyl group, a carboxyl group, a
vinyl group, an aryl group and a halogen, and, an organic group
which is bonded via an ether bond, an ester bond, a urethane bond
or a urea bond. This organic group may have --OH group, --O-group,
--C(O)-group, --S-group, --NH--C(O)--NH-group, --C(O)--O-group,
--O--C(O)-group, --OC(O)--NH-group, --NH--C(O)--O-group, an
aromatic hydrocarbon group, or a polymerizable functional group
capable of radical polymerization. Preferable is a hydroxyl group,
a carboxyl group, an aryl group and an organic group having an
ether bond, an ester bond, a urethane bond or a urea bond. More
preferable is an aryl group, a carboxyl group and an organic group
having an ester bond or a urethane bond because steric hindrance is
large or high electron withdrawing is expected. Furthermore,
preferable is a tertiary aliphatic amine compound in which the
amino group is disubstituted or more with an aryl group which may
have a substituent.
[0088] In the formula (1), an aliphatic tertiary amine compound in
which R.sub.1 and R.sub.2 have an aliphatic substituent consisting
of three or more carbons having an electron-withdrawing group at
.alpha.-carbon and/or .beta.-carbon is preferable. In this case,
further improvement in storage stability can be expected.
Furthermore, an aliphatic tertiary amine compound in which the
amino group is disubstituted or more with an aryl group which may
have a substituent, that is, an aliphatic tertiary amine compound
having an aryl group which may have a substituent at .alpha.-carbon
and/or .beta.-carbon is preferable. Specific examples include
tribenzylamine, dibenzylglycine ester compound and
dibenzylaminoalkyl (meth) acrylate. A compound having such a
structure is expected to have an effect of improving the adhesive
strength by improving the curability of the interface in the case
that a dental adhesive composition contains a photoacid generator
or in the case that a dental adhesive composition or a dental
photocurable composition for use with and contacting with a dental
adhesive composition contains a photoacid generator.
[0089] Specific examples of the (D-1) aliphatic tertiary amine
compound represented by formula (1) include triisopropanolamine,
2-(dibutylamino)-1-phenyl-1-propanol, 1-[(3,3-diphenylpropyl)
(methyl) amino]-2-methyl-2-propanol, 3,3',3''-nitrilotripropionic
acid, N-benzyl-3,3'-iminodipropionic acid, 1-benzhydrill
azetidine-3-carboxylic acid, 1-benzyl-3-pyrrolidone,
1-(2-phenylethyl)-4-piperidone, 1-benzylpiperidin,
1-phenyl-2-(1-pyrrolidinyl) propan-1-ol, 2-[hydroxy (diphenyl)
methyl]-1-methylpyrrolidin, N,N,N',N'-tetrakis (2-hydroxypropyl)
ethylenediamine, N,N,N',N'',N''-pentakis (2-hydroxypropyl)
diethylenetriamine, 2-piperidino-1,1,2-triphenylethanol, 2-[benzyl
(methyl) amino]-1-phenylethanol,
2-(dibenzylamino)-3-phenyl-1-propanol, 2,6-bis [2-(hydroxy
diphenylmethyl)-1-pyrrolidinyl-methyl]-4-methylphenol,
2-benzyl-1,2,3,4-tetrahydro isoquinolin-8-carboxylic acid,
2-benzyl-1,2,3,4-tetrahydro isoquinolin-3-carboxylic acid,
2-(dibenzylamino) propionaldehyde, 3-(dibenzylamino)-1-propanol,
2-(dibenzylamino)-1-propanol,
2-(N,N-dibenzylamino)-3-methylbutanol, 1-[(dibenzylamino)
methyl]-2-naphthanol, 2-(dibenzylamino)-4-methyl-1-pentanol,
4-dibenzylamino-cyclohexanone, N,N-dibenzyl-1,4-dioxaspiro [4.5]
decane-8-amine, N,N-dipropyl-L-alanine,
N,N-dibenzyl-2-aminoethanol, N,N-dibenzyl glycineethyl,
tribenzylamine, triallylamine, 1,1'-(methylimino) dipropane-2-ol,
1-(benzyl (2-methylallyl) amino)-2-methylpropan-2-ol,
2-piperidino-1,1,2-triphenylethanol, N,N-dibenzylaminoethanol,
N,N-dibenzylaminopropanol and 3-(N,N-dibenzylamino)
propyltriethoxysilane. In addition, examples include a
transesterification product of tertiary amine compound containing
OH group such as N,N-dibenzyl aminoethanol, N,N-dibenzyl
aminopropanol, N,N-dibutyl ethanolamine, N,N-diisopropyl
aminoethanol, N-methyldiethanolamine, N-ethyldiethanolamine,
N-butyldiethanolamine and N-tert-butyl diethanolamine and ester
compound containing (meth) acrylic acid ester such as methyl
methacrylate and butyl methacrylate, an urethane compound
synthesized by reaction of tertiary amine compound containing OH
group and compound having isocyanate such as 2-isocyanatoethyl
(meth) acrylate and 1,1-(bisacryloyloxymethyl) ethylisocyanate, a
transesterification product of an amine compound having a carboxyl
group or ester bond such as 3,3',3''-nitrillo tripropionic acid,
N-benzyl-3,3'-iminodipropionic acid, N-methylimino diacetic acid,
N-(2-hydroxyethyl) iminodiacetic acid, N-(2-carboxyethyl)
iminodiacetic acid, N, N-dipropyl-L-alanine and N,N-dibenzylglycine
and a compound having an OH group such as an alcohol and
2-hydroxyethyl methacrylate, and an urea compound synthesized by a
reaction of a secondary amine such as diisopropylamine and
dibenzylamine and a compound having an isocyanate such as
2-isocyanatoethyl (meth) acrylate or 1,1-(bisacryloyl oxymethyl)
ethyl isocyanate. Among these, a transesterification product, such
as dibenzylaminoethyl methacrylate and dibenzylaminopropyl
methacrylate, of a tertiary amine compound having OH group and an
ester compound having a polymerizable group such as (meth) acrylic
acid ester, an urethane compound synthesized by reaction with
compound having isocyanate such as 2-isocyanatoethyl (meth)
acrylate and 1,1-(bisacryloyl oxymethyl) ethylisocyanate,
N,N-dibenzylglycine ester compound, triisopropanolamine and
tribenzylamine are preferable.
[0090] When R.sub.2 or R.sub.3 of the formula (1) is an aliphatic
tertiary amine compound having an alkoxysilyl group, it can also be
used as a surface treatment agent for a filler. Specific examples
include 3-(N,N-dibenzylamino) propyltriethoxysilane having both a
benzylamino group and an alkoxysilyl group, and synthetic example
include synthesizing by benzyl-protecting aminopropylethoxysilane.
A dental adhesive composition containing a filler surface-treated
with 3-(N,N-dibenzylamino) propyltriethoxysilane can be expected to
exhibit a high curing depth as well as a dental adhesive
composition containing 3-(N,N-dibenzylamino) propyltriethoxysilane.
Even when the aliphatic tertiary amine compound is covalently
immobilized on the filler in this way, the storage stability is
lowered if the structure of the formula (1) is not satisfied.
[0091] The compounding amount of the (D-1) aliphatic tertiary amine
compound represented by formula (1) in the case that the dental
adhesive composition is one pack type dental adhesive composition
is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10
parts by mass, with respect to 100 parts by mass of total of the
(A) polymerizable monomer and the (F) volatile organic solvent or
with respect to 100 parts by mass of total of the (A) polymerizable
monomer, the (F) volatile organic solvent and (G) water in the case
of containing the (G) water, contained in the dental adhesive
composition. When the compounding amount of the (D-1) aliphatic
tertiary amine compound represented by formula (1) in the dental
adhesive composition is less than 0.01 parts by mass, there is a
case that the expected effect of improving the storage stability is
not exhibited, and when the compounding amount of the (D-1)
aliphatic tertiary amine compound represented by formula (1) in the
dental adhesive composition exceeds 20 parts by mass, there is a
case that the adhesive strength decreases.
[0092] The compounding amount of the (D-1) aliphatic tertiary amine
compound represented by formula (1) in the case that the dental
adhesive composition is two packs type dental adhesive composition
consisting of a first pack and a second pack is preferably 0.02 to
20 parts by mass, more preferably 0.1 to 10 parts by mass in the
first pack, with respect to 100 parts by mass of total of the (A)
polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water
contained in the first pack. When the compounding amount is less
than 0.02 parts by mass, there is a case that adhesive property to
the tooth substance and the prosthetic device is not imparted, and
when the compounding amount exceeds 20 parts by mass, there is a
case that the storage stability deteriorates.
[0093] The type of the (D) photopolymerization accelerator may be
appropriately selected according to the type and the compounding
amount of other components to be combined. In addition, the (D)
photopolymerization accelerator may be used not only singly but
also in combinations of two or more.
[0094] The dental adhesive composition of the present disclosure
may contain only the (D-1) aliphatic tertiary amine compound
represented by formula (1) as the (D) photopolymerization
accelerator. The dental adhesive composition of the present
disclosure may contain only the (D-1) aliphatic tertiary amine
compound represented by formula (1) which is an aliphatic tertiary
amine compound in which R.sub.1 and R.sub.2 have an aliphatic
substituent consisting of three or more carbons having an
electron-withdrawing group at .alpha.-carbon and/or .beta.-carbon,
as the (D) photopolymerization accelerator. The dental adhesive
composition of the present disclosure may contain only the (D-1)
aliphatic tertiary amine compound represented by formula (1) which
is an aliphatic tertiary amine compound in which R.sub.1 and
R.sub.2 have an aryl group which may have a substituent, at
.alpha.-carbon and/or .beta.-carbon, as the (D) photopolymerization
accelerator.
[0095] There is no problem even if these (B) photosensitizers, (C)
photoacid generators and (D) photopolymerization accelerators,
which are polymerization initiators, are subjected to a secondary
treatment such as finely pulverization, adsorption on a carrier and
encapsulation in a microcapsule, if necessary. Furthermore, these
photo polymerization initiators can be used not only singly but
also in combinations of two or more, regardless of the
polymerization manner or the polymerization method.
[(E) Filler]
[0096] The dental adhesive composition of the present disclosure
may contain (E) filler, a known filler commonly used can be used
without any limitation.
[0097] The type of the (E) filler is not limited as long as it is a
known filler, and a filler suitable for the application can be
compounded, and it is preferable that a filler such as an inorganic
filler, an organic filler and an organic-inorganic composite filler
is compounded. These fillers can be used not only singly but also
in combinations of a plurality thereof regardless of the types of
the fillers.
[0098] As the above described inorganic filler, the chemical
composition is not particularly limited, but specific examples
include silicon dioxide, alumina, silica-titania,
silica-titania-barium oxide, silica-zirconia, silica-alumina,
lanthanum glass, borosilicate glass, soda glass, barium glass,
strontium glass, glass ceramic, aluminosilicate glass, barium
boroaluminosilicate glass, strontium boroaluminosilicate glass,
fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass,
strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate
glass, strontium calcium fluoroaluminosilicate glass and the like.
Particularly, barium fluoroaluminosilicate glass, strontium
fluoroaluminosilicate glass, fluoroaluminosilicate glass and the
like, which are used in dental glass ionomer cement, resin
reinforced glass ionomer cement and resin cement and the like, can
also be suitably used. The fluoroaluminosilicate glass as used
herein has a basic structure of silicon oxide and aluminum oxide
and contains an alkali metal for introducing non-crosslinked
oxygen. The fluoroaluminosilicate glass further has an alkaline
earth metal including strontium and fluorine as
modified/coordinated ions. The fluoroaluminosilicate glass may be
also a composition in which a lanthanoid series element is
incorporated into the skeleton in order to impart further
radiopacity. This lanthanoid series element also participates in
the composition as a modified/coordinated ion.
[0099] Specific examples of the organic filler include polymers
such as polymethyl methacrylate, polyethyl methacrylate, methyl
methacrylate-ethyl methacrylate copolymer, ethyl methacrylate-butyl
methacrylate copolymer, methyl methacrylate-trimethylolpropane
methacrylate copolymer, polyvinylchloride, polystyrene, chlorinated
polyethylene, nylon, polysulfone, polyethersulfone and
polycarbonate.
[0100] In addition, examples of the organic/inorganic composite
filler include one obtained by covering the surface of a filler
with a polymerizable monomer by polymerization, one obtained by
mixing a filler and a polymerization monomer and polymerizing the
monomer, and thereafter grinding the resultant to a proper particle
size, or one obtained by dispersing a filler in a polymerizable
monomer in advance for emulsion polymerization or suspension
polymerization, but are not limited thereto at all.
[0101] The above described (E) filler can be treated with a surface
treatment material represented by a silane coupling material in
order to improve the affinity to the polymerizable monomer, the
dispersibility in the polymerizable monomer, and the mechanical
strength and water resistance of the cured product. The surface
treatment material and the surface treatment method are not
particularly limited, and known methods can be adopted without
limitation. As a silane coupling material used for surface
treatment of the filler, methyltrimethoxysilane,
methyltriethoxysilane, methyltrichlorosilane,
dimethyldichlorosilane, trimethylchlorosilane,
vinyltrichlorosilane, vinyltriethoxysilane, vinyltris
(2-methoxyethoxy) silane, 3-methacryloyloxypropyl trimethoxysilane,
3-chloropropyl trimethoxysilane, 3-glycidoxypropyl
trimethoxysilane, 3-(meth) acryloxypropyl trimethoxysilane,
8-(meth) acryloxyoctyl trimethoxysilane, 11-(meth) acryloxiundecyl
trimethoxysilane, hexamethyldisilazane and the like are preferable.
In addition to the silane coupling material, surface treatment of
the filler can be performed by a method using a titanate coupling
material or an aluminate coupling material. The treatment amount of
the surface treatment material in the filler is preferably 0.01 to
30 parts by mass, more preferably 0.5 to 20 parts by mass with
respect to 100 parts by mass of the filler before treatment.
[0102] The shape of the filler is not particularly limited, and any
shape of the filler such as an amorphous, a spherical shape, a
needle shape, a plate shape, a crushed shape or a scale shape can
be used. The average particle diameter of the filler is preferably
0.01 .mu.m to 50 .mu.m, more preferably 0.01 .mu.m to 30 .mu.m,
still more preferably 0.05 .mu.m to 20 .mu.m, and more preferably
0.05 .mu.m to 10 .mu.m.
[0103] When (E) filler is compounded in the dental adhesive
composition, the compounding amount is preferably 0.1 to 50 parts
by mass, with respect to 100 parts by mass of total of the (A)
polymerizable monomer and the (F) volatile organic solvent or with
respect to 100 parts by mass of total of the (A) polymerizable
monomer, the (F) volatile organic solvent and (G) water in the case
of containing the (G) water. When the compounding amount of the
filler is less than 0.1 parts by mass, there is a case that the
effect of improving the mechanical strength and of exhibiting the
thixotropy by compounding the filler becomes poor. When the
compounding amount is more than 50 parts by mass, there is a case
that adhesive strength decrease.
[0104] The dental adhesive composition of the present disclosure
contains (F) volatile organic solvent. The volatile organic solvent
is used for the purpose of dissolving a polymerizable monomer
component containing the (A-1) polymerizable monomer having an
acidic group and water in the composition or reducing the viscosity
of the dental adhesive composition. The volatile organic solvent
usually has a boiling point of 150.degree. C. or less under normal
pressure and a solubility of 5% by weight or more with respect to
water at 25.degree. C., more preferably 30% by weight or more, and,
most preferably, an organic solvent which can dissolved in water at
an arbitrary ratio is used. Among these, a water-soluble volatile
organic solvent having a boiling point of 100.degree. C. or less
under normal pressure is preferable, and specific examples include
ethanol, methanol, 1-propanol, isopropyl alcohol, acetone,
methylethyl ketone, 1,2-dimethoxyethane, 1,2-diethoxyethane and
tetrahydrofuran. Further, among the above-mentioned volatile
organic solvents, ethanol, isopropyl alcohol, acetone and
methylethyl ketone are more preferable.
[0105] The (F) volatile organic solvent may be used alone or in
combination of two or more. The compounding amount of the (F)
volatile organic solvent in the case that the dental adhesive
composition is one pack type dental adhesive composition is
preferably 1 to 99.9 parts by mass, more preferably 5 to 99.9 parts
by mass, most preferably 10 to 80 parts by mass, with respect to
100 parts by mass of total of the (A) polymerizable monomer and the
(F) volatile organic solvent or with respect to 100 parts by mass
of total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water,
contained in the dental adhesive composition.
[0106] The compounding amount of the (F) volatile organic solvent
in the case that the dental adhesive composition is two packs type
dental adhesive composition consisting of a first pack and a second
pack is preferably 1 to 99.9 parts by mass, more preferably 5 to
99.9 parts by mass, most preferably 10 to 80 parts by mass in the
first pack, with respect to 100 parts by mass of total of the (A)
polymerizable monomer and the (F) volatile organic solvent
contained in the first pack or with respect to 100 parts by mass of
total of the (A) polymerizable monomer, the (F) volatile organic
solvent and (G) water in the case of containing the (G) water.
[0107] The dental adhesive composition of the present disclosure
may contain (G) water in order to improve the wettability to the
adherend, and specific examples thereof include deionized water and
distilled water. Further, the compounding amount is preferably 5 to
80 parts by mass, more preferably 10 to 60 parts by mass with
respect to 100 parts by mass of total of the (A) polymerizable
monomer, the (F) volatile organic solvent and (G) water contained
in the dental adhesive composition.
[0108] The dental adhesive composition of the present disclosure
may contain a chemical polymerization initiator. Specific examples
of an organic peroxide as chemical polymerization initiator include
diacyl peroxides, peroxy esters, dialkyl peroxides, peroxy ketals,
ketone peroxides, peroxy dicarbonates, and hydro peroxides.
