U.S. patent application number 17/057188 was filed with the patent office on 2021-05-06 for polymerization initiator, curable composition, dental material, and preparation kit for curable composition.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. The applicant listed for this patent is MITSUI CHEMICALS, INC.. Invention is credited to Yoko KOSUGI, Takenori MITAMURA.
Application Number | 20210130580 17/057188 |
Document ID | / |
Family ID | 1000005371301 |
Filed Date | 2021-05-06 |
United States Patent
Application |
20210130580 |
Kind Code |
A1 |
MITAMURA; Takenori ; et
al. |
May 6, 2021 |
POLYMERIZATION INITIATOR, CURABLE COMPOSITION, DENTAL MATERIAL, AND
PREPARATION KIT FOR CURABLE COMPOSITION
Abstract
Provided is a polymerization initiator, which has an excellent
curing rate and is an alternative to a polymerization initiator
system using a benzoyl peroxide-aromatic amine compound, a curable
composition containing the polymerization initiator, a dental
material and dental filler material containing the composition, and
a kit for preparing the curable composition. The polymerization
initiator contains one or more compounds (A) selected from the
group consisting of a pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1), a salt (A2) of the compound
(A1), and a malonate compound (A3).
Inventors: |
MITAMURA; Takenori;
(Chiba-shi, Chiba, JP) ; KOSUGI; Yoko;
(Ichihara-shi, Chiba, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUI CHEMICALS, INC. |
Minato-ku, Tokyo |
|
JP |
|
|
Assignee: |
MITSUI CHEMICALS, INC.
Minato-ku, Tokyo
JP
|
Family ID: |
1000005371301 |
Appl. No.: |
17/057188 |
Filed: |
August 2, 2019 |
PCT Filed: |
August 2, 2019 |
PCT NO: |
PCT/JP2019/030517 |
371 Date: |
November 20, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 4/10 20130101; C08K
5/092 20130101; C08F 20/10 20130101; C08K 5/0025 20130101; C08K
5/3445 20130101; C08K 5/14 20130101 |
International
Class: |
C08K 5/3445 20060101
C08K005/3445; C08F 20/10 20060101 C08F020/10; C08F 4/10 20060101
C08F004/10; C08K 5/00 20060101 C08K005/00; C08K 5/14 20060101
C08K005/14; C08K 5/092 20060101 C08K005/092 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 9, 2018 |
JP |
2018-150314 |
Oct 29, 2018 |
JP |
2018-202660 |
Claims
1. A polymerization initiator comprising one or more compounds (A)
selected from the group consisting of a pyrazolidinedione compound
and/or pyrazolidine(di)thione compound (A1), a salt (A2) of the
compound (A1), and a malonate compound (A3).
2. The polymerization initiator according to claim 1, wherein the
compound (A) is one or more compounds selected from the group
consisting of a pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1), and a salt (A2) of the
compound (A1).
3. The polymerization initiator according to claim 1, wherein the
pyrazolidinedione compound and/or pyrazolidine(di)thione compound
(A1) is represented by the following general formula (1),
##STR00005## wherein R.sup.1 is a hydrogen atom or a hydrocarbon
group having 1 to 20 carbon atoms which may have a substituent, and
the hydrocarbon group may contain a hetero atom, R.sup.2 and
R.sup.3 are independently a hydrogen atom or a hydrocarbon group
having 1 to 12 carbon atoms which may have a substituent, and the
hydrocarbon group may contain a hetero atom, X represents an oxygen
atom or a sulfur atom, and R.sup.2 and R.sup.3 may be directly
bonded to each other to form a cyclic hydrocarbon group having 3 to
12 carbon atoms.
4. The polymerization initiator according to claim 1, which
comprises a transition metal compound (B).
5. The polymerization initiator according to claim 4, wherein the
transition metal compound (B) is a copper compound.
6. A curable composition comprising the polymerization initiator as
defined claim 1 and a polymerizable monomer (C).
7. The curable composition according to claim 6, comprising at
least one selected from the group consisting of a peroxide (D), a
filler (E), a reducing agent (F), and an aqueous solvent (G).
8. The curable composition according to claim 6, which comprises a
photopolymerization initiator (H).
9. A dental material comprising the curable composition as defined
in claim 6.
10. A dental filler material comprising the curable composition as
defined in claim 6.
11. A separately packed polymerization initiator comprising a first
pack containing the compound (A) as defined in claim 1 and a second
pack containing a transition metal compound (B).
12. A kit for preparing a curable composition, comprising a first
pack containing the compound (A) as defined in claim 1, and a
second pack containing a transition metal compound (B), wherein at
least one of the first pack and the second pack contains a
polymerizable monomer (C).
Description
TECHNICAL FIELD
[0001] The present invention relates to a polymerization initiator,
a curable composition, a dental material, and a kit for preparing a
curable composition.
BACKGROUND ART
[0002] In recent years, various restorative materials have been
used in dental treatment. Of these, dental curable compositions
containing a radical polymerizable monomer and a radical
polymerization initiator that are capable of curing the
polymerizable monomers under appropriate conditions are widely
used. Specific examples of the dental curable composition include
dental adhesive resin cements, dental composite resins (including
dental self-adhesive composite resins), dental adhesives, dental
backing materials, dental root canal fillers, orthodontic
adhesives, mobile tooth fixing materials, tooth fovea fissure
sealant (dental sealant), dental room-temperature polymerization
resins, and the like, and they are used in actual dental
practice.
[0003] The main types of radical polymerization initiators
contained in dental curable compositions are photopolymerization
initiators, which cause polymerization and curing through
irradiation with visible light, and chem cal polymerization
initiators, which cause polymerization and curing by mixing two or
more separately stored packs immediately before use. Recently, dual
cure type products containing both initiators have been also widely
used in dental practice.
[0004] Among the radical polymerization initiators, the
photopolymerization initiator is characterized in that
polymerization inhibition by oxygen is relatively small in the
course of the polymerization, and it is easy to obtain a high
polymerization rate by irradiating visible light for a short time.
On the other hand, since it is difficult to adapt to a part where
light of an irradiator is difficult to reach, such as when a
treatment part is a shaded part of a cavity or a deep part of a
tooth, in that case, a dental curable composition containing a
chemical polymerization initiator is mainly used.
[0005] One of common chemical polymerization initiator systems is a
redox polymerization initiator, which combines an oxidizing agent
and a reducing agent. A curable composition containing a redox
polymerization initiator is usually divided into a first pack
including an oxidizing agent and a second pack including a reducing
agent and stored until immediately before use, and the first pack
and the second pack are mixed at the time of use. For example, a
polymerization initiator system using a first pack including
benzoyl peroxide as the oxidizing agent and a second pack including
an aromatic amine compound as the reducing agent is known (see, for
example, Patent Literature 1).
CITATION LIST
Patent Literature
[0006] Patent Literature 1: JP 5878065 B1
SUMMARY OF INVENTION
Technical Problem
[0007] A curable composition for dental use is required to have an
appropriate curing time for performing an operation. However, a
polymerization initiator system using a benzoyl peroxide-aromatic
amine compound described in Patent Literature 1 and the like has
room for improvement in terms of curing time, and when the addition
amount of benzoyl peroxide and/or aromatic amine is increased in
order to improve curing rate, a cured product after curing may
change from yellow to brown, or the composition may be easily cured
during storage. Therefore, it is required a polymerization
initiator system having an appropriate curing rate, which is an
alternative to the polymerization initiator system using a benzoyl
peroxide-aromatic amine compound.
[0008] The present invention has been made in view of the above
circumstances, and an object thereof is to provide a polymerization
initiator, which has an excellent curing rate and is an alternative
to the polymerization initiator system using a benzoyl
peroxide-aromatic amine compound, a curable composition containing
the polymerization initiator, a dental material and dental filler
material containing the composition, and a kit for preparing the
curable composition.
Solution to Problem
[0009] The present inventors have found that a pyrazolidinedione
compound, a pyrazolidine(di)thione compound and salts of these
compounds known as anti-inflammatory agents can be used as a
polymerization initiator, and a malonate compound can be used as a
polymerization initiator, the compound (salt) exhibits an excellent
curing rate when used in combination with a transition metal, and
the cured product is suitable for a dental material, thereby
completing the present invention.
[0010] The present invention includes matters described in
following [1] to [12]. [0011] [1] A polymerization initiator
containing one or more compounds selected from the group consisting
of a pyrazolidinedione compound and/or pyrazolidine(di)thione
compound (A1), a salt (A2) of the compound (A1), and a malonate
compound (A3). [0012] [2] The polymerization initiator according to
[1], wherein the compound (A) is one or more compounds selected
from the group consisting of a pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1), and a salt (A2) of the
compound (A1). [0013] [3] The polymerization initiator according to
[1] or [2], wherein the pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1) is represented by the
following general formula (1).
##STR00001##
[0014] wherein R.sup.1 is a hydrogen atom or a hydrocarbon group
having 1 to 20 carbon atoms which may have a substituent, and the
hydrocarbon group may contain a hetero atom,
[0015] R.sup.2 and R.sup.3 are independently a hydrogen atom or a
hydrocarbon group having 1 to 12 carbon atoms which may have a
substituent, and the hydrocarbon group may contain a hetero
atom,
[0016] X represents an oxygen atom or a sulfur atom, and R.sup.2
and R.sup.3 may be directly bonded to each other to form a cyclic
hydrocarbon group having 3 to 12 carbon atoms. [0017] [4] The
polymerization initiator according to any one of [1] to [3], which
contains a transition metal compound (B). [0018] [5] The
polymerization initiator according to [4], wherein the transition
metal compound (B) is a copper compound. [0019] [6] A curable
composition containing the polymerization initiator as defined in
any one of [1] to [5] and a polymerizable monomer (C). [0020] [7]
The curable composition according to [6], including at least one
selected from the group consisting of a peroxide (D), a filler (E),
a reducing agent (F), and an aqueous solvent (G). [0021] [8] The
curable composition according to [6] or [7], which contains a
photopolymerization initiator (H). [0022] [9] A dental material
containing the curable composition as defined in any one of [6] to
[8]. [0023] [10] A dental filler material containing the curable
composition as defined in any one of [6] to [8]. [0024] [11] A
separately packed polymerization initiator including a first pack
containing the compound (A) as defined in [1] and a second pack
containing a transition metal compound (B). [0025] [12] A kit for
preparing a curable composition, including a first pack containing
the compound (A) as defined in [1], and a second pack containing a
transition metal compound (B), wherein at least one of the first
pack and the second pack contains a polymerizable monomer (C).
Advantageous Effects of Invention
[0026] According to the present invention, it is possible to
provide a polymerization initiator, which has an excellent curing
rate and is an alternative to the polymerization initiator system
using a benzoyl peroxide-aromatic amine compound, a curable
composition in which a cured product of the composition is
particularly suitable for a dental material by containing the
polymerization initiator, and a kit for preparing a curable
composition.
DESCRIPTION OF EMBODIMENTS
[0027] The present invention will be described in detail below.