Specific examples of diacyl peroxides include acetyl peroxide,
isobutyryl peroxide, benzoyl peroxide, decanoyyl peroxide,
3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and
lauroyl peroxide and the like. Specific examples of peroxyesters
include .alpha.-cumylperoxy neodecanoate, t-butylperoxy
neodecanoate, t-butylperoxy pivalate, 2,2,4-trimethylpentyl
peroxy-2-ethyl hexanoate, t-amylperoxy-2-ethylhexanoate,
t-butylperoxy-2-ethylhexanoate, di-t-butylperoxy isophthalate,
di-t-butylperoxy hexahydro terephthalate,
t-butylperoxy-3,3,5-trimethyl hexanoate, t-butylperoxy acetate,
t-butylperoxy benzoate and t-butylperoxy maleric acid. Specific
examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl
peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di
(t-butylperoxy) hexane, 1,3-bis (t-butylperoxy isopropyl) benzene,
2,5-dimethyl-2,5-di (t-butylperoxy)-3-hexyne and the like. Specific
examples of peroxyketals include 1,1-di (t-butylperoxy)
cyclohexane, 2,2-di (t-butylperoxy) butane, and
n-butyl-4,4-(t-butylperoxy) parerate, 1,1-di (t-amylperoxy)
cyclohexane and the like. Specific examples of ketone peroxides
include methyl ethyl ketone peroxide, methyl isobutyl ketone
peroxide, methyl cyclohexanone peroxide, cyclohexanone peroxide and
the like. Specific examples of peroxydicarbonates include
di-3-methoxyperoxy dicarbonate, di-2-ethylhexylperoxy dicarbonate,
bis (4-t-butylcyclohexyl) peroxy dicarbonate, diisopropylperoxy
dicarbonate, di-n-propylperoxy dicarbonate, di-2-ethoxyethylperoxy
dicarbonate, diallylperoxy dicarbonate and the like. Specific
examples of hydroperoxides include 2,5-dimethyl
hexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide,
cumene hydroperoxide, t-butyl hydroperoxide and 1,1,3,3-tetramethyl
butylhydroperoxide.
[0109] As the organic peroxide, the above-mentioned organic
peroxides may be used alone, or two or more kinds of organic
peroxides may be used in combination. Among these organic
peroxides, benzoyl peroxide and cumene hydroperoxide are preferable
from the viewpoint of curability. The compounding amount of the
organic peroxide as a chemical polymerization initiator is
preferably set to 0.1 to 5 parts by mass, more preferably set to
0.3 to 3 parts by mass with respect to 100 parts by mass of total
of the (A) polymerizable monomer and the (F) volatile organic
solvent or with respect to 100 parts by mass of total of the (A)
polymerizable monomer, the (F) volatile organic solvent and (G)
water in the case of containing the (G) water from the viewpoint of
improving the curability. When the compounding amount of the
organic peroxide is more than 5 parts by mass, it may be difficult
to ensure sufficient operation time. On the other hand, when the
compounding amount of the organic peroxide is less than 0.1 parts
by mass, there is a case in which mechanical strength may be
insufficient.
[0110] In the dental adhesive composition of the present
disclosure, in order to further improve the curability, a chemical
polymerization accelerator may further be compounded. Examples of
chemical polymerization accelerators include a transition metal
compound of the group 4 in the periodic table, a thiourea
derivative an aliphatic amine, an aromatic amine, a sulfinic acid
and a salt thereof, a borate compound, a sulfur-containing
reductive inorganic compound, a nitrogen-containing reductive
inorganic compound, a barbituric acid derivative, a triazine
compound, a halogen compound and the like. The compounding amount
of the chemical polymerization accelerator is preferably 0.01 to 5
parts by mass, more preferably 0.1 to 3 parts by mass, with respect
to 100 parts by mass of total of the (A) polymerizable monomer and
the (F) volatile organic solvent or with respect to 100 parts by
mass of total of the (A) polymerizable monomer, the (F) volatile
organic solvent and (G) water in the case of containing the (G)
water.
[0111] The transition metal compound of the period 4 in the
periodic table as a chemical polymerization accelerator refers to a
metal compound of groups 3 to 12 of the period 4 in the periodic
table, and specifically, each metal compound of scandium (Sc),
titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt
(Co), nickel (Ni), copper (Cu), and zinc (Zn) can be used without
any limitation. Although each of the above transition metal element
may have a multiple valences, they can be added to the dental
adhesive composition of the present disclosure as long as the
valence is stable. Examples include Sc (trivalent), Ti
(tetravalent), V (trivalent, tetravalent or pentavalent), Cr
(divalent, trivalent or hexavalent), Mn (divalent to heptavalent),
Fe (divalent or trivalent), Co (divalent or trivalent), Ni
(divalent), Cu (monovalent or divalent), Zn (divalent). Specific
examples of the transition metal compound include scandium iodide
(trivalent) and the like as a scandium compound, titanium chloride
(tetravalent), titanium tetraisopropoxide (tetravalent) and the
like as titanium compounds, acetylacetone vanadium (trivalent),
divanadium tetraoxide (tetravalent), vanadylacetyl acetonate
(tetravalent), vanadium stearate oxide (tetravalent), vanadyl
oxalate (tetravalent), vanazyl sulfate (tetravalent), oxobis
(1-phenyl-1,3-butandionate) vanadium (tetravalent), bis (maltlate)
oxovanadium (tetravalent), vanadium pentoxide (pentavalent), sodium
metavanadate (pentavalent) and the like as a vanadium compound,
manganese acetate (divalent), manganese naphthenate (divalent) and
the like as manganese compounds, iron acetate (divalent), iron
chloride (divalent), iron acetate (trivalent), iron chloride
(trivalent) and the like as an iron compound, cobalt acetate
(divalent), cobalt naphthenate (divalent) and the like as a cobalt
compound, nickel chloride (divalent) and the like as a nickel
compound, copper chloride (monovalent), copper bromide
(monovalent), copper chloride (divalent), copper acetate (divalent)
and the like as a copper compound, and zinc chloride (divalent),
zinc acetate (divalent) and the like as a zinc compound.
[0112] Among these, a trivalent or tetravalent vanadium compound
and a divalent copper compound are preferable. Among them, because
of having higher polymerization accelerating ability, a trivalent
or tetravalent vanadium compound is more preferable, and a
tetravalent vanadium compound is most preferable. A plurality of
kinds of these transition metal compounds in the period 4 in the
periodic table may be used in combination, if necessary. The
compounding amount of transition metal compound is preferably
0.0001 to 1 parts by mass with respect to 100 parts by mass of
total of the (A) polymerizable monomer and the (F) volatile organic
solvent or with respect to 100 parts by mass of total of the (A)
polymerizable monomer, the (F) volatile organic solvent and (G)
water in the case of containing the (G) water. When the compounding
amount is less than 0.0001 parts by mass, there is a case where the
polymerization accelerating effect is insufficient, and when the
compounding amount exceeds 1 part by mass, there is a case where it
causes discoloration or gelation of the dental adhesive composition
and the storage stability is lowered.
[0113] Any known thiourea derivatives can be used as the thiourea
derivative as the chemical polymerization accelerator without any
limitation. Specific examples of the thiourea derivatives include
dimethylthiourea, diethylthiourea, tetramethylthiourea, (2-pyridyl)
thiourea, N-methylthiourea, ethylenethiourea, N-allylthiourea,
N-allyl-N'-(2-hydroxyethyl) thiourea, N-benzylthiourea,
1,3-dicyclohexyl thiourea, N,N'-diphenylthiourea, 1,3-di (p-tolyl)
thiourea, 1-methyl-3-phenylthiourea, N-acetylthiourea,
N-benzoylthiourea, diphenylthiourea, dicyclohexylthiourea and the
like. Among these, (2-pyridyl) thiourea, N-acetylthiourea and
N-benzoylthiourea are preferable. A plurality of kinds of these
thiourea derivatives can be used in combination, if necessary. The
compounding amount of the thiourea derivative is preferably 0.1 to
5 parts by mass with respect to 100 parts by mass of total of the
(A) polymerizable monomer and the (F) volatile organic solvent or
with respect to 100 parts by mass of total of the (A) polymerizable
monomer, the (F) volatile organic solvent and (G) water in the case
of containing the (G) water. When the compounding amount is less
than 0.1 parts by mass, there is a case where the ability as a
polymerization accelerator is insufficient, and when the
compounding amount exceeds 5 parts by mass, the storage stability
may be lowered.
[0114] Examples of sulfinic acid and its salt include p-toluene
sulfinic acid, sodium p-toluene sulfinate, potassium p-toluene
sulfinate, lithium p-toluene sulfinate, calcium p-toluene
sulfinate, benzenesulfinic acid, sodium benzene sulfinate,
potassium benzene sulfinate, lithium benzenesulfinate, calcium
benzenesulfinate, 2,4,6-trimethyl benzenesulfinic acid, sodium
2,4,6-trimethyl benzenesulfinate, potassium 2,4,6-trimethyl
benzenesulfinate, lithium 2,4,6-trimethyl benzenesulfinate, calcium
2,4,6-trimethyl benzenesulfinate, 2,4,6-triethyl benzenesulfinic
acid, sodium 2,4,6-triethyl benzenesulfinate, potassium
2,4,6-triethyl benzenesulfinate, lithium 2,4,6-triethyl
benzenesulfinate, calcium 2,4,6-triethyl benzenesulfinate,
2,4,6-triisopropyl benzenesulfinic acid, sodium 2,4,6-triisopropyl
benzenesulfinate, potassium 2,4,6-triisopropyl benzenesulfinate,
lithium 2,4,6-triisopropyl benzenesulfinate, calcium
2,4,6-triisopropyl benzenesulfinate and the like. Among them,
sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium
2,4,6-triisopropyl benzenesulfinate are particularly
preferable.
[0115] As the borate compound, specific examples of the borate
compound having one aryl group in one molecule include
trialkylphenylboron, trialkyl (p-chlorophenyl) boron, trialkyl
(p-fluorophenyl) boron, trialkyl (3,5-bistrifluoro methyl) phenyl
boron, trialkyl [3,5-bis
(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, trialkyl
(p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl
(p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl
(p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron,
trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl)
boron (the alkyl group is at least one selected from the group
consisting of n-butyl group, n-octyl group and n-dodecyl group
etc.) and salts thereof (sodium salt, lithium salt, potassium salt,
magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium
salt, tetraethyl ammonium salt, methyl pyridinium salt, ethyl
pyridinium salt, butyl pyridinium salt, methyl quinolinium salt,
ethyl quinolinium salt, butyl quinolinium salt and the like).
Specific examples of the borate compound having two aryl groups in
one molecule include dialkyl diphenylboron, dialkyl di
(p-chlorophenyl) boron, dialkyl di (p-fluorophenyl) boron, dialkyl
di (3,5-bistrifluoro methyl) phenyl boron, dialkyl di [3,5-bis
(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyl
di (p-nitrophenyl) boron, dialkyl di (m-nitrophenyl) boron, dialkyl
di (p-butylphenyl) boron, dialkyl di (m-butylphenyl) boron, dialkyl
di (p-butyl oxyphenyl) boron, dialkyl di (m-butyl oxyphenyl) boron,
dialkyl di (p-octyl oxyphenyl) boron and dialkyl di (m-octyl
oxyphenyl) boron (the alkyl group is at least one selected from the
group consisting of n-butyl group, n-octyl group and n-dodecyl
group etc.) and salts thereof (sodium salt, lithium salt, potassium
salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl
ammonium salt, tetraethyl ammonium salt, methyl pyridinium salt,
ethyl pyridinium salt, butyl pyridinium salt, methyl quinolinium
salt, ethyl quinolinium salt, butyl quinolinium salt and the like).
Specific examples of the borate compound having three aryl groups
in one molecule include monoalkyl triphenylboron, monoalkyl tri
(p-chlorophenyl) boron, monoalkyl tri (p-fluorophenyl) boron,
monoalkyl tri (3,5-bistrifluoro methyl) phenyl boron, monoalkyl tri
[3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron,
monoalkyl tri (p-nitrophenyl) boron, monoalkyl tri (m-nitrophenyl)
boron, monoalkyl tri (p-butylphenyl) boron, monoalkyl tri
(m-butylphenyl) boron, monoalkyl tri (p-butyl oxyphenyl) boron,
monoalkyl tri (m-butyl oxyphenyl) boron, monoalkyl tri (p-octyl
oxyphenyl) boron and monoalkyl tri (m-octyl oxyphenyl) boron (the
alkyl group is at least one selected from the group consisting of
n-butyl group, n-octyl group and n-dodecyl group etc.) and salts
thereof (sodium salt, lithium salt, potassium salt, magnesium salt,
tetrabutyl ammonium salt, tetramethyl ammonium salt, tetraethyl
ammonium salt, methyl pyridinium salt, ethyl pyridinium salt, butyl
pyridinium salt, methyl quinolinium salt, ethyl quinolinium salt,
butyl quinolinium salt and the like). Specific examples of the
borate compound having four aryl groups in one molecule include
tetraphenylboron, tetra kis (p-chlorophenyl) boron, tetra kis
(p-fluorophenyl) boron, tetra kis (3,5-bistrifluoro methyl) phenyl
boron, tetra kis [3,5-bis
(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetra
kis (p-nitrophenyl) boron, tetra kis (m-nitrophenyl) boron, tetra
kis (p-butylphenyl) boron, tetra kis (m-butylphenyl) boron, tetra
kis (p-butyl oxyphenyl) boron, tetra kis (m-butyl oxyphenyl) boron,
tetra kis (p-octyl oxyphenyl) boron, tetra kis (m-octyl oxyphenyl)
boron, (p-fluorophenyl) triphenylboron, (3,5-bis trifluoromethyl)
phenyl triphenylboron, (p-nitrophenyl) triphenylboron, (m-butyl
oxyphenyl) triphenylboron, (p-butyl oxyphenyl) triphenylboron,
(m-octyl oxyphenyl) triphenylboron and (p-octyl oxyphenyl)
triphenylboron, and salts thereof (sodium salt, lithium salt,
potassium salt, magnesium salt, tetrabutyl ammonium salt,
tetramethyl ammonium salt, tetraethyl ammonium salt, methyl
pyridinium salt, ethyl pyridinium salt, butyl pyridinium salt,
methyl quinolinium salt, ethyl quinolinium salt, butyl quinolinium
salt and the like).
[0116] Among these aryl borate compounds, it is more preferable to
use a borate compound having 3 or 4 aryl groups in one molecule
from the viewpoint of storage stability. Further, these aryl borate
compounds can be used alone or as a mixture of two or more.
[0117] Examples of sulfur-containing reductive inorganic compound
include sulfites, bisulfites, pyrosulfites, thiosulfates, thionates
and dithionite. Specific examples include sodium sulfite, potassium
sulfite, calcium sulfite, ammonium sulfite, sodium bisulfite,
potassium bisulfite, 3-mercaptopropyl trimethoxysilane,
2-mercaptobenzoxazole, decanethiol, thiobenzoic acid and the
like.
[0118] Examples of nitrogen-containing reductive inorganic compound
include nitrites, and specific examples include sodium nitrite,
potassium nitrite, calcium nitrite, ammonium nitrite and the
like.
[0119] Specific examples of barbituric acid derivative include
salts (alkali metals or alkaline earth metals are preferred) of
barbituric acid, 1,3-dimethyl barbituric acid, 1,3-diphenyl
barbituric acid, 1,5-dimethyl barbituric acid, 5-butyl barbituric
acid, 5-ethyl barbituric acid, 5-isopropyl barbituric acid,
5-cyclohexyl barbituric acid, 1,3,5-trimethyl barbituric acid,
1,3-dimethyl-5-ethyl barbituric acid, 1,3-dimethyl-n-butyl
barbituric acid, 1,3-dimethyl-5-isobutyl barbituric acid,
1,3-dimethyl barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric
acid, 1,3-dimethyl-5-cyclohexyl barbituric acid
1,3-dimethyl-5-phenyl barbituric acid, 1-cyclohexyl-1-ethyl
barbituric acid, 1-benzyl-5-phenyl barbituric acid, 5-methyl
barbituric acid, 5-propyl barbituric acid, 1,5-diethyl barbituric
acid, 1-ethyl-5-methyl barbituric acid, 1-ethyl-5-isobutyl
barbituric acid, 1,3-diethyl-5-butyl barbituric acid,
1-cyclohexyl-5-methyl barbituric acid, 1-cyclohexyl-5-ethyl
barbituric acid, 1-cyclohexyl-5-octyl barbituric acid,
1-cyclohexyl-5-hexyl barbituric acid, 5-butyl-1-cyclohexyl
barbituric acid, 1-benzyl-5-phenyl barbituric acid and
thiobarbituric acids. Specifically, the salts of these barbituric
acids include sodium 5-butyl barbiturate, sodium1,3,5-trimethyl
barbiturate, sodium 1-cyclohexyl-5-ethyl barbiturate and the
like.
[0120] Specific examples of the halogen compound include dilauryl
dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium
chloride, benzyl trimethyl ammonium chloride, tetramethyl ammonium
chloride, benzyl dimethyl acetyl ammonium chloride, dilauryl
dimethyl ammonium bromide and the like.
[0121] The dental adhesive composition of the present disclosure
may not contain a chemical polymerization initiator and a chemical
polymerization accelerator. The dental adhesive composition of the
present disclosure may not contain a polymerization initiator
system other than the photopolymerization system.
<Other Component>
[0122] Further, the dental adhesive composition of the present
disclosure may contain a component other than above described
components within a range not to impair the effect of the present
disclosure. For example, an excipient typified by fumed silica,
benzophenone-based and benzotriazole-based ultraviolet absorbers,
polymerization inhibitors such as hydroquinone, hydroquinone
monomethyl ether and 2,5-ditershally butyl-4-methylphenol, chain
transfer materials such as .alpha.-alkylstyrene compound, mercaptan
compound such as n-butyl mercaptan and n-octyl mercaptan, and
terpenoid compound such as limonene, myrsen, .alpha.-terpinene,
.beta.-terpinene, .gamma.-terpinene, terpinoren, .beta.-pinene and
.alpha.-pinene, metal supplementary material such as
aminocarboxylic acid chelating agent and phosphonic acid chelating
agent, discoloration inhibitors, antibacterial materials, coloring
pigments, and other additives conventionally known in the art may
be added as necessary and as desired.
[0123] A preparing method of the dental adhesive composition of the
present disclosure is not particularly limited. Examples of a
general preparing method of a dental adhesive composition, for
example, include a method which comprises simultaneously mixing (A)
polymerizable monomer containing (A-1) polymerizable monomer having
an acidic group, (D) photopolymerization accelerator containing
(D-1) aliphatic tertiary amine compound represented by formula (1),
(F) volatile organic solvent and (G) water, and a method which
comprises mixing (A) polymerizable monomer containing (A-1)
polymerizable monomer having an acidic group, (D)
photopolymerization accelerator containing (D-1) aliphatic tertiary
amine compound represented by formula (1) and (F) volatile and then
adding (G) water and mixing. A mixer such as a mix rotor can be
used for mixing. In the present disclosure, it can be prepare by
the above-described method without any problem.
[0124] The dental adhesive composition of the present disclosure
can be used for a dental bonding material, a dental primer, a
dental coating material and a dental glass ionomer cement, which
are one pack type dental adhesive composition, two packs type
dental adhesive composition or the like. Further, it can be used as
a dental adhesive kit in which the dental adhesive composition of
the present disclosure and a dental curable composition are
combined. A dental curable compositions can be used for a dental
adhesive material, a dental composite resin, a dental core build-up
material, a dental resin cement, a dental coating material, a
dental sealant material, a dental manicure material and a dental
splinting material.
<One Pack Type Dental Adhesive Composition>
[0125] When the present disclosure is used in one pack type dental
adhesive composition, it is preferably used for a dental bonding
material, a dental primer and a dental coating material. In the
case of one pack type dental adhesive composition, since
complicated steps such as mixing are not required before use,
reduction of technical errors and reduction of burden on the
operator can be expected. The one pack type dental adhesive
composition may comprise (A) polymerizable monomer such as a
polymerizable monomer having an alkoxysilyl group and a
polymerizable monomer having a sulfur atom, (B) photosensitizer,
(C) photoacid generator, (D) photopolymerization accelerator and
the like in addition to (A-1) polymerizable monomer having an
acidic group, (D-1) aliphatic tertiary amine compound represented
by formula (1), (F) volatile organic solvent and (G) water. In
particular, when (B) photosensitizer and (C) photoacid generator
are contained, it is preferable that one pack type dental adhesive
composition is cured by irradiating light after using the one pack
type dental adhesive composition and therefore it can be expected
to improve the adhesive property with respect to the composition to
be applied next.
<Two Packs Type Dental Adhesive Composition>
[0126] When the present disclosure is used in two packs type dental
adhesive composition, it is preferably used for a dental bonding
material, a dental primer, a dental coating material and a dental
glass ionomer cement. The two packs type dental adhesive
composition is used by mixing the two packs before use. The
preferred mixing ratio is a mass ratio of 0.8 to 1.2:1.0. Curing
proceeds without light irradiation such as glass ionomer reaction
or redox reaction. Since the two packs type dental adhesive
composition cures without light irradiation, it is suitable for use
in a deep cavity where light is difficult to reach, and further, it
is expected that high adhesive strength is exhibited by performing
light irradiation. The two packs type dental adhesive composition
is packaged in a first pack and a second pack, and the first pack
contains (A-1) polymerizable monomer having an acidic group, (D-1)
aliphatic tertiary amine compound represented by formula (1), (F)
volatile organic solvent and (G) water, and a chemical
polymerization accelerator and an organic peroxide are separately
contained in the first pack and the second pack, respectively. The
first pack and the second pack may comprise (A) polymerizable
monomer such as a polymerizable monomer having an alkoxysilyl group
and a polymerizable monomer having a sulfur atom, (B)
photosensitizer, (C) photoacid generator, (D) photopolymerization
accelerator other than the (D-1) aliphatic tertiary amine compound
represented by formula (1) and the like
<Dental Adhesive Kit>
[0127] The dental adhesive composition of the present disclosure
can be used as a dental adhesive kit in combination with a dental
curable composition. As the dental adhesive composition, the above
described one pack type dental adhesive composition or two packs
type dental adhesive composition is used. Specific examples of a
dental curable composition include a dental adhesive material, a
dental composite resin, a dental core build-up material, a dental
resin cement, a dental coating material, a dental sealant material,
a dental manicure material, a dental splinting material and a glass
ionomer cement. Among them, in particular, it is used as a two-step
type dental bonding material combined with a dental adhesive
material, or a dental adhesive kit in which it combined with a
dental composite resin, a dental core build-up material, a dental
resin cement or a glass ionomer cement. It is preferable that the
dental curable composition contains (A) polymerizable monomer and a
polymerization initiator as an essential component, and (E) filler.
The polymerization initiator is classified into a
photopolymerization initiator and a chemical polymerization
initiator, and may contain either one or both of them. In
particular, when the dental curable composition contains (B)
photosensitizer and (C) photoacid generator as a
photopolymerization initiator, high adhesive strength and
improvement in mechanical properties can be expected in the case of
combining with the dental adhesive composition containing (D-1)
aliphatic tertiary amine compound represented by formula (1) of the
present disclosure. For preferable compounding amount in such a
dental curable composition, (B) photosensitizer is 0.001 to 2 parts
by mass and (C) photoacid generator is 0.01 to 10 parts by mass
with respect to 100 parts by mass of the (A) polymerizable monomer
contained in the dental curable composition, and it is preferable
that the composition is one pack type dental curable composition or
two packs type dental curable composition.
[0128] The dental adhesive composition of the present disclosure
may comprise only (A) polymerizable monomer, (D)
photopolymerization accelerator, and (F) volatile organic solvent.
Further, as the components other than (A), (D) and (F), only one or
more of the above-mentioned components may be contained.
Examples
[0129] Hereinafter, example of the present disclosure are
specifically described. However, the present disclosure is not
intended to be limited to these Examples.
[0130] The materials used in Examples and Comparative examples and
their abbreviations are listed below.
[(A) Polymerizable Monomer]
[0131] Bis-GMA: 2,2-bis [4-(3-methacryloyloxy-2-hydroxypropoxy)
phenyl] propane 2.6E: 2,2-bis (4-(meth) acryloyloxy
polyethoxyphenyl) propane in which the average addition mole number
of ethoxy groups is 2.6 UDMA: N,N-(2,2,4-trimethyl hexamethylene)
bis [2-(aminocarboxy) ethanol]methacrylate TEGDMA:
triethyleneglycol dimethacrylate HEMA: 2-hydroxyethyl
methacrylate
[(A-1) Polymerizable Monomer Having an Acidic Group]
[0132] MDP: 10-methacryloyloxydecyl dihydrogen phosphate MHPA:
6-methacryloxyhexyl phosphonoacetate MET: 4-methacryloxyethyl
trimellitic acid META: 4-methacryloyloxy ethoxycarbonylphthalic
anhydride
[Polymerizable Monomer Having Alkoxysilyl Group]
[0133] MPTMS: 3-methacryloxypropyl trimethoxysilane
[Polymerizable Monomer Having Sulfur Atom]
[0134] MDDT: 10-methacryloxydecyl-6,8-ditioctanate
[(B) Photosensitizer]
[0135] CQ: .alpha.-camphorquinone BAPO: phenyl bis
(2,4,6-trimethylbenzoyl) phosphine oxide
[(C) Photoacid Generator]
C1: Bis (4-tert-butylphenyl) iodonium Nonafluorobutane
Sulfonate
##STR00004##
[0136] C2: Bis (4-tert-butylphenyl) iodium Camphor Sulfonate
##STR00005##
[0137] C3: Bis (4-tert-butylphenyl) iodonium Tris
(pentafluoropropyl) trifluorophosphate
##STR00006##
[0138] C4: Bis (4-n-dodecylphenyl) iodonium Tetrakis
(pentafluorophenyl) borate
##STR00007##
[0139] C5: Bis [(4-tert-butyl) phenyl] iodonium Tetra
(nonafluoro-tert-butoxy) aluminate
##STR00008##
[0140] C6: Bis [4-(tert-butyl) phenyl] iodonium Tetra
(pentafluorophenyl) gallate
##STR00009##
[0141] C7: Diphenyliodonium Trifluoromethane Sulfonic Acid
##STR00010##
[0142] C8: Bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate
##STR00011##
[0143] C9: Bis (4-tert-butylphenyl) iodonium
Hexafluorophosphate
##STR00012##
[0144] C10: Bis (4-n-dodecylphenyl) iodonium
Hexafluorophosphate
##STR00013##
[0145] C11: 2,4,6-tris (trichloromethyl)-1,3,5-triazine
##STR00014##
[0146] C12: diphenyliodonium-2-carboxylate Monohydrate
##STR00015##
[0147] [(D) Photopolymerization Accelerator]
[(D-1) Aliphatic Tertiary Amine Compound Represented by Formula
(1)]
[0148] <Aliphatic Tertiary Amine Having One Substituent
Consisting of Three or More Carbons Having an Electron-Withdrawing
Group at .alpha.-Carbon and/or .beta.-Carbon of an Amine Starting
from N>
D1-1: N,N-Diisopropylaminoethyl Methacrylate
##STR00016##
[0149] D1-2:
3-isopropyl-2-methyl-7-oxo-6,11-dioxo-3,8-diazatridecane-13-yl
Methacrylate
##STR00017##
[0150] D1-3: 2-(((2-(dibutylamino) ethoxy) carbonyl) amino) ethyl
Methacrylate
##STR00018##
[0151] D1-4: 1-[(3,3-diphenylpropyl) (methyl)
amino]-2-methyl-2-propanol
##STR00019##
[0152] D1-5: (1R,2S)-1-phenyl-2-(1-pyrrolidinyl) propane-1-ol
##STR00020##
[0153] D1-6: (1S,2R)-2-(dibutylamino)-1-phenyl-1-propanol
##STR00021##
[0154] <Aliphatic Tertiary Amine Having Two or More Substituents
Consisting of Three or More Carbons Having an Electron-Withdrawing
Group at .alpha.-Carbon and/or .beta.-Carbon of an Amine Starting
from N>
D2-1: 1-benzhydryl azetidine-3-carboxylic Acid
##STR00022##
[0155] D2-2: Triisopanol Amine
##STR00023##
[0156] D2-3: N,N,N',N'-tetrakis (2-hydroxypropyl)
ethylenediamine
##STR00024##
[0157] D2-4: Diethylbenzylimino Diacetate
##STR00025##
[0158] D2-5:
11-benzyl-7,15-dioxo-3,8,14,19-tetraoxo-6,11,16-triazahenicosan-1,21-diyl-
bis (2-methacrylate)
##STR00026##
[0159] <Aliphatic Tertiary Amine Having Two or More Aryls which
May have a Substituent as a Substituent of N>
D3-1: 2-benzyl-6-oxo-1-phenyl-5,10-dioxo-2,7-diazadodecane-12-yl
Methacrylate
##STR00027##
[0160] D3-2: N,N-Dibenzylglycine Ethyl Ester
##STR00028##
[0161] D3-3: Dibenzylaminoethyl Methacrylate
##STR00029##
[0162] D3-4: (S)-(+)-2-(dibenzylamino)-3-phenyl-1-propanol
##STR00030##
[0163] D3-5: Dibenzylaminoethanol
##STR00031##
[0164] D3-6: Tribenzylamine
##STR00032##
[0165] D3-7: 2-(((2-(dibenzylamino) ethoxy) carbonyl)
amino)-2-methylpropane-1,3-diyl Dimethacrylate
##STR00033##
[0166] D3-8: 3-(N, N-dibenzylamino) propyltriethoxysilane
##STR00034##
[0167]<Other Aliphatic Tertiary Amine>
<<Aliphatic Tertiary Amine Compound Having No Primary
Hydroxyl Group>>
[0168] DMAEMA: N,N-dimethylamino ethylmethacrylate DEAEMA:
N,N-diethylamino ethylmethacrylate
<<Aliphatic Tertiary Amine Compound Having Two Primary
Hydroxyl Groups>>
[0169] MDEOA: methyl diethanolamine
<<Aliphatic Tertiary Amine Compound Having Three Primary
Hydroxyl Groups>>
[0170] TEA: triethanolamine
<Aromatic Tertiary Amine Compound>
[0171] DMBE: N,N-dimethylaminobenzoate ethyl
<Organic Metal Compound>
[0172] SnL: dioctyl-tin-dilaurate
[(F) Volatile Organic Solvent]
[0173] Ac: acetone EtOH: ethanol
[(G) Water]
[0174] DW: ion-exchanged water
[(E) Filler]
[0175] The preparing method of each filler used for preparing the
dental adhesive composition and/or the dental photocurable
composition is shown below.
(Filler E1)
[0176] A silane coupling treatment solution prepared by stirring
50.0 g of water, 35.0 g of ethanol, and 3.0 g of
3-methacryloyloxypropyl trimethoxysilane as a silane coupling
material at room temperature for 2 hours was added to 100.0 g of
fluoroaluminosilicate glass (average particle diameter: 0.9 .mu.m)
and stirred for 30 minutes. Thereafter, a heat treatment was
performed at 100.degree. C. for 15 hours to obtain a filler E1.
(Filler E2)
[0177] A silane coupling treatment solution prepared by stirring
50.0 g of water, 35.0 g of ethanol, and 5.0 g of
3-methacryloyloxypropyl trimethoxysilane as a silane coupling
material at room temperature for 2 hours was added to 100.0 g of
the zirconium silicate filler (average particle diameter: 0.8
.mu.m, zirconia: 85 wt. %, silica: 15 wt. %) and stirred for 30
minutes. Thereafter, a heat treatment was performed at 100.degree.
C. for 15 hours to obtain a filler E2.
(Filler E3)
[0178] A silane coupling treatment solution prepared by stirring 5
g of water, 100 g of ethanol, and 10.0 g of di3-(N,N-dibenzylamino)
propyltriethoxysilane as a silane coupling material at room
temperature for 2 hours was added to 100.0 g of Aerosil OX-50
(manufactured by Evonik Industries AG) and stirred for 24 minutes.
Thereafter, a heat treatment was performed at 100.degree. C. for 15
hours to obtain a filler E3.
(Filler E4)
[0179] Aerosil R7200 (manufactured by Evonik Industries AG)
(Filler E5)
[0180] Aerosil OX-50 (manufactured by Evonik Industries AG)
[Chemical Polymerization Initiator]
[0181] CHP: cumene hydroperoxide tBHP: tert-butyl hydroperoxide
TPE: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate
[Chemical Polymerization Accelerator]
[0182] PTU: (2-pyridyl) thiourea DMPT: N,N-dimethyl-p-toluidine
DEPT: N,N-dihydroxyethyl-p-toluidine GLA: copper gluconate VOA:
vanadyl acetylacetonate TMBA: trimethyl barbituric acid
[UV Absorber]
[0183] BT: 2-(2-hydroxy-5-methylphenyl) benzotriazole
[Polymerization Inhibitor]
[0184] BHT: 2,6-di-t-butyl-4-methylphenol MeHQ: p-methoxyphenol
[Fluorescent Agent]
[0185] FA: 2.5-dihydroxyterephthalate diethyl
<Preparing Method of One Pack Type Dental Adhesive
Composition>
[0186] Components shown in Table 1 to 2 were put into a wide
mouthed plastic container and mixed by using a mix rotor VMRC-5
under light-shielding condition at 100 rpm for 48 hours to prepare
a dental adhesive composition. The prepared dental adhesive
composition was filled into a light-shielding bottle to prepare a
dental adhesive composition of each composition P and each
composition CP. In the Tables 1 to 2, the content (parts by mass)
of each component is indicated by the numerical value in
parentheses after the abbreviation of each component.