[0028] <Polymerization Initiator>
[0029] The polymerization initiator which is one embodiment of the
present invention includes one or more compounds (A) selected from
the group consisting of a pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1), a salt (A2) of the compound
(A1), and a malonate compound (A3). These compounds (salts) are
compounds having a conjugated structure in which two carbonyl
groups (ketone groups) or thioxo groups (thioketone groups) are
bonded to one carbon atom.
[0030] (Pyrazolidinedione Compound and/or Pyrazolidine(di)thione
Compound (A1))
[0031] The polymerization initiator may contain a pyrazolidinedione
compound and/or pyrazolidine(di)thione compound (A1) (hereinafter,
also simply referred to as "compound (A1)").
[0032] The pyrazolidinedione compound of the present invention is a
compound having a skeleton in which carbon atoms at positions 3 and
5 of pyrazoljdine are substituted with ketone groups.
Pyrazolidine(di)thione compound means a pyrazolidinethione compound
or a pyrazolidinedithione compound, and the former is a compound
having a pyrazolidine skeleton in which a carbon atom at position 3
of pyrazolidine is substituted with a thioketone group, and the
latter is a compound having a pyrazolidine skeleton in which carbon
atoms at positions 3 and 5 of pyrazolidine are substituted with
thioketone groups. It is presumed that these skeletons contribute
to the effect of the present invention.
[0033] The pyrazolidinedione compound and/or pyrazolidine(di)thione
compound (A1) that can be contained in the polymerization initiator
of the present invention is preferably a compound represented by
the following general formula (1), in that excellent polymerization
properties can be imparted.
##STR00002##
[0034] In the general formula (1), R.sup.1 is a hydrogen atom or a
hydrocarbon group having 1 to 20 carbon atoms which may have a
substituent, and the hydrocarbon group has preferably 1 to 14
carbon atoms, and more preferably 1 to 8. The hydrocarbon group may
contain a hetero atom, for example, a sulfur atom, an oxygen atom,
a nitrogen atom, or the like. Further, the hydrocarbon group may be
a saturated hydrocarbon group or an unsaturated hydrocarbon group.
When R.sup.1 is a hydrocarbon group, it may be an aromatic
hydrocarbon group (aryl group (phenyl group, naphthyl group, toluyl
group, benzyl group, benzoyl group), heteroaryl group (pyridyl
group, etc.), aliphatic hydrocarbon group (alicyclic hydrocarbon
group (cyclohexyl group, cyclopentyl group, etc.)) or a chain
hydrocarbon group (alkyl group, alkenyl group, etc.), among which
the chain hydrocarbon group is preferred. Among the chain
hydrocarbon groups, a chain alkyl group having 1 to 14 carbon atoms
is preferable, a chain alkyl group having 2 to 12 carbon atoms is
more preferable, and a chain alkyl group having 3 to 8 carbon atoms
is particularly preferable.
[0035] R.sup.2 and R.sup.3 are independently a hydrogen atom or a
hydrocarbon group having 1 to 12 carbon atoms which may have a
substituent. In the case of a hydrocarbon group, they may be an
aromatic hydrocarbon group (aryl group (phenyl group, naphthyl
group, toluyl group, benzyl group, benzoyl group, etc.), a
heteroaryl group (pyridyl group, etc.)), an aliphatic hydrocarbon
group (alicyclic hydrocarbon group (cyclohexyl group, cyclopentyl
group, etc.) or a chain hydrocarbon group (alkyl group, alkenyl
group, etc.), and the aromatic hydrocarbon group is more preferred.
Among the aromatic hydrocarbon groups, the phenyl group is
particularly preferable. Moreover, R.sup.2 and R.sup.3 may be
directly bonded to each other to form a cyclic hydrocarbon group
having 3 to 12 carbon atoms. Further, the hydrocarbon group may
contain a hetero atom, for example, a sulfur atom, an oxygen atom,
a nitrogen atom, or the like. Furthermore, the hydrocarbon group
may be a saturated hydrocarbon group or an unsaturated hydrocarbon
group.
[0036] X is an oxygen atom or a sulfur atom, and preferably an
oxygen atom.
[0037] When R.sup.1, R.sup.2 and R.sup.3 are hydrocarbon groups,
examples of a substituent that R.sup.1, R.sup.2 and R.sup.3 may
have include a halogen atom, a hydroxyl group, a carboxy group, an
alkoxy group, an oxo group, an amino group, an amide group, a nitro
group, a cyano group, a sulfide group, a sulfinyl group, a sulfoxy
group, and the like.
[0038] Molecular weight of the pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1) that can be contained in the
polymerization initiator of the present invention may be, for
example, 100 to 800, and is preferably 150 to 600, and more
preferably 200 to 500.
[0039] Examples of the pyrazolidinedione compound include
1,2-diphenyl-3,5-pyrazolidinedione,
4-butyl-1,2-diphenyl-3,5-pyrazolidinedione (phenylbutazone),
1,2-diphenyl-4-propyl-3,5-pyrazolidinedione,
4-(1-methylethyl)-1,2-diphenyl-3,5-pyrazolidinedione,
1,2-diethyl-3,5-pyrazolidinedione,
1,2-dimethyl-4-(3-oxobutyl)-1,2-diphenyl-3,5-pyrazolidinedione
(ketophenylbutazone),
4-(2-oxopropyl)-1,2-diphenyl-3,5-pyrazolidinedione,
4-butyl-1,2-dimethyl-3,5-pyrazolidinedione,
4-(3-hydroxybutyl)-1,2-diphenyl-3,5-pyrazolidinedione
(.alpha.-hydroxyphenylbutazone),
4-butyl-1-(4-hydroxyphenyl)-2-phenyl-3,5-pyrazolidinedione
(oxyphenbutazone),
1-(4-(benzyloxy)phenyl)-4-butyl-2-phenyl-3,5-pyrazolidinedione
(4'-O-benzyloxyphenbutazone),
1,2-diphenyl-4-[2-(phenylsulfinyl)ethyl]-3,5-pyrazolidinedione
(sulfinpyrazone),
4-(2-aminoethyl)-1,2-diphenyl-3,5-pyrazolidinedione,
4-(3-methyl-2-butenyl)-1,2-diphenyl-3,5-pyrazolidinedione
(feprazone),
4-(4,4-dimethyl-3-ozophenyl)-1,2-diphenyl-3,5-pyrazolidinedione
(tribuzone),
4,4'-(4-butyl-3,5-dioxopyrazolidine-1,2-diyl)dibenzenesulfonamide
(butacuglionamide),
4-[2-(methylthio)ethyl]-1,2-diphenyl-3,5-pyrazolidinedione,
1,2-dimethyl-3,5-pyrazolidine-4-carbonitrile,
2-[(2-tetrahydrofuranyl)methyl]-1H-benzo[c]pyrazolo[1,2-a]cinnoline-1,3(2-
H)-dione (cinnofuradione) and
1,1',2,2'-tetraphenyl-(4,4'-bipyrazolidine)-3,3',5,5'-tetrone and
the like; and examples of the pyrazolidine(di)thione compound
include 1,2-diphenyl-3,5-pyrazolidinedione,
4-butyl-1,2-diphenyl-3,5-pyrazolidinedithione, and the like.
[0040] Of these, phenylbutazone and
4-butyl-1,2-diphenyl-3,5-pyrazolidinedithione are preferable, and
phenylbutazone is particularly preferable.
[0041] The compound (A1) can be produced by a known method. For
example, in the case of phenylbutazone, it can be obtained by
heating and refluxing hydrazobenzene and diethyl butylmalonate is
the presence of sodium sulfite using methanol as a solvent, and
oxidizing the obtained phenylbutazone salt with acetic acid.
[0042] In addition, a commercially available product can be
purchased as the compound (A1). As the commercially available
product, for example, phenylbutazone can be purchased from Tokyo
Chemical Industry Co., Ltd., FUJIFILM Wako Pure Chemical
Corporation, and the like. The compound (A1) may be used alone or
in combination of two kinds.
[0043] (Salt (A2) of Compound (A1))
[0044] The polymerization initiator may contain a salt (A2) of the
compound (A1) (i.e., a salt of a pyrazolidinedione compound and/or
a salt of a pyrazolidine(di)thione compound) (hereinafter, also
simply referred to as "salt (A2)").
[0045] The salt (A2), like the compound (A1), is excellent in that
it can give a curing rate and excellent mechanical strength. In
addition, the salt (A2) is excellent in usability because it does
not easily cure during storage when it is added to the curable
composition in a large amount.
[0046] The type of salt of the salt (A2) is not particularly
limited, but a metal salt is preferable. The metal is not
particularly limited, but is preferably one or more metals selected
from the group consisting of alkali metals, alkaline earth metals
and transition metals, and more preferably one or more metals
selected from the group consisting of alkali metals and alkaline
earth metals.
[0047] Examples of the alkali metal include lithium, sodium,
potassium, and the like.
[0048] Examples of the alkaline earth metal include magnesium,
calcium, strontium, and the like.
[0049] Examples of the transition metal salt include copper,
vanadium, titanium, manganese, iron, cobalt, nickel, and the
like.
[0050] Of these, the salt (A2) is preferably one or more metals
selected from the group consisting of calcium and sodium.
[0051] The salt (A2) is preferably a salt of the compound
represented by the general formula (1), while maintaining
sufficient polymerization properties, in that excellent operability
can be imparted, and more preferably a salt represented by the
following general formula (2).
##STR00003##
[0052] In the general formula (2), R.sup.1, R.sup.2, R.sup.3 and X
have the same meaning as in the general formula (1). Further, in
the general formula (2), preferred embodiments and specific
examples of R.sup.1, R.sup.2, R.sup.3 and X are the same as those
in the general formula (1). Furthermore, in the general formula
(2), M.sup.n+ represents an n-valent metal cation, and n represents
an integer of 1 to 5.
[0053] The metal M in M.sup.n+ is the same as a metal in a metal
salt of the salt (A2). That is, the metal is preferably one or more
metals of alkali metals, alkaline earth metals and transition
metals, more preferably one or more metals selected from the group
consisting of alkali metals and alkaline earth metals, and further
preferably one or more metals selected from the group consisting of
calcium ion and sodium ion.
[0054] The compound (A1) constituting the salt (A2) may have a
molecular weight of, for example, 100 to 800, and is preferably 150
to 600, and more preferably 200 to 500.
[0055] Examples of the salt of the pyrazolidinedione compound and
the salt of the pyrazolidine(di)thione compound include salts of
pyrazolidinedione compounds such as phenylbutazone, and
pyrazolidine(di)thione compounds such as
4-butyl-1,2-diphenyl-3,5-pyrazolidinedithione, exemplified as the
pyrazolidinedione compound and/or the pyrazolidine(di)thione
compound in the section of (Pyrazolidinedione compound and/or
pyrazolidine(di)thione compound (A1)).
[0056] Of these, salts of phenylbutazone and
4-butyl-1,2-diphenyl-3,5-pyrazolidinedithione are preferable, and
salts of phenylbutazone are particularly preferable.
[0057] The salt (A2) can be produced by a known method example, in
the case of the salt of phenylbutazone, the salt of phenylbutazone
can be obtained by heating and refluxing hydrazobenzene and diethyl
butylmalonate is the presence of sodium sulfite using methanol as a
solvent.