TABLE-US-00001 TABLE 1 (A) Polymerizable monomer
Photopolymerization (A-1) polymerizable initiator monomer having
(B) Photo Polymerizable monomer other than (A-1) an acidic group
sensitizer Example P1 Composition P1 -- MDP(5) -- Example P2
Composition P2 -- MDP(0.1) -- Example P3 Composition P3 -- MDP(20)
-- Example P4 Composition P4 -- MDP(10), META(10) -- Example P5
Composition P5 -- MDP(0.1) -- Example P6 Composition P6
Bis-GMA(35), TEGDMA(15) MDP(0.1) -- Example P7 Composition P7
Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.2) Example P8 Composition P8
Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.5) Example P9 Composition P9
Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.5) Example P10 Composition P10
Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.5) Example P11 Composition P11
Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.5) Example P12 Composition P12
Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(2) CQ(0.5) Example
P13 Composition P13 Bis-GMA(35), TEGDMA(15) MDP(2) CQ(0.5) Example
P14 Composition P14 Bis-GMA(35), TEGDMA(13), MPTMS(2) MDP(2)
CQ(0.5) Example P15 Composition P15 Bis-GMA(35), TEGDMA(12),
MPTMS(2), MDDT(1) MDP(2) CQ(0.5) Example P16 Composition P16
MPTMS(2), MDDT(1) MDP(3), META(9) CQ(0.5) Example P17 Composition
P17 MPTMS(2), MDDT(1) MDP(3), MET(9) CQ(0.5) Example P18
Composition P18 -- MDP(4) -- Example P19 Composition P19 -- MDP(4)
-- Example P20 Composition P20 -- MDP(4) -- Example P21 Composition
P21 MPTMS(2), MDDT(1) MDP(4) CQ(0.5) Example P22 Composition P22
Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(4) CQ(0.5) Example
P23 Composition P23 -- MDP(4) -- Example P24 Composition P24 --
MDP(4) -- Example P25 Composition P25 -- MDP(4) -- Example P26
Composition P26 MPTMS(2), MDDT(1) MDP(1) CQ(0.5) Example P27
Composition P27 Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(10)
CQ(0.5) Example P28 Composition P28 -- MDP(4) -- Example P29
Composition P29 -- MDP(4) -- Example P30 Composition P30 -- MDP(4)
-- Chemical Photopolymerization polymerization initiator initiator
or (D) Photo (F) Volatile Chemical (C) Photoacid polymerization
organic polymerization generator accelerator (E) Filler solvent (G)
Water accelerator Others Example P1 -- D3-1(1) -- EtOH(95) -- -- --
Example P2 -- D3-2(0.1) -- AC(99.9) -- -- -- Example P3 --
D3-3(0.1) -- Ac(80) -- -- BHT(0.1) Example P4 -- D3-4(2.0) --
EtOH(80) -- -- BHT(0.1) Example P5 -- D3-4(2.0) -- AC(99.9) -- --
-- Example P6 -- D3-1(0.1) -- Ac(49.9) -- -- BHT(0.1) Example P7
C1(0.5) D3-1(1) -- AC(48) -- -- BHT(0.1) Example P8 -- D3-1(1) --
AC(48) -- DMPT(1.0) BHT(0.1) Example P9 C1(0.5) D3-1(1) -- AC(48)
-- GLA(0.2) BHT(0.1) Example P10 C2(0.5) D3-1(1) -- AC(48) --
VOA(0.2) MeHQ(0.1) Example P11 C2(0.5) D3-1(1), DMBE(0.3) -- AC(48)
-- VOA(0.2) MeHQ(0.1) Example P12 C6(0.5) D3-1(1), DMBE(0.3) --
EtOH(28) DW(20) -- BHT(0.1) Example P13 C3(0.5) D3-1(1) -- EtOH(28)
DW(20) -- BHT(0.1) Example P14 C4(0.5) D3-1(1) -- EtOH(28) DW(20)
-- BHT(0.1) Example P15 C6(0.5) D3-1(1) -- EtOH(28) DW(20) --
BHT(0.1) Example P16 C6(0.5) D3-1(1) -- EtOH(60) DW(25) VOA(0.05)
MeHQ(0.1) Example P17 C6(0.5) D3-1(1) -- EtOH(40) DW(45) GLA(0.2)
BHT(0.1) Example P18 -- D1-1(1) -- EtOH(96) -- -- -- Example P19 --
D1-2(0.1) -- AC(96) -- -- -- Example P20 -- D1-3(20) -- EtOH(96) --
-- -- Example P21 C6(0.5) D1-4(2) -- EtOH(40) DW(53) -- BHT(0.1)
Example P22 C7(0.5) D1-5(2) -- Ac(26) DW(20) -- BHT(0.1) Example
P23 -- D2-1(1) -- EtOH(96) -- -- -- Example P24 -- D2-2(0.1) --
Ac(96) -- -- -- Example P25 -- D2-3(20) -- EtOH(96) -- -- --
Example P26 C6(0.5) D2-4(2) -- EtOH(40) DW(56) -- -- Example P27
C4(0.5) D2-5(2) -- Ac(20) DW(20) -- BHT(0.1) Example P28 -- D3-1(1)
-- EtOH(96) -- -- -- Example P29 -- D3-2(0.1) -- Ac(96) -- -- --
Example P30 -- D3-3(20) -- EtOH(96) -- -- --
TABLE-US-00002 TABLE 2 (A) Polymerizable monomer (A-1)
polymerizable Photopolymerization initiator monomer having (B)
Photo Polymerizable monomer other than (A-1) an acidic group
sensitizer Example P31 Composition P31 MPTMS(2), MDDT(1) MDP(4)
CQ(0.5) Example P32 Composition P32 Bis-GMA(35), TEGDMA(12),
MPTMS(2), MDDT(1) MDP(4) CQ(0.5) Example P33 Composition P33
Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(2), META(9) CQ(0.3)
Example P34 Composition P34 Bis-GMA(25), TEGDMA(8), MPTMS(2),
MDDT(1) MDP(2), MET(8) CQ(0.3) Example P35 Composition P35
Bis-GMA(25), TEGDMA(8), MPTMS(2), MDDT(1) MHPA(2), MET(8) CQ(0.3)
Example P36 Composition P36 Bis-GMA(25), TEGDMA(8), MPTMS(2),
MDDT(1) MHPA(2), META(8) CQ(0.3) Example P37 Composition P37
Bis-GMA(25), TEGDMA(8), MPTMS(2), MDDT(1) MDP(2), MET(8) CQ(0.3)
Example P38 Composition P38 Bis-GMA(25), TEGDMA(8), MPTMS(2),
MDDT(1) MDP(2), MET(8) CQ(0.3) Example P39 Composition P39
UDMA(35), TEGDMA(8), MPTMS(2), MDDT(1) MHPA(2), META(8) CQ(0.3)
Example P40 Composition P40 UDMA(35), GDMA(12), MPTMS(2), MDDT(1)
MHPA(2), META(8) CQ(0.3) Example P41 Composition P41 -- MDP(4) --
Example P42 Composition P42 Bis-GMA(35), TEGDMA(12), MPTMS(2),
MDDT(1) MDP(2) CQ(0.5) Example P43 Composition P43 Bis-GMA(35),
TEGDMA(12), MPTMS(2), MDDT(1) MDP(2) CQ(0.5) Example P44
Composition P44 Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(2)
CQ(0.5) Example P45 Composition P45 Bis-GMA(35), TEGDMA(12),
MPTMS(2), MDDT(1) MDP(2) CQ(0.5) Example P46 Composition P46
Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1) MDP(2) CQ(0.5) Example
P47 Composition P47 Bis-GMA(35), TEGDMA(12), MPTMS(2), MDDT(1)
MDP(2) BAPO(0.5) Comparative Composition CP1 UDMA(35), GDMA(12),
MPTMS(2), MDDT(1) MHPA(2), META(8) CQ(0.3) Example CP1 Comparative
Composition CP2 -- MDP(5) -- Example CP2 Comparative Composition
CP3 -- -- Example CP3 Comparative Composition CP4 -- MDP(5) --
Example CP4 Comparative Composition CP5 -- MDP(5) -- Example CP5
Comparative Composition CP6 -- MDP(5) -- Example CP6 Comparative
Composition CP7 -- MDP(5) -- Example CP7 Comparative Composition
CP8 Bis-GMA(36), TEGDMA(15) MDP(2) CQ(0.5) Example CP8 Comparative
Composition CP9 Bis-GMA(36), TEGDMA(15) MDP(2) CQ(0.5) Example CP9
Comparative Composition CP10 Bis-GMA(36), TEGDMA(15) MDP(2) CQ(0.5)
Example CP10 Comparative Composition CP11 Bis-GMA(36), TEGDMA(15)
MDP(2) CQ(0.5) Example CP11 Comparative Composition CP12
Bis-GMA(36), TEGDMA(15) MDP(2) CQ(0.5) Example CP12 Comparative
Composition CP13 Bis-GMA(36), TEGDMA(15) MDP(2) CQ(0.5) Example CP
13 Chemical polymerization Photopolymerization initiator initiator
or (D) Photo (F) Volatile Chemical (C) Photoacid polymerization
organic polymerization generator accelerator (E) Filler solvent (G)
Water accelerator Others Example P31 C1(0.5) D3-4(2) -- EtOH(40)
DW(53) -- BHT(0.1) Example P32 C2(0.5) D3-5(2) E5(10) Ac(26) DW(20)
-- BHT(0.1) Example P33 C2(1) D3-6(2) -- EtOH(14) DW(25) --
BHT(0.1) Example P34 C6(3) D3-6(2) E4(60) EtOH(29) DW(25) --
BHT(0.1) Example P35 C6(1) D3-6(2) -- EtOH(29) DW(25) -- BHT(0.1)
Example P36 C6(6) D3-6(2) E4(10) EtOH(29) DW(25) -- BHT(0.1)
Example P37 C6(1) D3-6(2) -- Ac(29) DW(25) VOA(0.01) MeHQ(0.1)
Example P38 C6(1) D3-6(2) -- Ac(29) DW(25) GLA(0.1) BHT(0.1)
Example P39 C6(1) D3-6(2) -- EtOH(20) DW(24) -- BHT(0.1) Example
P40 C6(1) D3-6(2) -- EtOH(20) DW(20) -- BHT(0.1) Example P41 --
D1-6(1) -- Ac(95) -- -- Example P42 C8(0.5) D3-6(2) -- EtOH(28)
DW(20) -- BHT(0.1) Example P43 C9(0.5) D3-6(2) -- EtOH(28) DW(20)
-- BHT(0.1) Example P44 C10(0.5) D3-6(2) -- EtOH(28) DW(20) --
BHT(0.1) Example P45 C11(0.5) D3-6(2) -- EtOH(28) DW(20) --
BHT(0.1) Example P46 C12(0.5) D3-6(2) -- EtOH(28) DW(20) --
BHT(0.1) Example P47 C6(0.5) D3-1(1) -- EtOH(28) DW(20) -- BHT(0.1)
Comparative C6(1) -- E3(10) EtOH(20) DW(20) -- BHT(0.1) Example CPI
Comparative -- -- -- Ac(95) -- -- Example CP2 Comparative --
D3-2(2) -- Ac(100) -- -- Example CP3 Comparative -- DMBE(0.5) --
Ac(95) -- -- Example CP4 Comparative -- DMAEMA(2) -- Ac(95) -- --
Example CPS Comparative -- TEA(1) -- Ac(95) -- -- Example CP6
Comparative -- MDEOA(0.6) -- Ac(95) -- -- Example CP7 Comparative
-- DMBE(0.5) -- Ac(48) -- -- Example CP8 Comparative -- DMAEMA(2)
-- Ac(48) -- -- Example CP9 Comparative 01(0.6) DMAEMA(2) --
EtOH(48) -- BHT(0.1) Example CP 10 Comparative 02(1) DMAEMA(2) --
EtOH(48) -- BHT(0.1) Example CP11 Comparative 03(2) TEA(1) --
EtOH(48) -- BHT(0.1) Example CP 12 Comparative C4(1) MDEOA(0.5) --
EtOH(48) -- BHT(0.1) Example CP 13
<Preparing Method of Two Packs Type Dental Adhesive
Composition>
[0187] Components of first pack shown in Tables 3 to 5 were put
into a wide mouthed plastic container and mixed by using a mix
rotor VMRC-5 under light-shielding condition at 100 rpm for 48
hours. Similarly, components of second pack were put into a wide
mouthed plastic container and mixed by using a mix rotor VMRC-5
under light-shielding condition at 100 rpm for 48 hours. The first
pack and the second pack were filled in different light-shielding
bottles to prepare a dental adhesive composition of each
composition Q and each composition CQ. Each composition Q and each
composition CQ were used after mixing in a weight ratio of 0.8 to
1.2:1.0 before use. In the Tables 3 to 5, the content (parts by
mass) of each component is indicated by the numerical value in
parentheses after the abbreviation of each component.
TABLE-US-00003 TABLE 3 (A) Polymerizable monomer (A-1)
polymerizable monomer having Polymerizable monomer other than (A-1)
an acidic group Example Q1 Composition Q1 First pack -- MDP(5)
Second pack MPTMS(2), MDDT(1) Example Q2 Composition Q2 First pack
-- MDP(0.1) Second pack MPTMS(2), MDDT(1) Example Q3 Composition Q3
First pack -- MDP(20) Second pack MPTMS(2), MDDT(1) Example Q4
Composition Q4 First pack -- MDP(10), META(10) Second pack
MPTMS(2), MDDT(1) Example Q5 Composition Q5 First pack -- MDP(0.1)
Second pack MPTMS(2), MDDT(1) Example Q6 Composition Q6 First pack
Bis-GMA(15) TEGDMA(15) MDP(0.1) Second pack MPTMS(2), MDDT(1)
Example Q7 Composition Q7 First pack Bis-GMA(15), TEGDMA(15) MDP(2)
Second pack MPTMS(2), MDDT(1) Example Q8 Composition Q8 First pack
Bis-GMA(15) TEGDMA(15) MDP(2) Second pack MPTMS(2), MDDT(1) Example
Q9 Composition Q9 First pack Bis-GMA(15), TEGDMA(15) MDP(2) Second
pack MPTMS(2), MDDT(1) Example Q10 Composition Q10 First pack
Bis-GMA(15), TEGDMA(15) MDP(2) Second pack MPTMS(2), MDDT(1)
Example Q11 Composition Q11 First pack Bis-GMA(15), TEGDMA(15)
MDP(2) Second pack -- Example Q12 Composition Q12 First pack
Bis-GMA(16), TEGDMA(12), MPTMS(2), MDDT(1) MDP(1) Second pack --
Example Q13 Composition Q13 First pack Bis-GMA(15), TEGDMA(15)
MDP(2) Second pack -- Example Q14 Composition Q14 First pack
Bis-GMA(15), TEGDMA(13), MPTMS(2) MDP(2) Second pack -- Example Q15
Composition Q15 First pack Bis-GMA(15), TEGDMA(12), MPTMS(2),
MDDT(1) MDP(2) Second pack -- Example Q16 Composition Q16 First
pack Bis-GMA(15), TEGDMA(12), MPTMS(2), MDDT(1) MDP(3), META(9)
Second pack -- Photopolymerization initiator (D) Photo (B) Photo
(C) Photoacid polymerization sensitizer generator accelerator (E)
Filler Example Q1 -- -- D3-6(1) -- -- -- Example Q2 -- -- D3-2(0.1)
-- -- -- Example Q3 -- -- D3-3(0.1) -- -- -- Example Q4 -- -- D
3-4(20) -- -- -- Example Q5 -- -- D 3-6(20) -- -- -- Example Q6 --
-- D3-1(0.1) -- -- -- Example Q7 CQ(0.2) -- D3-1(1) C1(0.5) --
Example Q8 CQ(0.5) -- D3-1(1) -- C1(0.5) -- Example Q9 CQ(0.5)
C1(0.5) D3-1(1) -- -- -- Example Q10 CQ(0.5) C2(0.5) D3-1(1) -- --
-- Example Q11 -- -- D3-1(1), DMBE(0.3) CQ(0.5) C2(0.5) -- Example
Q12 CQ(0.5) C5(0.5) D3-1(1), DMBE(0.3) -- -- -- Example Q13 CQ(0.5)
C3(0.5) D3-1(1) -- -- -- Example Q14 CQ(0.5) C4(0.5) D3-1(5) -- --
-- Example Q15 CQ(0.5) C5(0.5) D3-1(10) -- -- -- Example Q16
CQ(0.5) -- D3-1(20) -- C5(5) -- Chemical polymerization initiator
or (F) Volatile Chemical organic polymerization solvent (G) Water
accelerator Others Example Q1 EtOH(45) EtOH(20) DW(27) Example Q2
Ac(49.9) EtOH(20) DW(27) Example Q3 Ac(30) EtOH(20) DW(27) Example
Q4 EtOH(30) EtOH(20) DW(27) Example Q5 Ac(49.9) EtOH(20) DW(27)
Example Q6 Ac(19.9) BHT(0.1) EtOH(20) DW(27) Example Q7 Ac(18)
BHT(0.1) EtOH(20) DW(27) BHT(0.1) Example Q8 Ac(18) DMPT(1.0)
BHT(0.1) EtOH(20) DW(27) tBHP(1.0) BHT(0.1) Example Q9 Ac(18)
GLA(0.2) BHT(0.1) EtOH(20) DW(27) tBHP(1.0) BHT(0.1) Example Q10
Ac(18) VOA(0.2) MeHQ(0.1) EtOH(20) DW(27) tBHP(1.0) BHT(0.1)
Example Q11 Ac(18) VOA(0.2) MeHQ(0.1) EtOH(30) DW(20) tBHP(1.0)
Example Q12 EtOH(18) VOA(0.2) MeHQ(0.1) Ac(50) tBHP(1.0) Example
Q13 EtOH(8) DW(10) TPE(1.0) BHT(0.1) Ac(50) VOA(0.2) Example Q14
EtOH(8) DW(10) VOA(0.01) MeHQ(0.1) Ac(50) TPE(1.0) Example Q15
EtOH(8) DW(10) TPE(1.0) BHT(0.1) Ac(50) VOA(0.05), TMBA(1) Example
Q16 EtOH(10) DW(25) VOA(0.05) MeHQ(0.1) Ac(50) tBHP(2)
TABLE-US-00004 TABLE 4 (A) Polymerizable monomer Polymerizable
monomer other than (A-1) Example Q17 Composition Q17 First pack
MPTMS(2), MDDT(1) Second pack -- Example Q18 Composition Q18 First
pack -- Second pack -- Example Q19 Composition Q19 First pack --
Second pack MPTMS(2), MDDT(1) Example Q20 Composition Q20 First
pack -- Second pack MPTMS(2), MDDT(1) Example Q21 Composition Q21
First pack MPTMS(2), MDDT(1) Second pack -- Example Q22 Composition
Q22 First pack Bis-GMA(15), TEGDMA(12), MPTMS(2), MDDT(1) Second
pack -- Example Q23 Composition Q23 First pack Bis-GMA(15),
TEGDMA(12), MPTMS(2), MDDT(1) Second pack -- Example Q24
Composition Q24 First pack -- Second pack -- Example Q25
Composition Q25 First pack -- Second pack -- Example Q26
Composition Q26 First pack MPTMS(2), MDDT(1) Second pack -- Example
Q27 Composition Q27 First pack Bis-GMA(15), TEGDMA(12), MPTMS(2),
MDDT(1) Second pack -- Example Q28 Composition Q28 First pack --
Second pack Bis-GMA(15), TEGDMA(12), MPTMS(2), MDDT(1) Example Q29
Composition Q29 First pack -- Second pack Bis-GMA(15), TEGDMA(12),
MPTMS(2), MDDT(1) Example Q30 Composition Q30 First pack -- Second
pack Bis-GMA(15), TEGDMA(12), MPTMS(2), MDDT(1) Example Q31
Composition Q31 First pack MPTMS(2), MDDT(1) Second pack -- Example
Q32 Composition Q32 First pack Bis-GMA(15), TEGDMA(12), MPTMS(2),
MDDT(1) Second oack -- (A) Polymerizable monomer
Photopolymerization initiator (A-1) polymerizable (D) Photo monomer
having (B) Photo (C) Photoacid polymerization an acidic group
sensitizer generator accelerator Example Q17 MDP(3), MET(9) CQ(0.5)
C6(0.5) D3-1(1) -- -- -- Example Q18 MDP(4) -- -- D1-1(1) -- -- --
Example Q19 MDP(4) -- -- D1-2(0.1) CQ(0.5) C7(0.5) -- Example Q20
MDP(4) -- -- D1-3(20) CQ(0.5) C7(0.5) -- Example Q21 MDP(4) CQ(0.5)
C6(0.5) D1-4(2) -- -- -- Example Q22 MDP(4) -- -- D1-5(2) CQ(0.5)
C7(0.5) -- Example Q23 MDP(4) -- -- D2-1(1) -- -- -- Example Q24
MDP(4) -- -- D2-2(0.1) CQ(0.2) C1(0.5) -- Example Q25 MDP(4) -- --
D2-3(20) CQ(0.2) C1(0.5) -- Example Q26 MDP(4) CQ(0.5) C5(0.5)
D2-4(2) -- -- -- Example Q27 MDP(4) CQ(0.5) C4(0.5) D2-5(2) -- --
-- Example Q28 MDP(4) -- -- D3-1(1) CQ(0.5) C5(0.5) -- Example Q29
MDP(4) -- -- D3-2(0.1) CQ(0.5) C5(0.5) -- Example Q30 MDP(4) -- --
D3-3(20) CQ(0.5) C5(0.5) -- Example Q31 MDP(4) CQ(0.5) C1(0.5)
D3-4(2) -- -- -- Example Q32 MDP(4) CQ(0.5) C2(0.5) D3-5(2) -- --
-- Chemical polymerization initiator or (F) Volatile Chemical
organic polymerization (E) Filler solvent (G) Water accelerator
Others Example Q17 EtOH(20) DW(15) GLA(0.2) BHT(0.1) Ac(50) tBHP(2)
Example Q18 EtOH(46) BHT(0.1) E1(20) Ac(25) DW(25) Example Q19
Ac(46) BHT(0.1) EtOH(20) DW(27) Example Q20 EtOH(46) BHT(0.1)
EtOH(20) DW(27) BHT(0.1) Example Q21 EtOH(20) DW(23) BHT(0.1)
Ac(50) Example Q22 EtOH(10) DW(6) MeHQ(0.1) EtOH(50) Example Q23
EtOH(46) MeHQ(0.1) E1(20) EtOH(20) DW(30) Example Q24 Ac(46)
MeHQ(0.1) EtOH(50) Example Q25 EtOH(46) BHT(0.1) EtOH(50) Example
Q26 EtOH(20) DW(23) BHT(0.1) E1(20) Ac(50) Example Q27 EtOH(8)
DW(8) MeHQ(0.1) Ac(50) Example Q28 EtOH(46) BHT(0.1) E1(20)
EtOH(10) DW(10) MeHQ(0.1) Example Q29 Ac(6) DW(40) BHT(0.1)
EtOH(10) DW(10) BHT(0.1) Example Q30 EtOH(46) BHT(0.1) EtOH(10)
DW(10) BHT(0.1) Example Q31 EtOH(20) DW(23) BHT(0.1) E1(10)
EtOH(20) DW(30) Example Q32 E1(10) Ac(8) DW(8) MeHQ(0.1) EtOH(20)
DW(30)
TABLE-US-00005 TABLE 5 (A) Polymerizable monomer Polymerizable
monomer other than (A-1) Example Q33 Composition Q33 First pack
Bis-GMA(5), TEGDMA(12), MPTMS(2), MDDT(1) Second pack -- Example
Q34 Composition Q34 First pack Bis-GMA(10), TEGDMA(8) Second pack
MPTMS(2), MDDT(1) Example Q35 Composition Q35 First pack
Bis-GMA(10), TEGDMA(8), MPTMS(2), MDDT(1) Second pack MPTMS(2),
MDDT(1) Example Q36 Composition Q36 First pack Bis-GMA(10),
TEGDMA(8), MPTMS(2), MDDT(1) Second pack MPTMS(5), MDDT(0.1)
Example Q37 Composition Q37 First pack Bis-GMA(10), TEGDMA(8),
MPTMS(2), MDDT(1) Second pack MPTMS(3), MDDT(0.1) Example Q38
Composition Q38 First pack Bis-GMA(10), TEGDMA(8), MPTMS(2),
MDDT(1) Second pack -- Example Q39 Composition Q39 First pack
UDMA(15), TEGDMA(8), MPTMS(2), MDDT(1) Second pack -- Example Q40
Composition Q40 First pack UDMA(11), GDMA(12), MPTMS(2), MDDT(1)
Second pack -- Example Q41 Composition Q41 First pack Bis-GMA(11),
TEGDMA(11) Second pack MPTMS(2), MDDT(1) Example Q42 Composition
Q42 First pack Bis-GMA(11), TEGDMA(6) Second pack MPTMS(2), MDDT(1)
Comparative Composition CQ1 First pack -- Example CQ1 Second pack
MPTMS(2), MDDT(1) Comparative Composition CQ2 First pack -- Example
CQ2 Second pack MPTMS(2), MDDT(1) Comparative Composition CQ3 First
pack Bis-GMA(15), TEGDMA(15) Example CQ3 Second pack MPTMS(2),
MDDT(1) Comparative Composition CQ4 First pack Bis-GMA(10),
TEGDMA(8), MPTMS(2), MDDT(1) Example CQ4 Second pack MPTMS(2),
MDDT(1) (A) Polymerizable monomer Photopolymerization initiator
(A-1) polymerizable (D) Photo monomer having (B) Photo (C)
Photoacid polymerization an acidic group sensitizer generator
accelerator Example Q33 MDP(2), META(9) CQ(0.3) C2(1) D3-6(2) -- --
-- Example Q34 MDP(3), MET(10) -- -- D3-6(2) CQ(0.3) C6(1) --
Example Q35 MHPA(2), MET(8) -- -- D3-7(2) CQ(0.3) C6(1) -- Example
Q36 MHPA(2), META(8) CQ(0.3) C6(1) D3-8(2) -- -- -- Example Q37
MDP(2), MET(8) -- -- D3-6(2) CQ(0.3) C6(1) -- Example Q38 MDP(2),
MET(8) CQ(0.3) C6(1) D3-6(2) -- -- D3-5(2) Example Q39 MHPA(2),
META(8) CQ(0.3) C6(1) D3-6(2) -- -- -- Example Q40 MHPA(2), META(8)
CQ(0.3) C6(1) D3-6(2) -- -- -- Example Q41 MDP(10) CQ(0.2) --
D3-1(1) -- C1(0.5) -- Example Q42 MDP(0.01) CQ(0.2) -- D3-1(1) --
C1(0.5) -- Comparative MDP(5) -- -- -- Example CQ1 -- -- --
Comparative -- -- D3-6(1) Example CQ2 -- -- -- Comparative MDP(2)
CQ(0.2) -- -- Example CQ3 -- -- DMBE(1) Comparative MHPA(2), MET(8)
-- -- -- Example CQ4 CQ(0.3) C6(1) -- Chemical polym erization
initiator or (F) Volatile Chemical organic polym erization (E)
Filler solvent (G) Water accelerator Others Example Q33 EtOH(10)
DW(9) MeHQ(0.1) E1(10) EtOH(20) DW(30) Example Q34 E2(50) EtOH(10)
DW(9) MeHQ(0.1) EtOH(20) DW(27) BHT(0.1) Example Q35 EtOH(10) DW(9)
MeHQ(0.1) EtOH(20) DW(27) BHT(0.1) Example Q36 E2(10) EtOH(10)
DW(9) MeHQ(0.1) EtOH(20) DW(24.9) BHT(0.1) Example Q37 EtOH(10)
DW(9) VOA(0.05) MeHQ(0.1) EtOH(20) DW(26.9) tBHP(2) BHT(0.1)
Example Q38 EtOH(10) DW(9) GLA(0.1) BHT(0.1) EtOH(20) DW(30)
tBHP(2) Example Q39 EtOH(4) DW(10) GLA(0.1) BHT(0.1) EtOH(20)
DW(30) tBHP(2) Example Q40 EtOH(4) DW(10) GLA(0.1) BHT(0.1)
EtOH(20) DW(30) tBHP(2) Example Q41 Ac(18) BHT(0.1) EtOH(20) DW(27)
BHT(0.1) Example Q42 Ac(18) BHT(0.1) EtOH(20) DW(27) BHT(0.1)
Comparative EtOH(45) Example CQ1 EtOH(20) DW(27) Comparative
EtOH(50) BHT(0.1) Example CQ2 EtOH(20) DW(27) BHT(0.1) Comparative
Ac(18) Example CQ3 EtOH(20) DW(27) Comparative EtOH(10) DW(9)
VOA(0.05) Example CQ4 EtOH(20) DW(27) tBHP(2)
<Preparing Method of Dental Curable Composition>
[0188] All components shown in Tables 6 and 7 other than filler (E)
were mixed by using a mix rotor VMRC-5 under the condition of 100
rpm for 48 hours to prepare a binder resin. Then, the binder resin
and filler (E) were put into a rotation and revolution mixer
(ARV-300), mixed at 1400 rpm for 10 minutes, and then defoamed
under vacuum. The one pack type dental curable composition shown in
Table 6 was directly collected, and the two packs type dental
curable composition shown in Table 7 was filled in a double syringe
container manufactured by Mixpack Co., Ltd., to prepare a dental
curable composition of the compositions R1 to R7 and the
compositions S1 to S7. In the Tables 6 to 7, the content (parts by
mass) of each component is indicated by the numerical value in
parentheses after the abbreviation of each component.
TABLE-US-00006 TABLE 6 (D) Photo Others (B) Photo (C) Photoacid
polymerization Polymerization (A) Polymerizable monomer (E) Filler
sensitizer generator accelerator inhibitor Others Composition R1
Bis-GMA(60), TEGDMA(40) E1(250) CQ(0.3) C5(3) -- BHT(0.005)
FA(0.01) Composition R2 2.6E(80), TEGDMA(20) E2(250) CQ(0.2) C3(2)
-- MeHQ(0.005) -- Composition R3 Bis-GMA(60), TEGDMA(40) E1(250)
CQ(0.3) C4(0.2) MDEOA(0.5) MeHQ(0.005) FA(0.01) Composition R4
2.6E(80), TEGDMA(20) E2(250) CQ(0.2) C2(0.5) DEAEMA(1.5)
MeHQ(0.005) -- Composition R5 UDMA(70), TEGDMA(30) E1(250) CQ(0.1)
C3(2) D3-6(2) MeHQ(0.005) FA(0.01) Composition R6 Bis-GMA(60),
TEGDMA(40) E1(250) CQ(0.2) -- -- MeHQ(0.005) FA(0.01) Composition
R7 Bis-GMA(60), TEGDMA(40) E2(250) CQ(0.5) -- DMBE(0.5) MeHQ(0.005)
--
TABLE-US-00007 TABLE 7 Photopolymerization initiator (B) Photo (C)
Photoacid (A) Polymerizable monomer (E) Filler sensitizer generator
Composition S1 Paste 1 Bis-GMA(60), TEGDMA(40) E1(200) CQ(0.6) --
Paste 2 UDMA(70), TEGDMA(30) E1(200) -- C1(4) Composition S2 Paste
1 2.6E(80), TEGDMA(20) E2(200) CQ(0.4) -- Paste 2 Bis-GMA(60),
TEGDMA(40) E2(200) -- C2(2) Composition S3 Paste 1 UDMA(70),
TEGDMA(30) E1(200) CQ(0.2) C3(1) Paste 2 2.6E(80), TEGDMA(20)
E1(200) -- -- Composition S4 Paste 1 UDMA(70), TEGDMA(30) E2(200)
-- -- Paste 2 Bis-GMA(65), HEMA(25), MDP(10) E2(200) CQ(1) C4(2)
Composition S5 Paste 1 Bis-GMA(60), TEGDMA(20), MHPA(20) E1(200)
CQ(0.2) C5(0.5) Paste 2 Bis-GMA(60), TEGDMA(40) E1(200) -- --
Composition S6 Paste 1 2.6E(80), TEGDMA(20) E2(200) CQ(1.4) --
Paste 2 Bis-GMA(60), TEGDMA(40) E2(200) -- -- Composition S7 Paste
1 2.6E(80), TEGDMA(20) E2(200) CQ(0.2) -- Paste 2 Bis-GMA(60),
TEGDMA(40) E2(200) -- -- Chemical Photopolymerization
polymerization initiator initiator or (D) Photo Chemical Others
polymerization polymerization Polymerization accelerator
accelerator inhibitor Others Composition S1 Paste 1 -- PTU(1.0)
MeHQ(0.005) FA(0.01) Paste 2 -- CHP(1.5) BHT(0.1) -- Composition S2
Paste 1 -- PTU(1.0) MeHQ(0.005) -- Paste 2 MDEOA(0.5) CHP(1.5)
BHT(0.1) -- Composition S3 Paste 1 -- PTU(1), VOA(0.01) MeHQ(0.005)
FA(0.01) Paste 2 D3-6(2) CHP(1.5) BHT(0.1) -- Composition S4 Paste
1 DEAEMA(1.5) PTU(1), COA(0.1) MeHQ(0.005) -- Paste 2 -- CHP(1.5)
BHT(0.1) -- Composition S5 Paste 1 -- PTU(1), COA(0.1) MeHQ(0.005)
FA(0.01) Paste 2 -- CHP(1.5) BHT(0.1) -- Composition S6 Paste 1 --
PTU(2), VOA(0.01) MeHQ(0.005) -- Paste 2 -- CHP(3) BHT(0.1) --
Composition S7 Paste 1 -- PTU(2), VOA(0.01) MeHQ(0.005) -- Paste 2
-- CHP(3) BHT(0.1) --
[0189] The test method using each composition is as follows. For
the two packs type dental composition of the compositions S1 to S7,
a paste prepared by mixing the first paste and the second paste
with a mixing chip manufactured by Mixpack Co., Ltd. was used.
<Storage Stability of Dental Adhesive Composition (Acceleration
Test)>
[0190] In a dark room where the room temperature is 23.+-.2.degree.
C., 5 mL of each composition was collected with a plastic dropper
and filled in a black polypropylene bottle. Thereafter, the nozzle
and cap were attached in order, and it was confirmed that the
composition is not leak even if it is turned upside down. The
bottle filled with the composition was stored in an incubator at
50.degree. C. for 3 months, and it was confirmed that no
significant increase in viscosity or gelation occurred.
[Adhesive Strength to Enamel]
<Adhesion Test 1>
[0191] A test specimen of an epoxy resin embedded bovine central
incisor was polished with water-resistant abrasive paper #600 to
carve out an enamel plane. Thereafter, a tape (thickness 20 .mu.m)
with a hole having a diameter of 4 mm was affixed to the adherend
surface to prescribe an adhesion area. The composition was applied
into the tape with the hole and immediately air dried. For the two
packs type dental adhesive composition, the same weight were
weighed before application, sufficiently mixed, and thereafter
applied and then immediately air-dried. Light irradiation was
performed for 5 seconds with the dental polymerization LED light
irradiator (PEN Bright, SHOFU INC.). Aplastic mold with a hole
having 2 mm of the height and 4 mm of diameter was overlaid the
tape with the hole, and the dental composite resin (BEAUTIFIL Flow
Plus A3: SHOFU INC.) or the dental curable composition shown in
Table 3 was filled. Thereafter, the light was irradiated for 10
seconds by the dental polymerization LED light irradiator (PEN
Bright, SHOFU INC.). After immersing in water at 37.degree. C. for
24 hours, immersing both in cold water phase at 4.degree. C. for 60
seconds and in high temperature phase at 60.degree. C. for 60
seconds was repeated 5000 times by using a thermal shock tester
(manufactured by THOMAS KAGAKU Co., Ltd). The specimen was taken
out and an Instron universal tester (manufactured by Instron) was
used to measure the shear adhesive strength at a crosshead speed of
1 mm/min. Evaluation criteria were as follows.
Particularly good: adhesive strength was 20 MPa or more. Good:
adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[0192] In the test in which the dental curable composition of the
compositions R1 to R7 were combined with, immersing both in cold
water phase at 4.degree. C. for 60 seconds and in high temperature
phase at 60.degree. C. for 60 seconds was repeated 20000 times by
using a thermal shock tester (manufactured by THOMAS KAGAKU Co.,
Ltd). The specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the adhesive strength
at a crosshead speed of 1 mm/min. Evaluation criteria were as
follows.
Extremely good: adhesive strength was 28 MPa or more. Particularly
good: adhesive strength was 20 MPa or more and less than 28 MPa.
Good: adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
<Adhesion Test 2>
[0193] A test specimen of an epoxy resin embedded bovine central
incisor was polished with water-resistant abrasive paper #600 to
carve out an enamel plane. Thereafter, a tape (thickness 20 .mu.m)
with a hole having a diameter of 4 mm was affixed to the adherend
surface to prescribe an adhesion area. The composition was applied
into the tape with the hole and immediately air dried. For the two
packs type dental adhesive composition, the same weight were
weighed before application, sufficiently mixed, and thereafter
applied and then immediately air-dried. The adherend surface of the
stainless rod (.phi.4.5 mm) was sandblasted (0.2 MPa, 1 second)
with alumina (50 .mu.m), then was washed with water and dried, and
applied with a metal adhesive primer (METAL LINK, SHOFU INC.). The
adherend surface of the stainless rod was applied with appropriate
amount of resin cement (Resicem, SHOFU INC.) or a kneaded material
of the dental curable composition shown in Table 4, and a tooth
substance and the stainless rod were bonded so as to fit in the
frame of the double-sided tape with a hole. A load of 200 N was
applied from the vertical direction of the stainless rod, and
excess cement was wiped off with a cloth. Thereafter, Light
irradiation was performed for 10 seconds with the dental
polymerization LED light irradiator (PEN Bright, SHOFU INC.). After
removing the load, the prepared adhesive test piece was immersed in
water at 37.degree. C. for 24 hours, immersing both in cold water
phase at 4.degree. C. for 60 seconds and in high temperature phase
at 60.degree. C. for 60 seconds was repeated 5000 times by using a
thermal shock tester (manufactured by THOMAS KAGAKU Co., Ltd). The
specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the shear adhesive
strength at a crosshead speed of 1 mm/min. Evaluation criteria were
as follows.
Particularly good: adhesive strength was 20 MPa or more. Good:
adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[0194] In the test in which the dental curable composition of the
compositions S1 to S7 were combined with, immersing both in cold
water phase at 4.degree. C. for 60 seconds and in high temperature
phase at 60.degree. C. for 60 seconds was repeated 20000 times by
using a thermal shock tester (manufactured by THOMAS KAGAKU Co.,
Ltd). The specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the adhesive strength
at a crosshead speed of 1 mm/min. Evaluation criteria were as
follows.
Extremely good: adhesive strength was 28 MPa or more. Particularly
good: adhesive strength was 20 MPa or more and less than 28 MPa.
Good: adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[0195] When the adhesive strength is low, the risk of detachment of
the filler used in filling and repairing and the prosthetic device,
marginal leakage and secondary caries and the like increases,
therefore the adhesive strength is preferably high.
[Adhesive Strength to Dentin]
<Adhesion Test 1>
[0196] A test specimen of an epoxy resin embedded bovine central
incisor was polished with water-resistant abrasive paper #600 to
carve out a dentin plane. Thereafter, a tape (thickness 20 .mu.m)
with a hole having a diameter of 4 mm was affixed to the adherend
surface to prescribe an adhesion area. The composition was applied
into the tape with the hole and immediately air dried. For the two
packs type dental adhesive composition, the same weight were
weighed before application, sufficiently mixed, and thereafter
applied and then immediately air-dried. Light irradiation was
performed for 5 seconds with the dental polymerization LED light
irradiator (PEN Bright, SHOFU INC.). A plastic mold with a hole
having 2 mm of the height and 4 mm of diameter was overlaid the
tape with the hole, and the dental composite resin (BEAUTIFIL Flow
Plus A3: SHOFU INC.) or the dental curable composition shown in
Table 3 was filled. Thereafter, the light was irradiated for 10
seconds by the dental polymerization LED light irradiator (PEN
Bright, SHOFU INC.). After immersing in water at 37.degree. C. for
24 hours, immersing both in cold water phase at 4.degree. C. for 60
seconds and in high temperature phase at 60.degree. C. for 60
seconds was repeated 5000 times by using a thermal shock tester
(manufactured by THOMAS KAGAKU Co., Ltd). The specimen was taken
out and an Instron universal tester (manufactured by Instron) was
used to measure the shear adhesive strength at a crosshead speed of
1 mm/min. Evaluation criteria were as follows.