[0058] In addition, a commercially available product can be
purchased as the salt (A2). As the commercially available product,
for example, phenylbutazone calcium and phenylbutazone sodium can
be purchased from Woongjin Chemical Co., Ltd., and the like. The
salts (A2) may be used alone or in combination of two kinds.
[0059] (Malonate Compound (A3))
[0060] The polymerization initiator may contain a malonate compound
(A3) (hereinafter, also simply referred to as "compound (A3)"). The
malonate compound (A3) is a compound having an ester bond in at
least one carboxy group of malonic acid, and is preferably a
malonate compound represented by the following general formula
(3).
##STR00004##
[0061] wherein R.sup.4 and R.sup.5 are each independently a
hydrocarbon group having 1 to 12 carbon atoms which may have a
substituent, and the hydrocarbon group may contain a hetero atom,
R.sup.6 is a hydrocarbon group having 1 to 20 carbon atoms which
may have a substituent, and the hydrocarbon group may contain a
hetero atom.
[0062] Examples of the compound (A3) include diethyl phenylmalonate
(DEPM), triethyl methanetricarboxylate (TEMTC), diethyl
methylmalonate, diethyl ethylmalonate, diethyl allylmalonate,
dimethyl methoxymalonate, dimethyl benzylmalonate, dimethyl
cyclopentylmalonate, diethyl benzoylmalonate, diethyl
2-(2-cyanoethyl)malonate, diethyl phthalimidomalonate, diethyl
2-acetylmalonate, and the like. Of these, diethyl phenylmalonate
and triethyl methanetricarboxylate are preferable, and diethyl
phenylmalonate is more preferable.
[0063] The compound (A3) can be produced by a known method. For
example, in the case of diethyl phenylmalonate, ethyl oxalate is
reacted with ethyl phenylacetate in an ethanol solution in which
sodium is dissolved, and phenyloxaloacetate is released from the
obtained sodium salt with sulfuric acid, it can be synthesized by
heating under reduced pressure to remove carbon monoxide
produced.
[0064] Further, for example, in the case of triethyl
methanetricarboxylate, it can be synthesized by reacting anhydrous
alcohol, magnesium carbon tetrachloride and diethyl malonate,
reacting the obtained diethyl ethoxymagnesiomalonate with ethyl
chloroformate in the presence of diethyl ether, and decomposing the
obtained reaction product with dilute acetic acid.
[0065] In addition, a commercially available product can be
purchased as the compound (A3). As the commercially available
product, for example, diethyl phenylmalonate and triethyl
methanetricarboxylate can be purchased from FUJIFILM Wako Pure
Chemical Corporation, Tokyo Chemical Industry Co., Ltd., Kanto
Chemical Co., Inc and the like. The compound (A3) may be used alone
or in combination of two kinds.
[0066] The compound (A1), salt (A2) and compound (A3) may be used
in any combination. That is, they may be used in combinations of
compound (A1) and salt (A2), salt (A2) and compound (A3), compound
(A1) and compound (A3), and compound (A1), salt (A2) and compound
(A3).
[0067] (Transition Metal Compound (B))
[0068] The polymerization initiator of the present invention
preferably contains a transition metal compound (B). Polymerization
starts by using the compound (A) and a transition metal compound
(B) together in the presence of a polymerizable monomer (C)
described later. In addition, it is preferable that the transition
metal compound (B) is stored as a separately packed polymerization
initiator described later so that the transition metal compound (B)
does not contact and react with the compound (A) during storage.
Moreover, the transition metal compound (B) does not include a
transition metal salt of the salt (A2).
[0069] Examples of the transition metal compound (B) include copper
compounds, molybdenum compounds, vanadium compounds, scandium
compounds, titanium compounds, chromium compounds, manganese
compounds, iron compounds, cobalt compounds, nickel compounds, and
the like.
[0070] Examples of the copper compound include monovalent or
divalent copper compounds such as copper acetylacetonate, copper
oleate, copper acetate, copper gluconate, copper citrate, copper
phthalate, copper naphthenate, copper hydroxide, copper methoxide,
copper ethoxide, copper isopropoxide, copper chloride, and copper
bromide.
[0071] The vanadium compound is preferably at least one compound
selected from trivalent to pentavalent vanadium compounds, and
examples thereof include vanadium(III) acetylacetonate,
vanadium(III) naphthenate, vanadyl stearate, vanadium
benzoylacetonate, bis(maltolate) oxovanadium(IV),
oxobis(1-phenyl-1,3-butanedionate) vanadium (IV), and vanadyl(IV)
acetylacetonate.
[0072] Examples of the molybdenum compound include molybdenum(IV)
oxide, molybdenum oxide acetylacetonate, molybdenium ethoxide,
bis(2,4-pentadionato)molybdenium oxide, molybdenyl
diethyldithiocarbamate, and the like.
[0073] Examples of the iron compound include divalent or trivalent
iron compounds such as iron acetylacetonate, ferrocene, iron
acetate, iron stearate, iron 2-ethylhexanoate, iron oxalate, iron
citrate, iron gluconate, iron nitrate, iron sulfate, iron
phosphate, iron perchlorate, iron oxide, iron sulfide, iron
fluoride, iron chloride, iron bromide, potassium hexacyanoferrate,
and iron ethoxide.
[0074] Examples of the cobalt compound include divalent or
trivalent cobalt compounds such as cobalt acetylacetonate, cobalt
acetate, cobalt naphthenate, cobalt oleate, cobalt stearate, cobalt
2-ethylhexanoate, cobalt benzoate, cobalt oxalate, cobalt citrate,
cobalt carbonate, cobalt nitrate, cobalt sulfate, cobalt phosphate,
cobalt perchlorate, cobalt thiocyanate, cobalt oxide, cobalt
sulfide, cobalt fluoride, cobalt chloride, cobalt bromide, cobalt
hydroxide, and cobalt isopropoxide.
[0075] Examples of the nickel compound include divalent nickel
compounds such as nickel acetylacetonate, bis(dithiobenzil)nickel,
bis(cyclopentadienyl)nickel, nickel formate, nickel acetate, nickel
lactate, nickel naphthenate, nickel 2-ethylhexanoate, nickel
oxalate, nickel citrate, nickel stearate, nickel perchlorate,
nickel oxide, nickel sulfide, nickel fluoride, nickel chloride,
nickel bromide, nickel iodide, nickel carbonate, nickel nitrate,
nickel sulfate, nickel hydroxide, and nickel ethoxide.
[0076] Examples of the scandium compound include scandium(III)
iodide and the like. Examples of the titanium compound include
titanium(IV) chloride, titanium(IV) tetraisopropoxide, and the
like. Examples of the chromium compound include chromium(II)
chloride, chromium(III) chloride, chromic acid, chromate, and the
like. Examples of the manganese compound include manganese(II)
chloride, manganese(II) acetate, manganese(II) oxide,
manganese(III) oxide, manganese(II) nitrate, and the like.
[0077] Among these transition metals, a copper compound is
preferable because it has high polymerization properties to be
imparted to the composition.
[0078] The transition metal compound (B) may be used singly or in
combination of two or more thereof. Further, the content of the
transition metal compound (B) in the polymerization initiator of
the present invention is preferably 0.0001 to 200 parts by mass,
more preferably 0.0005 to 150 parts by mass, and particularly
preferably 0.001 to 100 parts by mass, based on 100 parts by mass
of the compound (A).
[0079] <Separately Packed Polymerization Initiator>
[0080] Another embodiment of the present invention is a separately
packed polymerization initiator including a first pack containing
the compound (A) and a second pack containing the transition metal
compound (B).
[0081] By storing the compound and the transition metal compound
(B) in separate containers or the like, it can be stored without
reacting the compound (A) with the transition metal compound (B)
during storage.
[0082] The content of the transition metal compound (B) in the
second pack is preferably 0.0001 to 200 parts by mass, more
preferably 0.0005 to 150 parts by mass, and particularly preferably
0.001 to 100 parts by mass, based on 100 parts by mass of the
compound (A) in the first pack.
[0083] <Curable Composition>
[0084] (Polymerizable Monomer (C))
[0085] The curable composition according to another embodiment of
the present invention contains the polymerization initiator and a
polymerizable monomer (C). Herein, "(meth)acryl" means acryl or
methacryl, and for example, "(meth)acrylic acid" means acrylic acid
or methacrylic acid. Similarly, "(meth)acryloyl" means "acryloyl"
or "methacryloyl", and "(meth)acrylate" means "acrylate" or
"methacrylate".
[0086] The polymerizable monomer (C) is not particularly limited as
long as polymerization can be initiated by the polymerization
initiator of the present invention, and examples thereof include a
radical polymerizable monomer. Further, the radical polymerizable
monomer preferably has, as a radical polymerizable unsaturated
group, a (meth)acryloyl group, a (meth)acrylamide group, a styryl
group, a vinyl group, an allyl group or the like, more preferably
has a (meth)acryloyl group or a (meth)acrylamide group, and further
preferably has a methacryloyl group.
[0087] Examples of the radical polymerizable monomer include
hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate, and 10-hydroxydecyl (meth)acrylate;
monofunctional monomers such as 2-(dimethylamino)ethyl
methacrylate, N-methyl-N-phenylaminoethyl (meth)acrylate,
N-ethyl-N-phenylaminoethyl (meth)acrylate, propyleneglycol
mono(meth)acrylate, glycerol mono(meth)acrylate, erythritol
mono(meth)acrylate, and N-hydroxyethyl(meth)acrylamide;
bifunctional monomers having an aromatic ring such as
2,2-bis((meth)acryloyloxyphenyl)propane,
2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy) phenyl]propane
(commonly known as "Bis-GMA"); bifunctional monomer having an
aliphatic carbon chain such as glycerol di(meth)acrylate,
triethyleneglycol di(meth)acrylate, neopentylglycol
di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
2,2,4-trimethylhexamethylene bis(2-carbamoyloxyethyl)
dimethacrylate (commonly known as "UDMA"),
1,2-bis(3-(meth)acryloyloxy-2-hydroxypropoxy)ethane, and
1,6-hexanediol dimethacrylate (HexDMA); trifunctional or more
polyfunctional monomers such as trimethylolpropane
tri(meth)acrylate, tris(2-(meth)acryloxyethyl)isocyanurate, and
dipentaerythritol penta(meth)acrylate; polymerizable monomers
synthesized by addition reaction of a compound having an isocyanate
group (--NCO) such as hexamethylene diisocyanate (HDI), tolylene
diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane
diisocyanate (MDI), isophorone diisocyanate (IPDI),
trimethylhexamethylene diisocyanate (TMHMDI) or norbornane
diisocyanate (NBDI) with a (meth)acrylate group having a hydroxyl
group (--OH) such as 2-hydroxyethyl (meth)acrylate or
2-hydroxypropyl (meth)acrylate (for example, described in WO
2012/157566 A, WO 2015/015220 A, WO 2015/015221 A, and JP
2016-094482 A); acid group-containing polymerizable monomers
containing a carboxylic acid group (4-methacryloyloxyethyl
trimellitic acid (4-MET), etc.), a carboxylic acid anhydride group,
a phosphoric acid group (10-methacryloyloxydecyl dihydrogen
phosphate (MDP), etc.), a thiophosphoric acid, a pyrophosphate
group, a thiopyrophosphate group, a phosphonic acid group,
thiophosphonic acid group, a sulfonic acid group and the like in
the same compound, and those in which these acidic groups are in
the form of an acid chloride, an alkali metal salt, an alkaline
earth metal salt, an ammonium salt, and the like; organosilicon
compounds having a polymerizable group such as
.gamma.-methacryloxyalkyltrimethoxysilane (.gamma.-MPTS); and the
like.