Particularly good: adhesive strength was 12 MPa or more. Good:
adhesive strength was 8 MPa or more and less than 12 MPa.
Applicable: adhesive strength was 3 MPa or more and less than 8
MPa. Insufficient: adhesive strength was less than 3 MPa.
[0197] In the test in which the dental curable composition of the
compositions R.sub.1 to R.sub.7 were combined with, immersing both
in cold water phase at 4.degree. C. for 60 seconds and in high
temperature phase at 60.degree. C. for 60 seconds was repeated
20000 times by using a thermal shock tester (manufactured by THOMAS
KAGAKU Co., Ltd). The specimen was taken out and an Instron
universal tester (manufactured by Instron) was used to measure the
adhesive strength at a crosshead speed of 1 mm/min. Evaluation
criteria were as follows.
Extremely good: adhesive strength was 19 MPa or more. Particularly
good: adhesive strength was 12 MPa or more and less than 19 MPa.
Good: adhesive strength was 8 MPa or more and less than 12 MPa.
Applicable: adhesive strength was 3 MPa or more and less than 8
MPa. Insufficient: adhesive strength was less than 3 MPa.
<Adhesion Test 2>
[0198] A test specimen of an epoxy resin embedded bovine central
incisor was polished with water-resistant abrasive paper #600 to
carve out a dentin plane. Thereafter, a tape (thickness 20 .mu.m)
with a hole having a diameter of 4 mm was affixed to the adherend
surface to prescribe an adhesion area. The composition was applied
into the tape with the hole and immediately air dried. For the two
packs type dental adhesive composition, the same weight were
weighed before application, sufficiently mixed, and thereafter
applied and then immediately air-dried. The adherend surface of the
stainless rod (.phi.4.5 mm) was sandblasted (0.2 MPa, 1 second)
with alumina (50 .mu.m), then was washed with water and dried, and
applied with a metal adhesive primer (METAL LINK, SHOFU INC.). The
adherend surface of the stainless rod was applied with appropriate
amount of resin cement (Resicem, SHOFU INC.) or a kneaded material
of the dental curable composition shown in Table 4, and a tooth
substance and the stainless rod were bonded so as to fit in the
frame of the double-sided tape with a hole. A load of 200 N was
applied from the vertical direction of the stainless rod, and
excess cement was wiped off with a cloth. Thereafter, Light
irradiation was performed for 10 seconds with the dental
polymerization LED light irradiator (PEN Bright, SHOFU INC.). After
removing the load, the prepared adhesive test piece was immersed in
water at 37.degree. C. for 24 hours, immersing both in cold water
phase at 4.degree. C. for 60 seconds and in high temperature phase
at 60.degree. C. for 60 seconds was repeated 5000 times by using a
thermal shock tester (manufactured by THOMAS KAGAKU Co., Ltd). The
specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the shear adhesive
strength at a crosshead speed of 1 mm/min. Evaluation criteria were
as follows.
Particularly good: adhesive strength was 12 MPa or more. Good:
adhesive strength was 8 MPa or more and less than 12 MPa.
Applicable: adhesive strength was 3 MPa or more and less than 8
MPa. Insufficient: adhesive strength was less than 3 MPa.
[0199] In the test in which the dental curable composition of the
compositions S1 to S7 were combined with, immersing both in cold
water phase at 4.degree. C. for 60 seconds and in high temperature
phase at 60.degree. C. for 60 seconds was repeated 20000 times by
using a thermal shock tester (manufactured by THOMAS KAGAKU Co.,
Ltd). The specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the adhesive strength
at a crosshead speed of 1 mm/min. Evaluation criteria were as
follows.
Extremely good: adhesive strength was 19 MPa or more. Particularly
good: adhesive strength was 12 MPa or more and less than 19 MPa.
Good: adhesive strength was 8 MPa or more and less than 12 MPa.
Applicable: adhesive strength was 3 MPa or more and less than 8
MPa. Insufficient: adhesive strength was less than 3 MPa.
[Adhesive Strength to Zirconia]
<Adhesion Test 1>
[0200] A test specimen having a thickness of 3 mm and a length and
a width of 20 mm was prepared by processing zirconia (SHOFU DISK
Lucent Supra, manufactured by SHOFU INC.) by a predetermined
method. Thereafter, the adherend surface was sandblast-treated and
a tape (thickness 20 .mu.m) with a hole having a diameter of 4 mm
was affixed to the adherend surface to prescribe an adhesion area.
The composition was applied into the tape with the hole and
immediately air dried. For the two packs type dental adhesive
composition, the same weight were weighed before application,
sufficiently mixed, and thereafter applied and then immediately
air-dried. Light irradiation was performed for 5 seconds with the
dental polymerization LED light irradiator (PEN Bright, SHOFU
INC.). A plastic mold with a hole having 2 mm of the height and 4
mm of diameter was overlaid the tape with the hole, and the dental
composite resin (BEAUTIFIL Flow Plus A3: SHOFU INC.) or the dental
curable composition shown in Table 3 was filled. Thereafter, the
light was irradiated for 10 seconds by the dental polymerization
LED light irradiator (PEN Bright, SHOFU INC.). After immersing in
water at 37.degree. C. for 24 hours, immersing both in cold water
phase at 4.degree. C. for 60 seconds and in high temperature phase
at 60.degree. C. for 60 seconds was repeated 5000 times by using a
thermal shock tester (manufactured by THOMAS KAGAKU Co., Ltd). The
specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the shear adhesive
strength at a crosshead speed of 1 mm/min. Evaluation criteria were
as follows.
Particularly good: adhesive strength was 20 MPa or more. Good:
adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[0201] In the test in which the dental curable composition of the
compositions R1 to R7 were combined with, immersing both in cold
water phase at 4.degree. C. for 60 seconds and in high temperature
phase at 60.degree. C. for 60 seconds was repeated 20000 times by
using a thermal shock tester (manufactured by THOMAS KAGAKU Co.,
Ltd). The specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the adhesive strength
at a crosshead speed of 1 mm/min. Evaluation criteria were as
follows.
Extremely good: adhesive strength was 28 MPa or more. Particularly
good: adhesive strength was 20 MPa or more and less than 28 MPa.
Good: adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
<Adhesion Test 2>
[0202] A test specimen having a thickness of 3 mm and a length and
a width of 20 mm was prepared by processing zirconia (SHOFU DISK
Lucent Supra, manufactured by SHOFU INC.) by a predetermined
method. Thereafter, the adherend surface was sandblast-treated and
a tape (thickness 20 .mu.m) with a hole having a diameter of 4 mm
was affixed to the adherend surface to prescribe an adhesion area.
The composition was applied into the tape with the hole and
immediately air dried. For the two packs type dental adhesive
composition, the same weight were weighed before application,
sufficiently mixed, and thereafter applied and then immediately
air-dried. The adherend surface of the stainless rod (.phi.4.5 mm)
was sandblasted (0.2 MPa, 1 second) with alumina (50 .mu.m), then
was washed with water and dried, and applied with a metal adhesive
primer (METAL LINK, SHOFU INC.). The adherend surface of the
stainless rod was applied with appropriate amount of resin cement
(Resicem, SHOFU INC.) or a kneaded material of the dental curable
composition shown in Table 4, and a tooth substance and the
stainless rod were bonded so as to fit in the frame of the
double-sided tape with a hole. A load of 200 N was applied from the
vertical direction of the stainless rod, and excess cement was
wiped off with a cloth. Thereafter, Light irradiation was performed
for 10 seconds with the dental polymerization LED light irradiator
(PEN Bright, SHOFU INC.). After removing the load, the prepared
adhesive test piece was immersed in water at 37.degree. C. for 24
hours, immersing both in cold water phase at 4.degree. C. for 60
seconds and in high temperature phase at 60.degree. C. for 60
seconds was repeated 5000 times by using a thermal shock tester
(manufactured by THOMAS KAGAKU Co., Ltd). The specimen was taken
out and an Instron universal tester (manufactured by Instron) was
used to measure the shear adhesive strength at a crosshead speed of
1 mm/min. Evaluation criteria were as follows.
Particularly good: adhesive strength was 20 MPa or more. Good:
adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[0203] In the test in which the dental curable composition of the
compositions S1 to S7 were combined with, immersing both in cold
water phase at 4.degree. C. for 60 seconds and in high temperature
phase at 60.degree. C. for 60 seconds was repeated 20000 times by
using a thermal shock tester (manufactured by THOMAS KAGAKU Co.,
Ltd). The specimen was taken out and an Instron universal tester
(manufactured by Instron) was used to measure the adhesive strength
at a crosshead speed of 1 mm/min. Evaluation criteria were as
follows.
Extremely good: adhesive strength was 28 MPa or more. Particularly
good: adhesive strength was 20 MPa or more and less than 28 MPa.
Good: adhesive strength was 12 MPa or more and less than 20 MPa.
Applicable: adhesive strength was 5 MPa or more and less than 12
MPa. Insufficient: adhesive strength was less than 5 MPa.
[Evaluation of Storage Stability of Acceleration Test Product]
[0204] In the evaluation of the storage stability of the
acceleration test product, the adhesive strength of the same
composition to the same adherend was measured before and after the
acceleration test, and the maintenance rate of the adhesive
strength was calculated according to formula 3. Evaluation criteria
were as follows.
Particularly good storage stability: maintenance rate was 90% or
more. Good storage stability: maintenance rate was 70% or more and
less than 90%. Applicable storage stability: maintenance rate was
50% or more and less than 70%. Poor storage stability: maintenance
rate was less than 50%.
(Adhesive strength after acceleration test [MPa]/Adhesive strength
before acceleration test [MPa]).times.100[%] [Formula 3]
[0205] Tables 8 and 9 show the results of each composition P and
each composition CP.
TABLE-US-00008 TABLE 8 Adhesion test 1 Enamel Dentin Zirconia
Initial Adhesive Initial Adhesive Initial adhesive strength
Maintenance adhesive strength Maintenance adhesive strength after
storage rate strength after storage rate strength (MPa) (MPa) (%)
(MPa) (MPa) (%) (MPa) Example P1 27.4 24.1 88.0 14.6 12.1 82.9 29.4
Example P2 19.4 18.5 95.8 8.6 9.0 105.4 16.8 Example P3 21.1 17.4
82.5 18.0 14.9 82.5 26.0 Example P4 27.5 24.3 88.2 17.6 14.5 82.6
26.4 Example P5 14.1 10.2 72.6 11.5 8.8 76.6 14.4 Example P6 14.5
10.3 70.6 9.4 7.0 74.4 15.1 Example P7 24.9 26.8 107.5 12.9 13.0
100.5 26.3 Example P8 24.3 25.3 103.9 15.9 15.5 97.5 27.3 Example
P9 28.8 28.0 97.0 16.9 15.5 91.7 28.5 Example P10 21.1 21.5 102.3
13.1 13.2 101.1 25.1 Example P11 26.8 28.0 104.6 17.7 18.2 102.8
28.4 Example P12 23.7 23.4 98.4 17.0 18.1 106.1 20.6 Example P13
27.0 25.5 94.7 17.5 15.8 90.6 20.9 Example P14 23.3 24.8 106.6 12.2
12.4 102.2 26.0 Example P15 25.8 24.9 96.7 13.8 13.1 95.1 24.7
Example P16 25.6 26.4 103.3 18.0 19.1 106.0 21.8 Example P17 23.6
22.9 97.0 14.3 13.7 95.8 20.5 Example P18 24.7 17.4 70.1 16.2 13.8
85.3 20.0 Example P19 29.1 22.2 76.2 12.2 10.4 85.6 28.1 Example
P20 21.1 15.8 74.9 16.0 12.6 79.0 20.4 Example P21 21.1 16.8 79.6
15.2 13.4 88.1 26.0 Example P22 29.7 23.5 79.2 14.8 12.5 83.9 28.4
Example P23 22.9 23.0 100.4 12.0 10.9 90.4 29.2 Example P24 27.1
23.1 85.5 15.9 13.6 85.6 28.2 Example P25 24.6 18.2 73.8 16.4 12.1
73.7 29.4 Example P26 29.7 32.6 109.8 17.4 18.9 108.6 27.8 Example
P27 28.9 26.0 90.1 12.3 13.0 105.5 22.8 Example P28 20.8 19.1 91.8
14.6 13.7 93.5 23.0 Example P29 23.2 16.4 70.9 13.3 9.6 72.5 29.5
Example P30 24.4 17.3 70.9 16.6 14.0 84.2 25.9 Adhesion test 1
Adhesion test 2(with light irradiation) Zirconia Enamel Dentin
Adhesive Initial Adhesive Initial strength Maintenance adhesive
strength Maintenance adhesive after storage rate strength after
storage rate strength (MPa) (%) (MPa) (MPa) (%) (MPa) Example P1
23.1 78.3 22.2 18.7 84.2 17.8 Example P2 16.4 98.1 18.2 17.7 97.1
11.0 Example P3 18.8 72.1 23.2 17.9 77.0 15.0 Example P4 19.6 74.2
26.6 23.2 87.0 17.8 Example P5 10.9 75.7 15.2 12.3 80.9 9.8 Example
P6 11.5 76.1 14.6 10.8 74.0 10.4 Example P7 25.6 97.3 21.6 22.6
104.3 12.5 Example P8 29.7 108.8 25.6 27.4 106.9 12.3 Example P9
31.2 109.5 25.4 26.3 103.7 13.2 Example P10 26.7 106.0 27.8 26.4
95.0 13.0 Example P11 25.9 91.2 28.9 27.7 95.9 16.2 Example P12
21.0 101.8 21.1 23.0 108.8 17.7 Example P13 19.8 95.0 22.4 23.7
105.7 15.4 Example P14 27.8 107.0 22.8 21.3 93.4 18.8 Example P15
24.2 98.0 29.2 26.6 91.0 15.0 Example P16 22.1 101.5 23.8 25.6
107.4 13.2 Example P17 19.5 94.8 29.3 31.5 107.7 16.5 Example P18
17.1 85.3 25.1 18.5 73.6 18.4 Example P19 24.4 86.7 29.7 23.1 77.9
14.4 Example P20 14.5 71.3 23.5 16.8 71.4 15.1 Example P21 18.8
72.1 24.3 19.4 80.0 14.7 Example P22 21.9 77.1 27.3 20.0 73.0 13.6
Example P23 31.3 107.2 29.7 29.5 99.3 15.7 Example P24 22.9 81.2
24.6 18.8 76.7 15.0 Example P25 26.1 88.6 23.0 20.6 89.5 16.5
Example P26 27.2 97.7 28.0 27.8 99.3 17.4 Example P27 21.1 92.6
27.5 24.9 90.7 18.3 Example P28 24.1 104.6 21.9 21.9 99.9 19.0
Example P29 23.6 79.9 27.0 19.5 72.1 14.4 Example P30 19.5 75.2
24.4 17.4 71.1 12.9 Adhesion test 2(with light irradiation) Dentin
Zirconia Adhesive Initial Adhesive strength Maintenance adhesive
strength Maintenance after storage rate strength after storage rate
(MPa) (%) (MPa) (MPa) (%) Example P1 15.5 86.7 29.8 21.9 73.4
Example P2 11.1 100.5 17.4 18.1 104.1 Example P3 12.1 81.0 29.1
24.4 84.0 Example P4 12.9 72.3 22.6 17.7 78.3 Example P5 8.6 88.5
15.1 12.2 81.1 Example P6 9.3 89.8 19.1 13.5 70.9 Example P7 13.6
109.2 21.1 21.4 101.7 Example P8 11.4 92.4 26.6 24.0 90.5 Example
P9 13.2 99.7 29.0 26.7 92.2 Example P10 13.4 102.7 22.3 21.7 97.4
Example P11 15.3 94.8 20.2 18.5 91.3 Example P12 18.6 105.0 28.2
27.6 97.6 Example P13 16.1 105.0 22.1 22.6 102.3 Example P14 17.1
90.7 24.8 26.6 107.5 Example P15 14.7 97.8 24.7 22.5 90.8 Example
P16 12.1 91.8 23.9 25.1 105.3 Example P17 17.0 103.4 21.1 20.5 97.6
Example P18 12.9 70.1 21.5 17.7 82.4 Example P19 11.4 78.6 27.7
20.6 74.2 Example P20 12.8 85.0 29.8 22.1 74.2 Example P21 13.1
88.8 26.7 23.8 89.0 Example P22 9.9 72.5 28.1 24.1 85.8 Example P23
16.8 107.1 27.1 25.1 92.5 Example P24 11.1 74.1 24.9 18.9 76.0
Example P25 13.1 79.1 29.1 20.9 71.9 Example P26 16.9 97.0 22.0
22.7 103.3 Example P27 17.6 96.3 27.6 25.6 92.8 Example P28 20.1
106.0 29.4 30.8 104.6 Example P29 12.5 86.7 22.9 16.2 70.9 Example
P30 10.8 83.2 20.1 16.4 81.6
TABLE-US-00009 TABLE 9 Adhesion test 1 Enamel Dentin Zirconia
Initial Adhesive Initial Adhesive Initial adhesive strength
Maintenance adhesive strength Maintenance adhesive strength after
storage rate strength after storage rate strength (MPa) (MPa) (%)
(MPa) (MPa) (%) (MPa) Example P31 24.4 24.7 101.3 16.1 15.0 92.6
21.4 Example P32 29.3 30.1 102.8 14.3 15.3 106.8 26.9 Example P33
29.5 27.5 93.2 16.6 15.3 92.3 22.5 Example P34 26.4 25.7 97.6 14.2
13.1 92.1 21.5 Example P35 26.8 25.8 96.1 16.0 17.3 108.2 24.2
Example P36 23.2 21.3 91.9 12.4 11.3 90.9 27.7 Example P37 21.2
20.9 98.9 12.4 12.9 104.1 21.3 Example P38 27.8 28.0 100.6 14.6
13.3 91.1 24.1 Example P39 28.8 30.5 106.0 17.1 17.0 99.7 29.5
Example P40 26.5 26.1 98.3 14.1 14.6 103.1 22.5 Example P41 26.8
23.9 88.9 18.6 15.5 83.3 28.6 Example P42 25.8 24.9 96.7 13.8 13.1
95.1 24.7 Example P43 27.4 27.1 98.9 13.9 12.9 92.3 25.6 Example
P44 25.3 27.4 108.4 12.5 11.4 90.8 22.7 Example P45 21.3 19.3 90.5
18.9 18.8 99.4 26.3 Example P46 25.9 25.4 98.3 12.9 12.9 99.8 23.8
Example P47 26.2 24.9 95.0 14.9 15.7 105.6 28.5 Comparative 26.9
3.6 13.5 18.3 2.6 14.3 25.2 Example CP1 Comparative 1.3 0.5 39.8
1.5 0.4 24.3 1.6 Example CP2 Comparative 6.4 4.4 69.2 7.5 4.4 58.4
11.4 Example CP3 Comparative 18.7 2.8 15.0 9.7 3.4 34.5 19.4
Example CP4 Comparative 16.5 1.9 11.2 9.5 4.7 49.3 14.6 Example CP5
Comparative 13.8 6.0 43.9 10.1 2.1 21.2 14.6 Example CP6
Comparative 19.2 6.2 32.2 11.8 2.8 23.7 19.3 Example CP7
Comparative 26.5 11.3 42.6 14.5 6.4 44.4 28.6 Example CP8
Comparative 16.7 8.0 47.7 10.4 2.3 21.6 15.9 Example CP9
Comparative 13.4 3.5 25.9 8.7 3.3 37.6 14.2 Example CP10
Comparative 16.1 7.3 45.2 9.9 1.9 19.1 15.6 Example CP11
Comparative 18.2 5.9 32.2 11.1 1.5 13.6 14.1 Example CP12
Comparative 14.5 6.1 42.1 9.1 1.7 18.5 17.1 Example CP13 Adhesion
test 1 Adhesion test 2(with light irradiation) Zirconia Enamel
Dentin Adhesive Initial Adhesive Initial strength Maintenance
adhesive strength Maintenance adhesive after storage rate strength
after storage rate strength (MPa) (%) (MPa) (MPa) (%) (MPa) Example
P31 20.4 95.3 21.4 21.7 101.5 14.8 Example P32 26.5 98.5 22.0 20.4
92.6 14.8 Example P33 23.7 105.2 20.6 22.4 108.9 14.0 Example P34
23.5 109.2 21.3 20.4 96.0 15.3 Example P35 25.3 104.5 28.0 28.6
102.2 15.1 Example P36 30.4 109.6 21.0 22.2 106.1 18.4 Example P37
22.3 104.6 25.0 25.7 102.9 16.5 Example P38 23.6 97.8 29.7 29.7
100.1 17.8 Example P39 28.7 97.3 22.6 22.6 100.4 16.8 Example P40
23.5 104.3 21.9 23.2 105.8 13.3 Example P41 22.8 79.5 24.8 20.0
80.4 12.9 Example P42 24.2 98.0 29.2 26.6 91.0 15.0 Example P43
23.5 91.8 22.1 24.2 109.5 16.7 Example P44 22.0 96.9 27.5 27.3 99.2
17.8 Example P45 27.7 105.3 27.1 27.3 100.7 13.2 Example P46 24.5
103.1 28.7 28.6 99.6 16.7 Example P47 27.2 95.7 27.0 28.9 106.8
13.3 Comparative 12.2 48.3 25.4 7.0 27.6 18.3 Example CP1
Comparative 0.4 28.4 1.5 0.4 24.4 2.6 Example CP2 Comparative 7.6
66.7 8.3 4.7 56.3 6.3 Example CP3 Comparative 9.2 47.3 14.8 6.2
42.0 9.9 Example CP4 Comparative 7.0 47.6 13.8 6.5 47.5 8.6 Example
CP5 Comparative 3.0 20.4 12.2 2.5 20.6 11.3 Example CP6 Comparative
3.6 18.8 15.1 4.5 29.6 10.6 Example CP7 Comparative 7.2 25.0 21.5
7.6 35.5 18.8 Example CP8 Comparative 7.6 47.5 15.6 5.4 34.9 10.2
Example CP9 Comparative 2.8 19.5 15.7 2.4 15.1 8.1 Example CP10
Comparative 6.9 44.2 15.4 4.6 30.0 11.9 Example CP11 Comparative
1.9 13.5 17.5 6.0 34.0 10.8 Example CP12 Comparative 3.2 18.9 17.8
8.3 46.4 11.8 Example CP13 Adhesion test 2(with light irradiation)
Dentin Zirconia Adhesive Initial Adhesive strength Maintenance
adhesive strength Maintenance after storage rate strength after
storage rate (MPa) (%) (MPa) (MPa) (%) Example P31 14.7 99.0 23.9
21.6 90.2 Example P32 14.3 96.6 28.8 27.0 93.8 Example P33 12.7
90.3 28.3 26.5 93.5 Example P34 15.4 100.6 20.6 21.1 102.5 Example
P35 13.8 91.4 29.7 28.7 96.6 Example P36 18.9 102.6 27.8 26.2 94.2
Example P37 15.5 94.2 22.4 24.4 109.1 Example P38 16.7 94.0 22.4
20.7 92.3 Example P39 18.3 109.0 24.2 23.3 96.4 Example P40 13.7
102.5 22.6 20.6 90.9 Example P41 9.1 70.8 29.8 25.0 83.9 Example
P42 14.7 97.8 24.7 22.5 90.8 Example P43 15.3 91.4 20.9 21.4 102.5
Example P44 17.1 96.5 20.6 19.9 96.4 Example P45 13.1 99.4 22.3
20.1 90.2 Example P46 15.1 90.7 27.1 27.1 99.8 Example P47 12.1
91.0 28.4 28.0 98.5 Comparative 6.8 37.3 29.9 13.3 44.5 Example CP1
Comparative 1.0 36.1 2.2 0.8 34.6 Example CP2 Comparative 3.7 58.7
7.3 4.2 56.9 Example CP3 Comparative 4.4 45.0 17.5 8.5 48.7 Example
CP4 Comparative 4.2 49.1 12.6 4.9 38.5 Example CP5 Comparative 5.2
45.9 12.4 4.4 35.5 Example CP6 Comparative 2.0 18.5 15.4 4.8 31.1
Example CP7 Comparative 8.3 44.4 24.3 8.4 34.6 Example CP8
Comparative 2.3 22.9 15.9 6.8 42.8 Example CP9 Comparative 1.8 22.4
16.9 2.8 16.2 Example CP10 Comparative 4.6 38.6 15.5 2.9 18.7
Example CP11 Comparative 4.5 41.7 18.3 4.0 21.9 Example CP12
Comparative 5.4 45.5 18.3 2.2 12.2 Example CP13
[0206] The compositions P1 to P47 showed good adhesive property and
maintenance rate. Among them, it was confirmed that Examples P1, P7
to P17, P23, P24, P26, P27, P31 to 40, and P42 to 47 had both high
adhesive strength and extremely high maintenance rate.
[0207] On the other hand, since the compositions CP1 and CP2 did
not contain an amine compound, the adhesive strength after storage
was significantly reduced. Since the composition CP3 did not
contain the (A-1) polymerizable monomer having an acidic group, it
was confirmed that the adhesive strength was hardly exhibited.
Although the compositions CP4 to CP13 contained an amine compound,
since the structure of the amine compound differed from the
structure represented by the formula (1), the adhesive strength
after storage is remarkably reduced. Based on the above, it is
presumed that when the (A-1) polymerizable monomer having an acidic
group and the (D-1) aliphatic tertiary amine compound coexist and
the compounded amount thereof are appropriate, adhesive property is
high and the property is maintained.
[0208] Tables 10 to 12 show the results of each composition Q and
each composition CQ.
TABLE-US-00010 TABLE 10 Adhesion test 1 Enamel Dentin Zirconia
Initial Adhesive Initial Adhesive Initial adhesive strength
Maintenance adhesive strength Maintenance adhesive strength after
storage rate strength after storage rate strength (MPa) (MPa) (%)
(MPa) (MPa) (%) (MPa) Example Q1 22.0 18.8 85.4 18.1 16.1 88.9 21.6
Example Q2 15.2 12.1 79.4 11.9 9.5 80.1 18.5 Example Q3 27.4 23.0
83.7 12.7 10.8 85.0 25.2 Example Q4 24.3 18.8 77.3 12.3 8.7 70.7
27.2 Example Q5 12.6 9.9 78.5 11.5 9.9 85.7 12.2 Example Q6 17.7
13.2 74.5 8.1 7.0 86.4 19.8 Example Q7 23.3 21.4 91.9 16.3 15.2
93.7 27.4 Example Q8 23.3 23.2 99.6 15.5 16.3 104.9 25.5 Example Q9
26.7 24.4 91.4 13.8 14.0 101.5 21.3 Example Q10 20.5 21.0 102.2
19.0 19.1 100.9 22.5 Example Q11 28.2 29.8 105.4 16.1 17.5 108.9
22.3 Example Q12 29.8 32.4 108.7 13.2 12.6 95.4 29.8 Example Q13
20.2 20.0 99.0 16.9 18.0 106.6 27.7 Example Q14 21.9 22.6 103.2
18.3 18.0 98.7 22.8 Example Q15 25.6 23.7 92.4 18.4 17.1 93.4 20.4
Example Q16 26.5 20.4 77.2 14.7 11.9 80.4 28.3 Adhesion test 1
Adhesion test 2(with light irradiation) Zirconia Enamel Dentin
Adhesive Initial Adhesive Initial strength Maintenance adhesive
strength Maintenance adhesive after storage rate strength after
storage rate strength (MPa) (%) (MPa) (MPa) (%) (MPa) Example Q1
19.2 89.1 28.0 24.0 85.7 18.7 Example Q2 13.3 71.6 14.3 12.3 85.8
10.3 Example Q3 20.7 82.2 28.4 25.4 89.5 12.4 Example Q4 22.4 82.2
25.0 19.7 78.7 14.7 Example Q5 10.5 86.3 16.8 14.9 88.3 10.0
Example Q6 15.5 78.5 16.8 12.4 73.7 9.2 Example Q7 27.4 99.7 22.3
24.0 107.7 14.2 Example Q8 25.6 100.2 25.1 27.6 109.7 19.0 Example
Q9 21.9 102.4 24.0 25.8 107.6 18.4 Example Q10 21.3 94.6 28.8 27.9
96.8 14.9 Example Q11 21.2 95.1 28.7 31.5 109.9 15.8 Example Q12
31.9 106.8 20.6 21.2 103.0 15.4 Example Q13 29.3 105.9 26.1 26.7
102.3 16.6 Example Q14 22.2 97.2 20.9 20.0 95.7 14.6 Example Q15
21.0 102.9 28.3 29.7 105.0 18.3 Example Q16 22.8 80.5 29.6 22.3
75.3 15.7 Adhesion test 2(with light irradiation) Dentin Zirconia
Adhesive Initial Adhesive strength Maintenance adhesive strength
Maintenance after storage rate strength after storage rate (MPa)
(%) (MPa) (MPa) (%) Example Q1 16.7 89.3 22.0 17.7 80.5 Example Q2
8.5 82.6 15.3 13.4 87.7 Example Q3 10.5 84.8 27.7 24.2 87.4 Example
Q4 12.2 82.8 23.4 17.0 72.6 Example Q5 7.5 74.6 19.5 14.8 76.0
Example Q6 6.7 73.1 12.3 9.6 78.4 Example Q7 14.6 102.3 25.8 27.4
106.0 Example Q8 20.4 107.7 27.7 30.0 108.2 Example Q9 18.6 101.3
22.8 21.2 93.0 Example Q10 15.8 106.6 27.8 26.4 95.0 Example Q11
14.5 91.3 28.9 26.8 92.8 Example Q12 16.7 108.4 28.1 29.9 106.5
Example Q13 16.2 97.8 23.7 24.2 102.0 Example Q14 14.3 98.1 30.0
27.6 91.9 Example Q15 17.1 93.7 26.7 27.6 103.2 Example Q16 12.6
80.1 25.1 18.1 72.2
TABLE-US-00011 TABLE 11 Adhesion test 1 Enamel Dentin Zirconia
Initial Adhesive Initial Adhesive Initial adhesive strength
Maintenance adhesive strength Maintenance adhesive strength after
storage rate strength after storage rate strength (MPa) (MPa) (%)
(MPa) (MPa) (%) (MPa) Example Q17 23.6 25.2 107.0 13.0 13.9 107.4
25.7 Example Q18 21.3 16.4 76.9 17.3 15.6 89.9 24.6 Example Q19
21.5 16.5 76.8 17.8 15.7 87.9 25.5 Example Q20 22.1 18.2 82.5 12.9
11.3 87.7 25.4 Example Q21 23.2 16.3 70.4 17.2 14.2 82.2 26.0
Example Q22 23.8 16.7 70.2 18.2 14.8 81.2 25.9 Example Q23 21.8
17.8 81.7 17.2 14.8 85.8 25.2 Example Q24 29.3 25.1 85.6 16.7 11.9
71.5 24.1 Example Q25 27.7 19.5 70.4 16.0 11.5 71.8 20.6 Example
Q26 21.9 21.9 100.3 16.5 15.0 91.4 28.6 Example Q27 29.5 32.4 109.7
16.7 16.8 100.7 20.7 Example Q28 27.6 22.3 80.8 17.8 14.5 81.6 24.5
Example Q29 25.3 19.5 76.8 13.9 11.0 78.9 25.5 Example Q30 21.8
16.7 76.9 16.7 12.9 77.4 28.7 Example Q31 26.4 24.9 94.3 18.5 18.1
98.2 26.2 Example Q32 26.7 25.0 93.6 16.9 18.0 106.6 21.4 Adhesion
test 1 Adhesion test 2 (with light irradiation) Zirconia Enamel
Dentin Adhesive Initial Adhesive Initial strength Maintenance
adhesive strength Maintenance adhesive after storage rate strength
after storage rate strength (MPa) (%) (MPa) (MPa) (%) (MPa) Example
Q17 24.1 93.8 28.4 30.6 107.6 18.3 Example Q18 21.7 87.9 26.1 21.4
81.9 12.6 Example Q19 18.5 72.5 23.9 17.2 72.1 16.7 Example Q20
18.5 72.8 26.3 21.1 80.2 19.0 Example Q21 20.8 79.8 28.9 21.5 74.4
18.3 Example Q22 21.9 84.7 24.8 17.7 71.2 16.2 Example Q23 20.6
81.6 29.7 24.5 82.6 18.4 Example Q24 17.7 73.2 25.8 22.8 88.7 13.0
Example Q25 14.6 71.0 29.1 24.2 83.4 16.7 Example Q26 29.3 102.4
27.4 27.2 99.0 13.6 Example Q27 19.5 94.4 22.5 21.1 93.7 15.5
Example Q28 21.3 87.2 28.3 25.2 88.9 12.4 Example Q29 20.6 80.8
22.6 18.1 80.0 12.5 Example Q30 22.7 79.0 24.8 17.8 71.9 17.4
Example Q31 26.6 101.8 27.5 25.2 91.7 16.9 Example Q32 21.2 99.1
26.9 25.3 94.0 17.2 Adhesion test 2 (with light irradiation) Dentin
Zirconia Adhesive Initial Adhesive strength Maintenance adhesive
strength Maintenance after storage rate strength after storage rate
(MPa) (%) (MPa) (MPa) (%) Example Q17 16.8 91.8 29.1 31.8 109.1
Example Q18 10.3 81.7 22.1 17.9 80.9 Example Q19 11.9 71.1 28.0
24.2 86.3 Example Q20 15.9 84.0 22.2 18.1 81.7 Example Q21 15.8
86.1 26.5 19.8 74.8 Example Q22 14.1 87.0 25.1 18.0 71.7 Example
Q23 15.1 81.9 29.8 24.3 81.7 Example Q24 9.2 71.1 21.3 16.9 79.0
Example Q25 14.7 88.3 24.3 17.8 73.2 Example Q26 14.3 105.6 28.2
30.6 108.8 Example Q27 14.5 94.0 23.3 25.6 109.8 Example Q28 10.9
88.0 23.5 19.6 83.6 Example Q29 9.2 73.6 26.5 22.6 85.3 Example Q30
12.9 74.0 28.2 22.2 78.8 Example Q31 16.1 95.3 25.0 25.8 103.2
Example Q32 16.6 96.5 20.4 19.5 95.6
TABLE-US-00012 TABLE 12 Adhesion test 1 Enamel Dentin Zirconia
Initial Adhesive Initial Adhesive Initial adhesive strength
Maintenance adhesive strength Maintenance adhesive strength after
storage rate strength after storage rate strength (MPa) (MPa) (%)
(MPa) (MPa) (%) (MPa) Example Q33 27.6 29.7 107.9 14.1 14.3 101.2
25.7 Example Q34 29.9 28.6 95.7 12.9 12.3 95.0 25.4 Example Q35
28.3 25.7 90.9 17.9 17.2 95.8 30.0 Example Q36 20.9 22.2 106.1 17.0
18.0 105.9 25.0 Example Q37 20.1 19.4 96.6 14.7 15.5 105.6 22.6
Example Q38 23.9 22.8 95.3 13.8 13.0 94.7 27.3 Example Q39 26.6
26.8 100.6 14.3 13.4 93.7 22.2 Example Q40 27.0 26.8 99.4 14.3 14.0
97.5 28.0 Example Q41 24.1 22.8 94.5 15.7 17.1 108.8 26.8 Example
Q42 29.3 23.3 79.5 14.3 10.5 73.5 28.3 Comparative 18.6 6.1 32.9
9.8 4.7 47.9 19.7 Example CQ1 Comparative 1.4 1.2 83.4 1.9 1.4 76.8
3.6 Example CQ2 Comparative 16.4 6.4 39.2 10.3 3.6 35.0 16.1
Example CQ3 Comparative 18.7 3.6 19.5 9.8 4.9 49.4 14.0 Example CQ4
Adhesion test 1 Adhesion test 2(with light irradiation) Zirconia
Enamel Dentin Adhesive Initial Adhesive Initial strength
Maintenance adhesive strength Maintenance adhesive after storage
rate strength after storage rate strength (MPa) (%) (MPa) (MPa) (%)
(MPa) Example Q33 24.6 95.5 23.7 24.7 104.3 18.1 Example Q34 27.2
107.2 27.0 28.1 104.0 15.9 Example Q35 28.1 93.6 20.7 21.4 103.4
18.7 Example Q36 24.1 96.1 28.6 25.8 90.1 12.9 Example Q37 22.5
99.6 23.0 24.9 108.1 15.8 Example Q38 24.9 91.0 26.6 24.1 90.7 14.0
Example Q39 20.4 92.3 28.9 28.6 98.8 18.8 Example Q40 26.3 93.9
27.9 26.1 93.5 18.0 Example Q41 26.4 98.2 21.5 22.6 105.2 14.6
Example Q42 24.7 87.1 29.5 22.3 75.7 14.2 Comparative 8.8 44.8 12.3
1.9 15.4 8.4 Example CQ1 Comparative 3.2 89.2 4.6 3.5 75.1 2.3
Example CQ2 Comparative 4.3 27.0 16.3 4.5 27.6 10.4 Example CQ3
Comparative 3.6 25.4 15.1 2.5 16.8 11.1 Example CQ4 Adhesion test
2(with light irradiation) Dentin Zirconia Adhesive Initial Adhesive
strength Maintenance adhesive strength Maintenance after storage
rate strength after storage rate (MPa) (%) (MPa) (MPa) (%) Example
Q33 18.9 104.4 27.3 28.4 104.1 Example Q34 16.2 102.1 26.6 27.6
103.5 Example Q35 17.3 92.3 29.3 28.6 97.5 Example Q36 13.4 104.1
26.6 29.2 109.8 Example Q37 14.9 94.2 24.5 24.3 99.2 Example Q38
13.3 95.1 22.6 24.1 106.7 Example Q39 19.8 105.4 28.1 29.5 104.9
Example Q40 19.5 108.4 20.2 20.5 101.6 Example Q41 15.4 105.4 27.9
27.8 99.3 Example Q42 11.7 82.5 27.1 21.0 77.6 Comparative 1.9 22.8
14.7 3.2 21.5 Example CQ1 Comparative 1.7 70.8 2.6 1.8 70.1 Example
CQ2 Comparative 4.0 38.5 13.7 1.4 10.2 Example CQ3 Comparative 3.8
34.3 12.2 3.3 27.5 Example CQ4
[0209] The compositions Q1 to Q40 showed good adhesive property and
maintenance rate. Among them, it was confirmed that Examples Q7 to
17, Q26, Q27 and Q31 to 40 had both high adhesive strength and
extremely high maintenance rate.