[0088] Among these, from the viewpoint of physical properties and
ease of handling, 2,2,4-trimethylhexamethylene
bis(2-carbamoyloxyethyl) dimethacrylate (UDMA), bisphenol A
diglycidyl methacrylate (Bis-GMA), 2-hydroxyethyl methacrylate
(HEMA), triethylene glycol dimethacrylate (TEGDMA), 1,6-hexanediol
dimethacrylate (HexDMA), NBDI-HEA (synthetic compound of norbornane
diisocyanate and 2-hydroxyethyl acrylate), 10-methacryloyloxydecyl
dihydrogen phosphate (MDP) and 4-methacryloyloxyethyl trimellitic
acid (4-MET) are preferred.
[0089] The polymerizable monomer (C) may be used singly or in
combination of two or more thereof. Further, the content of the
polymerizable monomer (C) in the curable composition of the present
invention is preferably 100 to 100,000 parts by mass, more
preferably 500 to 50,000 parts by mass, and particularly preferably
1,000 to 20,000 parts by mass, based on 100 parts by mass of the
polymerization initiator 100 parts by mass of pyrazolidinedione
salt compound and/or pyrazolidine(di)thione salt compound (A2).
[0090] The curable composition of the present invention preferably
contains at least one selected from the group consisting of a
peroxide (D), a filler (E), a reducing agent (F), and an aqueous
solvent (G). Further, the curable composition of the present
invention may contain a photopolymerization initiator (H).
[0091] (Peroxide (D))
[0092] A peroxide (D) is preferably contained in the curable
composition of the present invention, in that polymerization
properties of the composition are improved and the obtained cured
product tends to have excellent mechanical strength and adhesive
strength. Examples of the peroxide (D) include peroxy ester
compounds, hydroperoxide compounds, alkyl peroxides, and the like.
Of these, the peroxyester compound is preferable from the viewpoint
of storage stability and reactivity.
[0093] As the peroxyester compound, any known one can be used
without any limitation as long as it has an acyl group on one side
of a peroxy group (--OO--) and a hydrocarbon group on the other
side (or an organic group similar thereto). Examples of the
peroxyester compound include t-butyl peroxyneodecanoate, t-butyl
peroxyisobutyrate, t-butyl peroxymaleic acid, t-butyl
peroxyisopropyl monocarbonate, t-butyl peroxyester isononanoate,
t-butyl peroxyacetate, t-butyl peroxybenzoate (tBPB), t-butyl
peroxy-m-toluoylbenzoate, cumyl peroxyneodecanoate,
1,1,3,3-tetramethylbutyl peroxyneodecanoate,
1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl
peroxyneodecanoate, 2,5-bis(benzoylperoxy)hexane, t-amyl
peroxyisononanoate (tAPiN), and the like.
[0094] As the peroxyester compound, any known one can be used
without any limitation as long as it has a hydrocarbon group (or an
organic group similar thereto) on one side of a peroxy group
(--OO-- group), and hydrogen on the other side. Specific examples
thereof include p-menthane hydroperoxide, diisopropylbenzene
hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide (TMBHP),
cumene hydroperoxide, t-hexyl hydroperoxide, and t-amyl
hydroperoxide.
[0095] As the alkyl peroxide, any known one can be used without any
limitation as long as it has a hydrocarbon group (or an organic
group similar thereto) in both sides of a peroxy group (--OO--
group). Examples of the alkyl peroxide include di-t-butyl peroxide,
di-t-hexyl peroxide, 1,1-bis(t-butylperoxy)cyclohexane (tBPCy), and
the like.
[0096] Among these peroxides (D), from the viewpoint of storage
stability and reactivity, t-butyl peroxybenzoate (tBPB), t-butyl
peroxyester isononanoate, t-amyl peroxyisononanoate (tAPiN),
1,1,3,3-tetramethylbutyl hydroperoxide (TMBHP), cumene
hydroperoxide and 1,1-di(t-butylperoxy)cyclohexane (tBPCy) are
preferable, t-butyl peroxybenzoate (tBPB), t-amyl
peroxyisononanoate (tAPiN), 1,1,3,3-tetramethylbutyl hydroperoxide
(TMBHP), cumene hydroperoxide are more preferable, and t-butyl
peroxybenzoate (tBPB) and t-amyl peroxyisononanoate (tAPiN) are
particularly preferred.
[0097] The peroxide (D) may be used singly or in combination of two
or more thereof. Further, the content of the peroxide (D) in the
curable composition of the present invention is preferably 1 to
1000 parts by mass, more preferably 10 to 700 parts by mass, and
particularly preferably 50 to 500 parts by mass, based on 100 parts
by mass of the polymerization initiator.
[0098] (Filler E))
[0099] A filler (E) is preferably contained in the curable
composition of the present invention, in that fluidity and
consistency, color tone, curability and the like of the composition
are adjusted, radiodensity is imparted, and mechanical strength of
the obtained cured product is improved. As the filler (E), a
general filler used in the dental field can be used. Fillers are
generally broadly classified into organic fillers and inorganic
fillers.
[0100] Examples of the organic filler include powdered polymer
fillers obtained by pulverization of a polymer or dispersion
polymerization, and fillers obtained by polymerizing a
polymerizable monomer with a crosslinking agent and then
pulverizing the resulting polymer. Specific examples of such an
organic filler include fine powders of a homopolymer or copolymer
of a polymerizable monomer, such as polymethyl methacrylate (PMMA),
polybutyl methacrylate (PBMA), polyvinyl acetate (PVAc),
polyethylene glycol (PVA), polyurethane, polyurea, methyl
methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl
methacrylate, ethylene-vinyl acetate copolymer, and
styrene-butadiene copolymer. Further, the organic filler may also
be a product obtained by adding a component such as a known
pigment, a fluorescent agent, a biologically active component, a
polymerization initiator, and the like during preparation of the
organic filler.
[0101] Examples of the inorganic filler include fine powders of
various glasses (mainly composed of silicon dioxide, containing
oxides such as heavy metals, boron and aluminum as necessary),
various ceramics, diatomaceous earth, kaolin, clay mineral
(montmorillonite, etc.), activated clay, synthetic zeolite, mica,
calcium fluoride, ytterbium fluoride, calcium. carbonate, calcium
phosphate, aluminum sulfate, barium sulfate, calcium sulfate,
zirconium dioxide, titanium dioxide, aluminum oxide, boron oxide,
barium oxide, lanthanum oxide, strontium oxide, zinc oxide, calcium
oxide, lithium oxide, sodium oxide, bismuth oxide, yttrium oxide,
calcium phosphate, hydroxyapatite, aluminum hydroxide, sodium
fluoride, potassium fluoride, sodium monofluorophosphate, lithium
fluoride, and the like. Specific examples of such inorganic fillers
include, for example, fine powders of barium borosilicate glasses
(such as Kimble RAY-SORB T3000, Schott 8235, Schott GM27884, and
Schott G018-053), fine powders of strontium boroaluminosilicate
glasses (such as RAY-SORB T4000, Schott G018-093 and G018-163),
fine powders of lanthanum glass (such as Schott GM31684 and
G018-161), fine powders of fluoroaluminosilicate glasses (such as
Schott G018-091 and Schott G018-117), and fine powders of
boroaluminosilicate glasses containing zirconium and/or cesium
(such as Schott G018-307, G018-308 and G018-310).
[0102] It is also possible to use an organic-inorganic composite
filler obtained by: adding a polymerizable monomer to the
above-mentioned inorganic fillers in advance to form a paste, then
polymerizing and curing, and pulverizing the resultant product.
Examples of the organic-inorganic composite filler include a filler
(TMPT.f) obtained by polymerizing and coating fine powder silica,
zirconium oxide or the like of an inorganic filler with a
polymerizable monomer having trimethylolpropane tri(meth)acrylate
(TMPT) as a main component, and then pulverizing the obtained
polymer, and the like.
[0103] When a microfiller with a particle size of 0.1 .mu.m or less
is incorporated in a dental material, it is advantageous in
obtaining polishing smoothness and abrasion resistance of the cured
product, and it is one preferred mode of the dental composite
resin. As a material of the filler with such a particle size,
silica (trade name: Aerosil R812, R972, etc.), alumina, zirconia,
titania and the like are preferable.
[0104] These fillers (E) are subjected to surface treatment with a
silane coupling agent or the like according to the purpose. For
example, when using an inorganic filler or an organic-inorganic
composite filler, it is preferred to treat a filler surface with a
known surface treating agent to improve affinity and dispersibility
with the polymerizable monomer (C) used in the present invention.
As such a surface treatment agent, a known silane coupling agent
can be used without any limitation. For example,
.gamma.-methacryloxyalkyltrimethoxysilane (number of carbons
between methacryloxy group and silicon atom: 3 to 12),
.gamma.-methacryloxyalkyltriethoxysilane (number of carbons between
methacryloxy group and silicon atom: 3 to 12), or an organosilicon
compound such as vinyltrimethoxysilane, vinylethoxysilane, and
vinyltriacetoxysilane can be used. In addition to the silane
coupling agent, a surface treatment may be performed with a
titanate coupling agent, an aluminate coupling agent, a
zirco-aluminate coupling agent, or the like.
[0105] These fillers (E) can be appropriately added according to
the application. The filler (E) may be used singly or in
combination of two or more thereof. Moreover, when the filler (E)
is added, the content is preferably 1 to 900 parts by mass, more
preferably 10 to 600 parts by mass, and particularly preferably 60
to 500 parts by mass, based on 100 parts by mass of the
polymerizable monomer (C) contained in the composition of the
present invention.
[0106] (Reducing Agent (F))
[0107] A reducing agent (F) is preferably contained in the curable
composition of the present invention, in terms of polymerization
efficiency. As the reducing agent (F), any known one can be used
without any limitation. As the reducing agent (F), an amine
compound or a salt thereof, a sulfinic acid compound or a salt
thereof, an ascorbic acid compound or a salt thereof can be used,
and a sulfinic acid compound or a salt thereof is preferable.
[0108] Examples of the amine compound include aromatic-substituted
glycine compounds or salts thereof, and aromatic tertiary amines.
Examples of the aromatic-substituted glycine compound or salt
thereof include aromatic-substituted glycine, or usual alkali metal
salts, alkaline earth metal salts, amine salts, and ammonium salts
thereof. Examples of the alkali metal salt include lithium salts,
sodium salts, potassium salts, and the like. Examples of the
alkaline earth metal salt include magnesium salts, calcium salts,
strontium salts, and barium salts. Examples of the amine salt
include salts of primary amines such as methylamine; secondary
amine salts such as dimethylamine; salts of tertiary amines such as
trimethylamine. Examples of the salt of the ammonium compound
include ammonium salts, tetramethylammonium salts,
tetraethylammonium salts, tetrapropylammonium salts, and
trimethylbenzylammonium salts.
[0109] Examples of the aromatic tertiary amine include
N,N-dimethylaniline (DMA), N,N-dimethyl p-toluidine (DMPT),
N,N-diethyl p-toluidine, N,N-diethanol p-toluidine (DEPT); methyl
N,N-dimethylaminobenzoate, ethyl N,N-dimethylaminobenzoate
(DMABAE), butoxyethyl N,N-dimethylaminobenzoate (DMABABE),
N,N-diethylaminobenzoic acid (DEABA) and alkyl esters thereof,
N,N-dimethylaminobenzaldehyde (DMABAd),
N,N-dimethylaminobenzophenone, and the like.
[0110] As the sulfinic acid compound or salt thereof, a sulfinic
acid or a usual alkali metal salt, alkaline earth metal salt, amine
salt or ammonium salt of a sulfinic acid can be used. Examples of
the alkali metal salt include lithium salts, sodium salts,
potassium salts, and the like. Examples of the alkaline earth metal
salt include magnesium salts, calcium salts, strontium salts,
barium salts, and the like. Examples of the amine salt include
salts of primary amines such as methylamine; secondary amine salts
such as dimethylamine; salts of tertiary amines such as
trimethylamine. Examples of the salt of the ammonium compound
include ammonium salts, tetramethylammonium salts,
tetraethylammonium salts, tetrapropylammonium salts, and
trimethylbenzylammonium salts.
[0111] Further, as the sulfinic acid compound or salt thereof, an
organic sulfinic acid or a salt thereof can be used. Examples of
the organic sulfinic acid compound include alkanesulfinic acids
such as methanesulfinic acid; alicyclic sulfinic acids such as
cyclohexanesulfinic acid and cyclooctanesulfinic acid; and aromatic
sulfinic acids such as benzenesulfinic acid, p-toluenesulfinic acid
decylbenzenesulfinic acid chlorobenzenesulfinic acid,
fluorobenzenesulfinic acid, and naphthalenesulfinic acid.
[0112] Examples of the salt of an organic sulfinic acid compound
include salts of alkali metals such as lithium, sodium and
potassium, salts of alkaline earth metals such as magnesium,
calcium and strontium, amine salts such as triethylamine, and
ammonium salts such as tetrabutylammonium of the above organic
sulfinic acid compounds, and the like. Examples thereof include
sodium p-toluenesulfinate (p-TSS), potassium p-toluenesulfinate,
calcium p-toluenesulfinate, and the like.
[0113] Among the sulfinic acid compounds or salts thereof, sodium
p-toluenesulfinate (p-TSS) is preferable in terms of reactivity and
easy handling.
[0114] When the reducing agent (F) is added, the content is
preferably 0.00001 to 20 parts by mass, more preferably 0.00005 to
10 parts by mass, and particularly preferably 0.0001 to 5 parts by
mass, based on 100 parts by mass of the polymerizable monomer (C)
contained is the composition of the present invention.
[0115] (Aqueous Solvent (G))
[0116] The curable composition of the present invention can also
contain an aqueous solvent (G). As the aqueous solvent (G), any
known one can be used without any limitation, and water,
physiological saline, an organic solvent miscible with water, or a
mixed solvent thereof can be used. Examples of water that can be
used include distilled water and ion-exchanged water. Examples of
the organic solvent miscible with water include alcohols such as
methanol, ethanol and isopropanol, ketones such as acetone and
methyl ethyl ketone, ethers such as tetrahydrofuran, amides such as
N,N-dimethylformamide, and aprotic solvents such as dimethyl
sulfoxide. Among these organic solvents, it is preferable to use
ethanol or acetone in consideration of harmfulness and irritation
to dental pulp.
[0117] These aqueous solvents (G) can be appropriately added
according to the application. When the aqueous solvent is added,
the content is preferably 10 to 900 parts by mass, more preferably
25 to 500 parts by mass, and particularly preferably 100 to 300
parts by mass, based on 100 parts by mass of the polymerizable
monomer (C) contained in the composition of the present
invention.
[0118] (Photopolymerization Initiator (H))
[0119] The curable composition of the present invention can also
contain a photopolymerization initiator (H). As the
photopolymerization initiator (F), any known one can be used
without any limitation. As the photopolymerization initiator, for
example, .alpha.-diketone/reducing agent, ketal/reducing agent,
thioxanthone/reducing agent, an acylphosphine oxide compound and
the like can be used.
[0120] Examples of the .alpha.-diketone include camphorquinone
(CQ), camphorquinonesulfonic acid, camphorquinonecarboxylic acid,
1,2-cyclohexanedione, methylglyoxal, phenylglyoxal, pyruvic acid,
benzoylformic acid, phenylpyruvic acid, methyl pyruvate, ethyl
benzoylformate, methyl phenylpyruvate, and the like.
[0121] Examples of the ketal include benzyl dimethyl ketal, benzyl
diethyl ketal, and the like.
[0122] Examples of the thioxanthone include 2-chlorothioxanthone,
2,4-diethylthioxanthone, and the like.
[0123] Examples of the acylphosphine oxide compound include
2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO),
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the
like.
[0124] Examples of the reducing agent include hydrogen peroxide,
Michler's ketone; aldehydes such as citronellal, lauryl aldehyde,
phthaldialdehyde, dimethylaminobenzaldehyde and terephthalaldehyde;
mercaptans such as 2-mercaptobenzoxazal, decanethiol,
3-mercaptopropyltrimethoxysilane, 4-mercaptoacetophenone,
thiosalicylic acid, and thiobenzoic acid;
[0125] aromatic amine compounds such as N,N-dimethylaminobenzoic
acid and alkyl esters thereof, such as N,N-dimethylaminobenzoic
acid ethyl (DMABAE) and N,N-dimethylaminobenzoic acid butoxyethyl
(DMABABE), N,N-diethylaminobenzoic acid (DEABA) and alkyl esters
thereof, N,N-dimethylaminobenzaldehyde (DMABAd),
N,N-dimethylaminobenzophenone, N,N-dimethylaniline
N,N-dimethyl-p-toluidine (DMPT), and
N,N-di(2-hydroxyethyl)-p-toluidine (DEPT); and the like.
[0126] Among the above photopolymerization initiators (H), in view
of having an absorption wavelength in the visible light region and
being polymerizable by visible light, a photopolymerization
initiator containing camphorquinone or TPO having an absorption
wavelength at 400 nm or more is preferred, and in particular, a
photopolymerization initiator containing camphorquinone having an
absorption wavelength at 468 nm is preferred, and a
photopolymerization initiator containing camphorquinone and ethyl
N,N-dimethylaminobenzoate is more preferred.
[0127] Examples of the photopolymerization initiator containing
camphorquinone/reducing agent includes a photopolymerization
initiator containing camphorquinone/aromatic amine compound, a
photopolymerization initiator containing camphorquinone/peroxide, a
photopolymerization initiator camphorquinone/aldehyde, and a
photopolymerization initiator containing
camphorquinone/mercaptan.
[0128] The photopolymerization initiator (H) may be used singly or
in combination of two or more thereof. Further, the content of the
photopolymerization initiator (H) is preferably 0.001 to 5 parts by
mass, more preferably 0.005 to 3 parts by mass, and particularly
preferably 0.01 to 1 part by mass, based on 100 parts by mass of
the polymerizable monomer (C) contained in the composition of the
present invention.
[0129] (Other Ingredients)
[0130] The curable composition of the present invention may contain
components other than those described above as appropriate
according to the purpose as long as such components do not impair a
function as the curable composition.
[0131] For example, the curable composition of the present
invention may contain various stabilizers such as a polymerization
inhibitor and an ultraviolet absorber in order to enhance storage
stability of the polymerizable monomer (C) and the like, and may
contain known pigments, dyes, fluorescent agents and the like in
order to adjust color tone. In addition, the curable composition
may contain a calcium-containing compound such as calcium chloride,
a fluorine-containing compound such as sodium fluoride, known
biologically active components such as an antifungal agent and an
antibacterial agent, and the like. Further, in order to improve
strength of the obtained cured product, the curable composition may
contain a known reinforcing material such as fiber.
[0132] The content of each of the other components is preferably
0.00001 to 20 parts by mass, more preferably 0.00005 to 10 parts by
mass, and particularly preferably 0.0001 to 5 part by mass, based
on 100 parts by mass of the polymerizable monomer (C) contained in
the curable composition of the present invention, from the
viewpoint of not impairing the effects of the present invention,
and exhibiting characteristics of the other components.
[0133] Examples of the form of the curable composition of the
present invention include forms such as liquid and paste. The
curable composition of the present invention is preferably a paste
from the viewpoint of easy handling.
[0134] The curing time at 37.degree. C. of the curable composition
of the present invention is preferably 0.5 to 5 minutes, more
preferably 0.8 to 4 minutes, further preferably 1.0 to 3.0 minutes,
and particularly preferably 1.0 to 2.9 minutes. Further,
three-point bending strength is preferably 80 MPa or more, more
preferably 100 MPa or more, and further preferably 120 MPa or
more.
[0135] (Application)
[0136] The curable composition of the present invention can be
suitably used as a dental material. Examples thereof include dental
adhesives, dental filler materials, dental sealant (tooth fovea
fissure sealant), core build-up materials, denture base resins,
denture base lining materials, crown prosthetic resins (hard resins
for crowns), dental room-temperature polymerization resins, and the
like.
[0137] Examples of the dental adhesive include dental adhesive
resin cements, orthodontic adhesives, mobile tooth fixing
adhesives, adhesives for application to cavity, dental bonding
materials, and the like.
[0138] Examples of the dental filler material include dental
composite resins (including dental self-adhesive composite resins),
root canal fillers, temporary sealing materials, backing materials,
and the like.
[0139] Of these, the curable composition of the present invention
is suitable for a dental filler material in that it is excellent in
bending strength, bending elastic modulus, and adhesion to
tooth.
[0140] The curable composition of the present invention can be used
by a method generally used as the dental material. For example,
when the curable composition of the present invention is used as a
dental adhesive resin cement, it can be used by a method of
subjecting an adhesive surface such as enamel and a metal surface
to treatment such as washing with water and drying, then preparing
an adhesive liquid obtained by mixing resin cement powder and the
curable composition of the present invention, applying the adhesive
liquid to a tooth surface, and adhering a bracket, or the like.
[0141] For example, when the curable composition of the present
invention is used as a root canal filler, it can be used by a
method of removing adhesion inhibitors such as NaOCl adhered in a
root canal and removing a smear layer adhered to a root canal wall,
preparing a sealer-mixed mud in which the curable composition of
the present invention and a powder material for sealer are mixed,
transferring it to a root canal, filling it, and curing it at a
predetermined temperature, or the like.