[0210] On the other hand, since the composition CQ1 did not contain
an amine compound, the adhesive strength after storage was
significantly reduced. Since the composition CQ2 did not contain
the (A-1) polymerizable monomer having an acidic group, it was
confirmed that the adhesive strength was hardly exhibited. The
composition of Composition CQ3 showed good adhesive property, but
its maintenance rate was low. Although it contains an amine
compound, it is considered to be derived from the fact that the
amine compound is an aromatic amine. The composition CQ4 showed
good adhesive property by containing a photoacid generator, but the
adhesive strength after storage was significantly reduced. It was
confirmed that good adhesive strength and its maintenance rate were
exhibited in the test of composition Q in the same manner as in the
adhesion test 1 in which after applying each composition, air
drying was performed, and then light irradiation was performed for
5 seconds with the dental polymerization LED light irradiator (PEN
Bright, SHOFU INC.).
[0211] Table 13 shows the test results of kit R and kit CR, which
consist of a combination of a curable composition R1 to R7 and an
adhesive compositions P4, P14, P35, CP3, CP5 or CP11.
TABLE-US-00013 TABLE 13 Adhesion test Enamel Initial Adhesive
adhesive strength Maintenance Dental adhesive Dental curable
strength after storage rate composition composition (MPa) (MPa) (%)
Example R1 Composition P4 Composition R1 30.9 33.8 109.7 Example R2
Composition R2 33.5 36.9 110.0 Example R3 Composition R3 31.5 33.9
107.7 Example R4 Composition R4 28.6 26.6 92.9 Example R5
Composition R5 33.1 30.6 92.5 Example R6 Composition R6 22.0 18.8
85.5 Example R7 Composition R7 21.1 18.4 86.8 Example R8
Composition P14 Composition R1 20.1 18.9 94.3 Example R9
Composition R2 22.9 25.1 109.6 Example R10 Composition R3 21.5 19.8
92.1 Example R11 Composition R4 22.7 23.3 102.8 Example R12
Composition R5 23.9 23.9 99.7 Example R13 Composition R6 15.2 14.1
92.9 Example R14 Composition R7 16.3 15.0 92.0 Example R15
Composition P35 Composition R1 32.4 32.4 100.0 Example R16
Composition R2 32.4 34.5 106.4 Example R17 Composition R3 31.7 32.1
101.2 Example R18 Composition R4 28.4 27.5 96.8 Example R19
Composition R5 32.8 32.9 100.4 Example R20 Composition R6 23.6 24.1
102.2 Example R21 Composition R7 20.6 20.5 99.5 Comparative
Composition CP3 Composition R1 4.7 4.5 95.1 Example CR1 Comparative
Composition R2 3.8 4.0 106.8 Example CR2 Comparative Composition R3
2.8 3.0 109.6 Example CR3 Comparative Composition R4 2.2 2.4 106.8
Example CR4 Comparative Composition R5 2.2 2.3 105.6 Example CR5
Comparative Composition R6 1.6 1.6 101.5 Example CR6 Comparative
Composition R7 1.8 1.8 99.9 Example CR7 Comparative Composition CP5
Composition R1 24.6 11.7 47.5 Example CR8 Comparative Composition
R2 23.3 4.4 18.8 Example CR9 Comparative Composition R3 22.9 4.8
20.9 Example CR10 Comparative Composition R4 22.9 8.0 35.0 Example
CR11 Comparative Composition R5 23.9 3.1 13.1 Example CR12
Comparative Composition R6 23.7 3.1 13.2 Example CR13 Comparative
Composition R7 22.0 8.7 39.7 Example CR14 Comparative Composition
CP11 Composition R1 22.4 2.3 10.0 Example CR15 Comparative
Composition R2 20.3 5.6 27.7 Example CR16 Comparative Composition
R3 24.1 10.9 45.3 Example CR17 Comparative Composition R4 22.9 6.7
29.4 Example CR18 Comparative Composition R5 23.6 10.0 42.5 Example
CR19 Comparative Composition R6 22.6 8.3 36.6 Example CR20
Comparative Composition R7 20.7 6.3 30.4 Example CR21 Adhesion test
Dentin Zirconia Initial Adhesive Initial Adhesive adhesive strength
Maintenance adhesive strength Maintenance strength after storage
rate strength after storage rate (MPa) (MPa) (%) (MPa) (MPa) (%)
Example R1 23.4 21.5 91.9 30.1 28.5 94.5 Example R2 24.7 24.1 97.8
33.9 30.8 90.8 Example R3 20.4 18.6 91.1 32.7 31.9 97.7 Example R4
23.8 23.9 100.4 31.6 31.5 99.6 Example R5 19.1 18.1 94.5 28.6 28.0
97.9 Example R6 17.8 13.0 73.0 20.4 16.6 81.4 Example R7 15.9 11.5
72.1 21.6 15.2 70.5 Example R8 12.2 12.8 104.3 24.8 24.9 100.4
Example R9 16.5 17.6 106.4 20.2 21.7 107.4 Example R10 14.3 13.2
92.4 20.8 22.5 108.4 Example R11 16.5 15.2 92.2 22.6 21.8 96.4
Example R12 18.4 18.2 98.9 22.4 22.8 101.8 Example R13 9.1 8.4 92.5
14.0 13.1 93.7 Example R14 11.3 12.0 105.6 18.3 19.8 108.3 Example
R15 25.0 27.1 108.3 32.0 33.8 105.5 Example R16 20.0 18.2 91.1 31.7
29.7 93.8 Example R17 21.7 22.9 105.2 30.2 30.1 99.8 Example R18
20.4 18.9 92.7 29.4 30.6 104.0 Example R19 23.1 24.9 107.8 31.2
33.3 106.6 Example R20 16.7 16.1 96.5 24.9 22.9 91.7 Example R21
15.6 15.0 96.0 21.8 20.6 94.6 Comparative 2.7 2.8 102.3 1.5 1.7
109.6 Example CR1 Comparative 2.8 2.9 102.4 2.8 2.8 101.5 Example
CR2 Comparative 2.6 2.4 90.9 3.2 3.3 103.8 Example CR3 Comparative
2.7 2.7 102.3 4.6 4.6 99.5 Example CR4 Comparative 1.5 1.5 97.4 4.1
3.7 90.8 Example CR5 Comparative 1.6 1.4 90.6 3.8 4.2 108.6 Example
CR6 Comparative 1.3 1.3 99.0 2.8 2.8 99.3 Example CR7 Comparative
15.4 4.7 30.4 21.8 8.6 39.2 Example CR8 Comparative 18.7 3.8 20.4
22.9 9.4 41.1 Example CR9 Comparative 13.2 4.7 35.8 24.8 5.3 21.5
Example CR10 Comparative 13.5 1.8 13.2 23.7 8.0 33.9 Example CR11
Comparative 12.0 1.4 12.1 24.1 5.2 21.5 Example CR12 Comparative
15.5 5.2 33.2 24.3 4.1 17.0 Example CR13 Comparative 17.0 5.8 34.2
21.0 2.8 13.2 Example CR14 Comparative 14.6 4.5 30.7 24.2 2.8 11.6
Example CR15 Comparative 15.4 2.5 16.3 23.2 3.7 16.0 Example CR16
Comparative 16.5 2.5 14.9 24.1 4.9 20.2 Example CR17 Comparative
12.8 2.2 17.4 24.3 5.8 24.0 Example CR18 Comparative 14.6 6.0 41.4
23.2 2.7 11.6 Example CR19 Comparative 13.9 5.8 41.9 23.9 7.4 30.9
Example CR20 Comparative 15.5 1.8 11.4 21.2 10.5 49.5 Example
CR21
[0212] Examples R1 to R5, R8 to R12 and R15 to R19 showed good
adhesive property and maintenance rate. Among them, Examples R1 to
R5 and R15 to R19 showed extremely high adhesive property, and a
synergistic effect exhibited by containing (A-1) polymerizable
monomer having an acidic group and (D-1) aliphatic tertiary amine
compound represented by formula (1) in the dental adhesive
composition and containing a photoacid generator in the curable
composition was confirmed. Although the adhesive strength of
Examples R6 and R7 was reduced after storage, it is presumed that
it was derived from the fact that it does not contain (C) photoacid
generator. In Comparative Examples CR1 to CR7 which were a
combination with the composition CP3, since CP3 did not contain
(A-1) polymerizable monomer having an acidic group, it was
confirmed that the adhesive strength was hardly exhibited. It was
confirmed that in Comparative Examples CR8 to CR21 containing the
composition CP5 or CP11, adhesive strength after storage was low
and maintenance rate was reduced. Since the adhesive composition
contained only the (D-1) aliphatic tertiary amine compound
represented by formula (1), like other compositions, it is presumed
that the adhesive strength decreased after storage.
[0213] Table 14 shows the test results of the kits of Examples S1
to S42 consisting of a combination of the two-packs type dental
curable composition S1 to S7 and the adhesive composition P1, P15,
P36, Q1, Q7 or Q14.
TABLE-US-00014 TABLE 14 Adhesion test 2 Enamel Dentin Initial
Adhesive Initial adhesive strength Maintenance adhesive Dental
adhesive Dental curable strength after storage rate strength
composition composition (MPa) (MPa) (%) (MPa) Example S1
Composition P1 Composition S1 31.8 34.0 107.0 25.4 Example S2
Composition S2 28.5 27.5 96.3 22.5 Example S3 Composition S3 29.0
27.2 93.8 25.5 Example S4 Composition S4 33.9 30.8 90.8 20.7
Example S5 Composition S5 31.0 32.2 104.1 24.1 Example S6
Composition S6 24.6 25.4 103.3 15.8 Example S7 Composition S7 24.6
23.4 95.1 16.1 Example S8 Composition P15 Composition S1 30.8 30.3
98.3 21.5 Example S9 Composition S2 28.4 29.4 103.8 19.9 Example
S10 Composition S3 29.5 26.9 91.3 19.1 Example S11 Composition S4
28.3 28.0 99.0 19.9 Example S12 Composition S5 33.5 36.3 108.4 24.4
Example S13 Composition S6 24.7 25.8 104.5 18.6 Example S14
Composition S7 24.1 22.1 91.5 14.1 Example S15 Composition P36
Composition S1 30.4 32.5 107.0 23.7 Example S16 Composition S2 32.4
35.0 108.1 25.2 Example S17 Composition S3 33.6 30.7 91.5 20.5
Example S18 Composition S4 29.8 28.6 96.1 20.3 Example S19
Composition S5 33.9 36.3 107.2 22.7 Example S20 Composition S6 20.8
19.3 92.6 14.8 Example S21 Composition S7 21.0 19.1 91.0 18.4
Example S22 Composition Q1 Composition S1 30.2 29.0 96.1 19.9
Example S23 Composition S2 30.8 28.9 94.0 23.0 Example S24
Composition S3 32.1 35.2 109.6 22.1 Example S25 Composition S4 32.8
32.9 100.4 24.3 Example S26 Composition S5 31.5 31.8 101.0 24.9
Example S27 Composition S6 23.6 25.9 109.7 17.8 Example S28
Composition S7 21.5 22.8 106.2 15.9 Example S29 Composition Q7
Composition S1 31.9 29.9 93.6 23.0 Example S30 Composition S2 33.1
35.0 105.7 19.3 Example S31 Composition S3 28.9 30.4 105.1 24.4
Example S32 Composition S4 30.2 29.5 97.9 23.6 Example S33
Composition S5 33.6 34.0 101.3 24.4 Example S34 Composition S6 20.9
19.6 93.6 12.6 Example S35 Composition S7 23.2 23.6 101.7 18.0
Example S36 Composition Q14 Composition S1 32.8 35.0 106.8 21.1
Example S37 Composition S2 28.7 27.8 96.6 25.9 Example S38
Composition S3 31.0 28.7 92.4 22.5 Example S39 Composition S4 29.1
27.3 93.7 25.6 Example S40 Composition S5 34.0 31.9 94.0 21.8
Example S41 Composition S6 24.0 25.5 106.5 15.5 Example S42
Composition S7 21.2 22.6 106.8 18.0 Adhesion test 2 Dentin Zirconia
Adhesive Initial Adhesive strength Maintenance adhesive strength
Maintenance after storage rate strength after storage rate (MPa)
(%) (MPa) (MPa) (%) Example S1 25.0 98.5 31.0 31.3 101.2 Example S2
22.2 98.9 30.7 31.2 101.6 Example S3 27.7 108.9 31.6 31.2 98.9
Example S4 19.1 92.2 31.0 31.5 101.8 Example S5 21.8 90.7 30.6 27.6
90.4 Example S6 14.3 90.5 24.1 23.0 95.4 Example S7 15.6 96.7 20.9
19.8 94.5 Example S8 19.7 91.8 33.4 32.4 96.8 Example S9 21.4 107.6
30.3 30.9 101.9 Example S10 18.3 95.6 32.2 33.8 105.1 Example S11
19.9 99.8 28.1 27.9 99.1 Example S12 24.8 101.6 31.9 32.3 101.3
Example S13 17.6 94.5 23.0 23.6 102.4 Example S14 13.3 94.2 20.3
20.2 99.6 Example S15 23.8 100.3 32.1 28.9 90.1 Example S16 25.8
102.4 30.3 31.9 105.0 Example S17 22.1 107.4 29.0 30.9 106.6
Example S18 21.3 104.6 28.7 31.3 108.8 Example S19 22.8 100.4 31.8
34.1 107.4 Example S20 14.9 100.9 23.7 24.6 103.8 Example S21 19.6
106.8 20.1 21.0 104.5 Example S22 21.6 108.7 30.5 30.1 98.7 Example
S23 21.5 93.2 30.6 32.8 107.2 Example S24 20.4 92.0 31.9 33.3 104.2
Example S25 22.9 94.2 28.5 30.3 106.1 Example S26 26.5 106.4 32.6
30.2 92.8 Example S27 16.3 92.0 20.7 19.0 92.1 Example S28 16.0
100.5 20.4 21.0 102.6 Example S29 21.4 93.1 29.4 28.0 95.1 Example
S30 21.1 109.4 32.8 30.1 91.8 Example S31 23.7 97.3 30.2 31.9 105.5
Example S32 23.4 99.1 29.7 28.6 96.3 Example S33 22.9 93.8 28.8
31.3 108.5 Example S34 12.0 95.5 21.7 21.8 100.5 Example S35 16.5
91.6 23.9 22.0 92.1 Example S36 22.9 108.7 32.7 30.6 93.6 Example
S37 26.0 100.4 33.9 33.6 99.4 Example S38 21.6 96.2 33.3 34.2 102.7
Example S39 25.9 101.2 29.8 30.8 103.2 Example S40 22.5 103.4 29.9
28.6 95.8 Example S41 16.6 107.3 24.2 25.5 105.1 Example S42 16.2
90.1 20.5 21.6 105.5
[0214] Examples S1 to S42 showed good adhesive property and
maintenance rate. In particular, kits S1 to S5, S8 to S12, S15 to
S19, S22 to S26, S29 to S33 and S36 to S40 showed extremely high
adhesive property, and a synergistic effect exhibited by containing
(A-1) polymerizable monomer having an acidic group and (D-1)
aliphatic tertiary amine compound represented by formula (1) in the
dental adhesive composition and containing a photoacid generator in
the curable composition was confirmed.
[0215] The dental adhesive composition of the present disclosure
evaluated in Examples can be used for any known dental adhesive
material, dental composite resin, dental core build-up material,
dental resin cement, dental coating material, dental sealant
material, dental manicure material, dental splinting material and
dental glass ionomer cement and the like.
[0216] With respect to the use of substantially any plural and/or
singular terms herein, those having skill in the art can translate
from the plural to the singular and/or from the singular to the
plural as is appropriate to the context.
[0217] Although the description herein has been given with
reference to the drawings and embodiments, it should be noted that
those skilled in the art may make various changes and modifications
on the basis of this disclosure without difficulty. Accordingly,
any such changes and modifications are intended to be included in
the scope of the embodiments.
INDUSTRIAL APPLICABILITY
[0218] According to the present disclosure, it is possible to
provide a dental adhesive composition having excellent storage
stability and adhesive strength.
* * * * *