[0142] For example, when the curable composition of the present
invention is used as a composite resin for filling and restoration,
it can be used in a method of subjecting a formed cavity to dental
pulp protection, a bonding treatment, and the like, and then
filling to the cavity a paste in which the curable composition of
the present invention and a powder such as silica are mixed, and,
for example, irradiating light of a predetermined wavelength for a
predetermined time to cure the paste, or the like.
[0143] <Kit for Preparing Curable Composition>
[0144] Another embodiment of the present invention, a kit for
preparing a curable composition is composed of a first pack
containing the compound (A), a second pack containing the
transition metal compound (B), and the like, and the polymerizable
monomer (C) is contained in one or both of the first pack and the
second pack.
[0145] In the presence of the polymerizable monomer (C), when the
compound (A) in the first pack and the transition metal compound
(B) in the second pack are mixed, polymerization starts. Therefore,
sufficient operation time and appropriate curing time can be
secured by storing separately the compound (A) and the transition
metal compound (B), and mixing these when curing the curable
composition.
[0146] The first pack may contain, in addition to the compound (A),
the polymerizable monomer (C), peroxide (D), filler (E), reducing
agent (F), aqueous solvent (G) and photopolymerization initiator
(H) described above, and a polymerization inhibitor, and the like.
These components may be used singly or in combination of two or
more thereof.
[0147] The second pack may contain, in addition to the transition
metal compound (B), the polymerizable monomer (C), peroxide (D),
filler (E), reducing agent (F), aqueous solvent (G) and
photopolymerization initiator (H) described above, and a
polymerization inhibitor, and the like. These components may be
used singly or in combination of two or more thereof.
[0148] From the viewpoint of reactivity with the compound (A), when
camphorquinone is contained as the photopolymerization initiator
(H), the camphorquinone is preferably contained in the second pack
rather than the first pack. Moreover, from the viewpoint of
reactivity with the transition metal compound (B), the reducing
agent (F) and the peroxide (D) are preferably contained in the
first pack rather than the second pack. When used as the
photopolymerization initiator (H), the aromatic amine compound may
be added to either the first pack or the second pack.
[0149] The total content of the polymerizable monomer (C) in the
first pack and the second pack is, like the curable composition of
the present invention, preferably 100 to 200,000 parts by mass,
more preferably 500 to 100,000 parts by mass, and more preferably
1,000 to 50,000 parts by mass, based on 100 parts by mass of the
compound in the first pack. The total content of other components
in the first pack and the second pack is also the same as that of
the curable composition of the present invention.
[0150] The kit for preparing a curable composition of the present
invention can be used by a method generally known as a dental
material as described above. For example, when used as a dental
filler material, for example, it can be used in a method of
removing adhesion inhibitors such as NaOCl adhered in a root canal
and removing a smear layer adhered to a root canal wall, then
preparing a mixed mud in which the first pack and the second pack,
and a powder material for sealer are mixed in a container,
transferring it to a root canal, filling it, and curing it at a
predetermined temperature, or the like.
[0151] The kit for preparing a curable composition of the present
invention may contain, in addition to the first pack and the second
pack, equipment, a pretreatment agent and the like according to the
purpose. For example, when used as a root canal filler, a pottery
or a container made of aluminum or the like used for mixing the
first pack and the second pack, a dental spatula used for mixing, a
brush handle made of aluminum alloy, pretreatment agents for
removing adhesion inhibitors and for removing a smear layer and the
like may be included in the kit.
EXAMPLES
[0152] Hereinafter, the present invention will be described in
detail with reference to examples and comparative examples, but the
present invention is not limited to these examples. Abbreviations
for compounds used in examples are shown below. [0153]
[Pyrazolidinedione Compound and/or Pyrazolidine(di)thione Compound
(A1)]
[0154] PBZ: Phenylbutazone (manufactured by Tokyo Chemical Industry
Co., Ltd.) [0155] [Salt of Pyrazolidinedione Compound and/or Salt
(A2) of Pyrazolidine(di)thione Compound]
[0156] PBZCa: Phenylbutazone calcium (manufactured by Woongjin
Chemical Co., Ltd.)
[0157] PBZNa: Phenylbutazone sodium (manufactured by Woongjin
Chemical Co., Ltd.) [0158] [Malonate Compound (A3)]
[0159] DEPM: Diethyl phenylmalonate (manufactured by Tokyo Chemical
Industry Co., Ltd.)
[0160] TEMTC: Triethyl methanetricarboxylate (manufactured by Tokyo
Chemical Industry Co., Ltd.) [0161] [Transition Metal Compound
(B)]
[0162] CuCl.sub.2: Copper(II) chloride (manufactured by FUJIFILM
Wako Pure Chemical Corporation)
[0163] Cu(acac).sub.2: Copper acetylacetonate (manufactured by
Tokyo Chemical industry Co., Ltd.) [0164] [Polymerizable Monomer
(C)]
[0165] UDMA:
1,6-Bis(methacryloxyethyloxycarbonylamino)-2,2,4-trimethylhexane (a
compound synthesized by reacting 2,2,4-trimethylhexyl diisocyanate
(TMHDI, Tokyo Chemical Industry Co., Ltd.) and 2-hydroxyethyl
methacrylate (HEMA, Mitsubishi Chemical Corporation) at a ratio of
1:2, according to a known urethanization reaction method)
[0166] Bis-GMA: Bisphenol A dilycidyl methacrylate (manufactured by
Shin-Nakamura Chemical Co, Ltd.)
[0167] NBDI-HEA: A compound synthesized by reacting a mixture
(NBDI, manufactured by Mitsui Chemicals, Inc.) of
2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane and
2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane with 2-hydroxyethyl
acrylate (HEA, manufactured by Nippon Shokubai Co., Ltd.) at a
ratio of 1:2, according to a known urethanization reaction
method.
[0168] TEGDMA: Triethylene glycol dimethacrylate (manufactured by
Shin-Nakamura Chemical Co, Ltd.)
[0169] HexDMA: 1,6-hexanediol dimethacrylate (manufactured by
Shin-Nakamura Chemical Co, Ltd.)
[0170] GDMA: Glycerol dimethacrylate (manufactured by Shin-Nakamura
Chemical Co, Ltd.)
[0171] HEMA: 2-Hydroxyethyl methacrylate (manufactured by
Mitsubishi Chemical Corporation)
[0172] 4-MET: 4-Methacryloyloxyethyl trimellitic acid (obtained by
adding 1.2 equivalents of pure water to 4-methacryloyloxyethyl
trimellitic anhydride (4-META, manufactured by FUJIFILM Wako Pure
Chemical Corporation) and stirring the mixture overnight, and then
pulverizing the mixture)
[0173] MDP: 10-Methacryloyloxydecyl dihydrogen phosphate
(manufactured by FUJIFILM Wako Pure Chemical Corporation) [0174]
[Peroxide (D)]
[0175] tBPB: t-Butyl peroxybenzoate (trade name "Luperox P",
manufactured by Sigma-Aldrich Co. Ltd.)
[0176] tAPiN: t-Amyl peroxyisononanoate (trade name "Luperox 570",
manufactured by ARKEMA Yoshitomi, Ltd.)
[0177] TMBHP: 1,1,3,3-Tetramethylbutyl hydroperoxide (trade name
"Luperox 215", manufactured by ARKEMA Yoshitomi, Ltd.)
[0178] tBPCy: 1,1-Di(t-butylperoxy)cyclohexane (trade name "Luperox
331XL", manufactured by ARKEMA Yoshitomi, Ltd.)
[0179] BPO: Benzoyl peroxide (manufactured by Tokyo Chemical
Industry Co., Ltd.)
[0180] [Filler (E)]
[0181] GM27884: Silane-treated barium glass powder (trade name
"GM27884", manufactured by SCHOTT, particle size 1.5 .mu.m, treated
with .gamma.-MPTS at 1.6% based on filler weight)
[0182] 8235: Silane-treated barium glass powder (trade name "8235",
manufactured by SCHOTT, particle size 0.7 .mu.m, treated with
.gamma.-MPTS at 6% based on filler weight))
[0183] R812: Fine particle silica (trade name "AEROSIL R812",
manufactured by Nippon Aerosil Co., Ltd.) [0184] [Reducing Agent
(F)]
[0185] p-TSS: Sodium p-toluenesulfinate (manufactured by FUJIFILM
Wako Pure Chemical Corporation, dried at 70.degree. C. under
reduced pressure after purchase, and pulverized by a mortar)
[0186] DEPT: N,N-Diethanol-p-toluidine (manufactured by FUJIFILM
Wako Pure Chemical Corporation) [0187] [Aqueous Solvent (G)]
[0188] Acetone: Acetone (manufactured by FUJIFILM Wako Pure
Chemical Corporation)
[0189] EtOH: Ethanol (manufactured by FUJIFILM Wako Pure Chemical
Corporation)
[0190] Distilled water: manufactured using a distilled water
production equipment (manufactured by Tokyo Rikakikai Co., Ltd.)
[0191] [Photopolymerization Initiator (H)]
[0192] CQ: d,l-Camphorquinone (manufactured by FUJIFILM Wako Pure
Chemical Corporation)
[0193] DMABAE: Ethyl N,N-dimethylaminobenzoate (manufactured by
FUJIFILM Wako Pure Chemical Corporation)
[0194] TPO: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide: (trade
name "Irgacure TPO", manufactured by BASF Corporation) [0195]
[Other Components: Polymerization Inhibitor]
[0196] BHT: 2,6-Di-t-butyl-4-methylphenol (manufactured by Tokyo
Chemical Industry Co., Ltd.)
[0197] MEHQ: 4-Methoxyphenol (manufactured by FUJIFILM Wako Pure
Chemical Corporation)
[0198] <Preparation of First Pack and Second Pack for Preparing
Curable Composition>
[0199] Paste-like first pack and second pack to be used for
preparing the curable compositions of examples and comparative
examples were prepared by blending and mixing components in
proportions (parts by mass) shown in Table 1.
[0200] <Measurement Method of Curing Time>
[0201] The curing time in examples and comparative examples shown
in Tables 1 and 2 were measured by differential thermal analysis
using a differential scanning calorimeter (DSC). As the measuring
apparatus, a DSC 3500 Sirius (manufactured by NETZSCH) was
used.
[0202] Specifically, the first pack and the second pack taken in
equal amounts were mixed on a dental kneading paper with a dental
spatula for 10 seconds at room temperature set to 20 to 25.degree.
C. to obtain a polymerizable mixture. The obtained polymerizable
mixture was filled is a sample pan made of Al for DSC
measurement.
[0203] The sample pan made of Al filled with the polymerizable
mixture was placed in a DSC thermostat set at 37.+-.1.degree. C.
just before measurement, and measurement was started 40 seconds
after the start of kneading. The time until the point at which the
temperature rises due to the start of the curing reaction of the
polymerizable mixture and reached the maximum temperature was
recorded as the curing time.
[0204] <Measurement Method of Pot Life>
[0205] Equal amounts of the first pack and the second pack of the
composition shown in Table 3 were taken on a dental kneading paper,
and kneaded with a dental spatula at experimental room temperature,
and a time until curing behavior could be confirmed was recorded
and defined as a pot life. The time measurement was started at the
same time as the start of kneading.
[0206] <Measurement Method of Three-Point Bending
Strength>
[0207] The first pack and the second pack shown in Tables 1 to 3
taken in equal amounts were mixed on a dental kneading paper with a
dental spatula for 10 seconds at room temperature set to 20 to
25.degree. C. to obtain a homogeneous polymerizable mixture. The
obtained polymerizable mixture was filled in a 2 mm.times.2
mm.times.25 mm mold for test piece preparation, pressed from both
sides with a Lumirror film, and polymerized in a thermostat set to
37.+-.1.degree. C. for 1 hour, and the obtained cured body was used
as a test piece.
[0208] When preparing a test piece by chemical polymerization, a
cured body obtained by polymerization in a mold filled with the
mixture within a thermostat set to 37.+-.1.degree. C. for 1 hour
was used as a test piece.
[0209] When preparing a test piece by photopolymerization, a cured
body obtained by irradiating with light on back and front for 1
minute and 30 seconds using a technical LED irradiator was used as
a test piece.
[0210] In addition, "LC mode" and values marked with an asterisk
(*) in Tables 1 to 3 show a case where a test piece was prepared by
photopolymerization and measurement results of three-point bending
strength and bending elastic modulus of the test piece.
[0211] Each test piece was removed from the mold, immersed in
distilled water, stored in a thermostat set to 37.+-.1.degree. C.
for 18 hours. The test piece was then taken out, and a three-point
bending test was performed using a universal testing machine
(manufactured by Intesco Co., Ltd.). The test was performed by
applying a load until the test piece broke at a crosshead speed of
1 mm/min, and the strength of the cured body was calculated from
the obtained maximum point stress. At that time, the bending
elastic modulus was also calculated.
[0212] As shown in Table 1, Comparative Example 1 containing no PBZ
had a curing time of 3 minutes or more and sufficient
polymerization properties were not obtained, whereas Examples 1 to
11 all had a curing time in the range of 1 minute or more and less
than 3 minutes, which was appropriate curing time. In addition,
Examples 1 to 11 were excellent in bending strength and bending
elastic modulus, whereas Comparative Examples 1 and 2 were
insufficient in polymerization properties and sufficient bending
strength and bending elastic modulus were not also obtained.
Furthermore, in Example 11, it was also possible to use a CQ-based
photopolymerization initiator in combination.
[0213] As shown in Table 2, Examples 14 to 26 containing PBZCa or
PBZNa all had a curing time in the range of 1 minute or more and
less than 3 minutes, which was appropriate curing time. Further,
Examples 14 to 26 were excellent in bending strength and bending
elastic modulus. On the other hand, Comparative Examples 1 and 2
containing no PBZCa and PBZNa had a curing time of 3 minutes or
more and had insufficient polymerization properties, and sufficient
bending strength and bending elastic modulus were not also
obtained. Further, in Examples 25 and 26, it was also possible to
use a CQ-based or TPO-based photopolymerization initiator in
combination.
[0214] On the other hand, as shown in Tables 1 and 2, Comparative
Example 2 and Comparative Example 3 are both compositions
containing a BPO-aromatic amine compound (DEPT) polymerization
initiator system, and Comparative Example 3 contains a larger
amount of DEPT than Comparative Example 2. Even though sufficient
polymerization properties were not obtained in Comparative Example
2, in Comparative Example 3 in which the amount of DEPT was
increased, the curing time was improved to some extent, and the
bending strength and bending elastic modulus were improved, but a
yellowed cured body was obtained.
[0215] Based on this, it was found that a polymerization initiator
system utilizing PBZ or a salt of PBZ and a transition metal
compound is a polymerization initiator system excellent in curing
time, bending strength and bending elastic modulus while
suppressing discoloration due to an amine compound.
[0216] Although not shown in Table 1, as Example 12 or Example 13,
when the first pack and the second pack were prepared in the same
formulation as in Example 2, except for using 3 parts by mass of
DEPM (Example 12) or 3 parts by mass of TEMTC (Example 13) as a
malonate compound (A3) instead of 1 part by mass of PBZ contained
is the first pack, and the curing time was measured for Example 12
or Example 13 as well, the curing time of Example 12 was 2.4
minutes and the curing time of Example 13 was 2.6 minutes. From
this result, it was shown that the curing time was excellent by
utilizing the malonate compound.
[0217] When the pot life was evaluated in Examples 27 to 37 shown
in Table 3, it was in the range of 1 minute or more and less than 3
minutes, and it was found that they have an appropriate length of
pot life. On the other hand, Comparative Examples 4 and 5
containing no PBZ and a PBZ salt, and Comparative Example 6
constituted by BPO/aromatic amine chemical polymerization system
did not show sufficient polymerization properties.
[0218] Further, the curable compositions of Examples 27 to 37
showed excellent three-point bending strength and bending elastic
modulus.
[0219] From the above, when the curing time is in the range of 1
minute to less than 3 minutes is the curing time measurement, or
when the pot life was in the range of 1 minute to less than 3
minutes in the pot life measurement, it can be determined that the
evaluated curable composition has an appropriate curability.
Further, when the three-point bending strength of the obtained
cured product is 80 MPa or more, it can be determined that the
polymerization initiator of the present invention gives a cured
product having sufficient strength.
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Example 7 First Pack UDMA 70 70 70 70 70 70 70
NBDI-HEA -- -- -- -- -- -- -- TEGDMA 30 30 30 30 30 30 30 PBZ 1 1 1
1 1 1 1 TMBHP 1 -- -- 1 -- -- -- tBPB -- 1 -- -- 1 -- -- tBPCy --
-- 5 -- -- 3 5 BPO -- -- -- -- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2
0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10 8235
70 70 10 70 70 70 70 GM27884 150 150 150 150 150 150 150 Second
UDMA 70 70 70 70 70 70 70 Pack Bis-GMA -- -- -- -- -- -- -- TEGDMA
30 30 30 -- -- -- -- GDMA -- -- -- 30 30 30 30 CuCl.sub.2 0.1 0.1
0.1 0.1 0.05 0.1 0.1 CQ -- -- -- -- -- -- -- DMABAE -- -- -- -- --
-- -- DEPT -- -- -- -- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2
MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10 8235 70
70 70 70 70 70 70 GM27884 150 150 150 150 150 150 150 Evaluation
Curing time 2.3 min 2.4 min 2.3 min 1.1 min 1.2 min 2.0 min 1.7 min
Results Three-point 135.4 MPa 132.9 MPa 124.0 MPa 136.1 MPa 133.5
MPa 133.2 MPa 168.4 MPa bending (SD 14.1) (SD 4.4) (SD 0.7) (SD
0.8) (SD 7.8) (SD 19.8) (SD 12.7) strength (SD) Bending elastic 6.9
GPa 5.2 GPa 5.4 GPa 6.5 GPa 7.4 GPa 7.6 GPa 7.9 GPa modulus (SD)
(SD 0.7) (SD 0.9) (SD 0.5) (SD 0.6) (SD 0.5) (SD 0.5) (SD 0.1)
Comparative Comparative Comparative Example 8 Example 9 Example 10
Example 11 Example 1 Example 2 Example 3 First Pack UDMA -- 70 70
70 70 70 70 NBDI-HEA 70 -- -- -- -- -- -- TEGDMA 30 30 30 30 30 30
30 PBZ 1 1 1 1 -- -- -- TMBHP -- -- -- -- -- -- -- tBPB 2 1 3 1 1
-- -- tBPCy -- -- -- -- -- -- -- BPO -- -- -- -- -- 3 3 BHT 0.2 0.2
0.2 0.2 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10
10 10 10 10 8235 70 70 70 70 70 70 70 GM27884 150 150 150 150 150
150 150 Second UDMA 70 -- -- -- 70 70 70 Pack Bis-GMA -- 70 70 70
-- -- -- TEGDMA -- 30 30 30 30 30 30 GDMA 30 -- -- -- -- -- --
CuCl.sub.2 0.1 0.001 0.001 0.001 0.1 -- -- CQ -- -- -- 0.1 -- -- --
DMABAE -- -- -- 0.3 -- -- -- DEPT -- -- -- -- -- 1 3 BHT 0.2 0.2
0.2 0.2 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10
10 10 10 10 8235 70 70 70 70 70 70 70 GM27884 150 150 150 150 150
150 150 Evaluation Curing time 1.5 min 1.3 min 1.1 min 1.6 min LC
mode 8.8 min >10 min 3.0 min Results Three-point 129.6 MPa 160.4
MPa 151.2 MPa 144.0 MPa *148.6 MPa -- -- 122.5 MPa bending (SD
11.4) (SD 4.5) (SD 11.6) (SD 8.8) (SD 10.2) (SD 3.0) strength (SD)
Bending elastic 6.9 GPa 10.6 GPa 8.8 GPa 8.7 GPa *8.9 GPa -- -- 6.2
GPa modulus (SD) (SD 0.3) (SD 0.2) (SD 0.5) (SD 0.3) (SD 0.6) (SD
0.2)
TABLE-US-00002 TABLE 2 Example Example Example Example Example
Example Example Example 14 15 16 17 18 19 20 21 First Pack UDMA 70
70 70 70 70 70 70 70 TEGDMA 30 30 30 30 30 30 30 30 HexDMA -- -- --
-- -- -- -- -- PBZCa 5 1 1 1 -- -- -- 5 PBZNa -- -- -- -- 1 1 1 --
tBPB 1 1 1 5 1 1 5 -- tAPiN -- -- -- -- -- -- -- 5 BPO -- -- -- --
-- -- -- -- TPO -- -- -- -- -- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2
0.2 0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10
10 10 8235 70 70 70 70 70 70 70 70 GM27884 150 150 150 150 150 150
150 150 Second UDMA 70 70 -- 70 70 -- -- -- Pack Bis-GMA -- -- 70
-- -- 70 70 70 TEGDMA 30 -- 30 -- -- 30 30 30 GDMA -- 30 -- 30 30
-- -- -- CuCl.sub.2 0.1 0.1 0.001 0.1 0.1 0.005 0.001 0.001 DEPT --
-- -- -- -- -- -- -- CQ -- -- -- -- -- -- -- -- DMABAE -- -- -- --
-- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10 10 8235 70 70 70 70
70 70 70 70 GM27884 150 150 150 150 150 150 150 150 Evaluation
Curing 2.9 min 1.8 min 1.5 min 1.6 min 1.0 min 1.2 min 2.2 min 1.2
min Results time Three- 130.6 134.8 144.2 126.0 136.2 133.3 134.9
125.5 point MPa (SD MPa (SD MPa (SD MPa (SD MPa (SD MPa (SD MPa (SD
MPa (SD bending 11.1) 11.7) 10.5) 8.4) 6.4) 4.7) 4.4) 15.8)
strength (SD) Bending 6.8 GPa 6.6 GPa 7.8 GPa 5.8 GPa 6.4 GPa 7.6
GPa 6.6 GPa 6.5 GPa elastic (SD 0.3) (SD 0.4) (SD 0.3) (SD 0.4) (SD
0.4) (SD 0.2) (SD 0.4) (SD 0.3) modulus (SD) Example Example
Example Example Example Comparative Comparative Comparative 22 23
24 25 26 Example 1 Example 2 Example 3 First Pack UDMA 70 70 70 70
70 70 70 70 TEGDMA 30 30 30 30 30 30 30 30 HexDMA -- 30 30 -- -- --
-- -- PBZCa 1 1 1 5 5 -- -- -- PBZNa -- -- -- -- -- -- -- -- tBPB
-- 1 1 1 1 1 -- -- tAPiN 5 -- -- -- -- -- -- -- BPO -- -- -- -- --
-- 3 3 TPO -- -- -- 0.5 -- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2
0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10
10 8235 70 70 70 70 70 70 70 70 GM27884 150 150 150 150 150 150 150
150 Second UDMA -- 70 -- 70 70 70 70 70 Pack Bis-GMA 70 -- 70 -- --
-- -- -- TEGDMA 30 -- 30 30 30 30 30 30 GDMA -- 30 -- -- -- -- --
-- CuCl.sub.2 0.001 0.1 0.005 0.1 0.1 0.1 -- -- DEPT -- -- -- -- --
-- 1 3 CQ -- -- -- -- 0.1 -- -- -- DMABAE -- -- -- -- 0.3 -- -- --
BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 R812 10 10 10 10 10 10 10 10 8235 70 70 70 70 70 70 70 70
GM27884 150 150 150 150 150 150 150 150 Evaluation Curing 2.5 min
2.0 min 1.0 min 1.5 min LC 1.5 min LC 8.8 min >10 min 3.0 min
Results time mode mode Three- 134.7 123.5 144.1 132.4 *129.5 139.6
*155.0 -- -- 122.5 MPa point MPa (SD MPa (SD MPa (SD MPa MPa MPa
MPa (SD 3.0) bending 7.8) 8.1) 3.6) (SD 7.3) (SD 1.1) (SD (SD 4.2)
strength 13.4) (SD) Bending 6.7 GPa 5.9 GPa 6.6 GPa 6.9 GPa *7.3
7.2 GPa 7.9 -- -- 6.2 GPa (SD elastic (SD 0.9) (SD 0.1) (SD 0.2)
(SD 0.0) GPa (SD 0.3) GPa 0.2) modulus (SD 0.1) (SD 0.2) (SD)
TABLE-US-00003 TABLE 3 Example Example Example Example Example
Example Example 27 28 29 30 31 32 33 First UDMA 70 70 70 70 70 70
70 Pack TEGDMA 30 30 30 30 30 30 30 PBZ 2 2 2 2 2 2 -- PBZCa -- --
-- -- -- -- 1 tBPB 0.5 -- 0.5 0.5 0.5 -- 0.5 tAPiN -- 0.5 -- -- --
0.5 -- DEPT -- -- -- -- -- -- -- DMABAE -- -- -- -- -- -- -- p-TSS
2 2 2 2 2 2 2 BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1 0.1
0.1 0.1 0.1 R812 10 10 10 10 10 10 10 GM27884 70 70 70 70 70 70 70
8235 70 70 70 70 70 70 70 Second UDMA 60 60 60 -- 35 35 60 Pack
Bis-GMA -- -- -- 60 35 35 -- TEGDMA 20 20 -- 20 25 25 20 GDMA -- --
20 -- -- -- -- 4-MET 20 20 20 -- 5 5 20 MDP -- -- -- 20 -- -- -- Cu
(acac).sub.2 0.01 0.01 0.02 0.002 0.002 0.002 0.02 CQ -- -- -- --
-- -- -- BPO -- -- -- -- -- -- -- BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2
MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10 GM27884
70 70 70 70 70 70 70 8235 70 70 70 70 70 70 70 Evaluation Pot life
1.5 min 1.5 min 1.8 min 2.3 min 1.0 min 1.5 min 1.8 min Results
Three-point 129.4 MPa 117.6 MPa 125.9 MPa 133.5 MPa 130.1 MPa 134.7
MPa 124.4 MPa bending (SD 0.4) (SD 3.9) (SD 11.4) (SD 3.6) (SD 7.0)
(SD 9.3) (SD 4.1) strength (SD) Bending 6.0 GPa 5.9 GPa 7.0 GPa 6.3
GPa 7.0 GPa 6.2 GPa 5.6 GPa elastic (SD 0.5) (SD 0.3) (SD 0.1) (SD
0.2) (SD 0.2) (SD 0.1) (SD 0.3) modulus (SD) Example Example
Comparative Comparative Comparative 34 35 Example 36 Example 37
Example 4 Example 5 Example 6 First UDMA 70 70 70 70 70 70 70 Pack
TEGDMA 30 30 30 30 30 30 30 PBZ -- -- 2 -- -- -- -- PBZCa 1 1 -- 1
-- -- -- tBPB 0.5 0.5 0.5 0.5 0.5 -- -- tAPiN -- -- -- -- -- -- --
DEPT -- -- -- -- -- -- 0.5 DMABAE -- -- 0.3 0.3 -- -- -- p-TSS 2 2
2 2 2 2 5 BHT 0.2 0.2 0.2 0.2 0.2 0.2 02 MEHQ 0.1 0.1 0.1 0.1 0.1
0.1 0.1 R812 10 10 10 10 10 10 10 GM27884 70 70 70 70 70 70 70 8235
70 70 70 70 70 70 70 Second UDMA -- 35 60 60 60 60 60 Pack Bis-GMA
60 35 -- -- -- -- -- TEGDMA 20 25 20 20 20 20 20 GDMA -- -- -- --
-- -- 4-MET -- 5 20 20 20 20 20 MDP 20 -- -- -- -- -- -- Cu
(acac).sub.2 0.002 0.002 0.01 0.02 0.01 0.01 -- CQ -- -- 0.05 0.1
-- -- -- BPO -- -- -- -- -- -- 1 BHT 0.2 0.2 0.2 0.2 0.2 0.2 0.2
MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 R812 10 10 10 10 10 10 10 GM27884
70 70 70 70 70 70 70 8235 70 70 70 70 70 70 70 Evaluation Pot life
2.3 min 1.7 min 1.8 min LC mode 2.1 min LC mode >10 min 3.8 min
4.0 min Results Three-point 107.0 MPa 134.5 MPa 119.7 *129.4 127.7
*130.0 -- 55.3 MPa 114.0 MPa bending (SD 20.4) (SD 3.2) MPa (SD MPa
(SD MPa (SD MPa (SD (SD 3.4) (SD 5.0) strength (SD) 5.2) 11.1)
13.9) 8.0) Bending 5.9 GPa 6.6 GPa 6.0 GPa *6.1 GPa 6.0 GPa *6.1
GPa -- 1.9 GPa (SD 5.7 GPa (SD elastic (SD 0.2) (SD 0.3) (SD 0.1)
(SD 0.2) (SD 0.1) (SD 0.2) 0.2) 0.2) modulus (SD)
[0220] <Evaluation Method of Adhesive Strength to Tooth>
[0221] A bovine tooth adherend was removed, then frozen and
preserved bovine mandibular anterior teeth were thawed under water
injection, and their roots were cut and demyelinated. This was
placed in a plastic cylindrical container with a diameter of 25 mm
and a depth of 25 mm and embedded in an acrylic resin. Immediately
before use, the bovine tooth adherend was polished with
water-resistant emery paper (P400), and smooth surfaces of bovine
tooth enamel and bovine tooth dentin were carved and used.
Measurement was carried out with test pieces used for measuring
adhesive strength according to technical standards corresponding to
compositions shown in Table 4 or Table 5 (described below). A shear
load was applied at a crosshead speed of 1.0 mm/min, in parallel to
bovine tooth enamel or dentin surface and in contact with the
surface, and the adhesive strength was determined by a shear load
when a cured product formed into a column on the bovine tooth
surface peels from the surface.
[0222] Compressed air was blown onto an adhered surface of the test
piece to dry it. After that, equal amounts of the first pack and
the second pack described in Table 4 were taken in a dappen, and a
curable composition obtained by mixing them was applied to a flat
surface of enamel or dentin, and after 20 seconds, a volatile
solvent contained in the composition was distilled off with an air
syringe. Thereafter, a plastic mold with a diameter of 2.38 mm
(manufactured by Ultradent Japan K.K.) was installed, a
photopolymerizable material (Fantasista V, manufactured by Sun
Medical Company, Ltd) was filled therein, and a cylindrical column
was cured by irradiating with light for 20 seconds using a LED
visible light irradiator (Translux 2Wave, manufactured by Kulzer
GmbH). Then, after immersion in water and storage in a 37.degree.
C. thermostat for 18 hours, the adhesive strength was measured.
TABLE-US-00004 TABLE 4 Example 38 Example 39 Example 40 Example 41
Example 42 Example 43 Example 44 Second UDMA 50 50 -- -- -- -- --
Pack Bis-GMA -- -- 50 50 50 60 65 GDMA 10 -- -- -- -- -- -- TEGDMA
-- 20 20 20 -- 20 25 HEMA 10 -- -- -- 20 -- -- MDP -- -- 30 -- 30
20 -- 4-MET 30 30 -- 30 -- -- 10 CuCl.sub.2 0.3 0.3 0.3 0.3 0.3 0.3
0.3 BHT 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acetone -- 70 70 70 70 70 70
H.sub.2O -- 10 10 10 10 10 10 First EtOH 210 210 210 210 210 210
210 Pack H2O 60 60 60 60 60 60 60 PBZ 10 10 10 10 10 10 10 p-TSS 20
20 20 20 20 20 20 tBPB 4 4 4 4 4 4 4 Adhesion to tooth Bovine tooth
enamel 10.4 MPa 10.4 MPa 17.7 MPa 13.6 MPa 12.0 MPa 14.9 MPa 12.0
MPa SD 2.2 1.4 3.6 2.2 2.1 3.3 3.1
[0223] A pretreatment material composition (second pack) prepared
by the composition of Table 5 was applied to the adhered surface of
the bovine dentin dried by blowing compressed air for about 1
second, and after 20 seconds, a solvent component in the
composition was distilled off using an air syringe to prepare a
primer coating. Next, a paste composition of the prepared first
pack was applied to an adherend surface of a cylindrical column
cured product (Fantasista V, manufactured by Sun Medical Company,
Ltd, one in which an adherend surface was previously polished with
water-resistant emery paper P180) of the previously prepared filler
composition (first pack), and the cylindrical column cured product
was placed on a coating part formed on the bovine dentin tooth
adherend, and pressed with a force of 5 N using a dedicated jig.
Thereafter, an excess of adapted composition was removed, and the
cylindrical column was cured by irradiating using the LED visible
light irradiator (Translux 2Wave, manufactured by Kulzer GmbH) from
4 directions for 10 seconds. Then, after immersion in water and
storage in a 37.degree. C. thermostat for 18 hours, the adhesive
strength was measured.
TABLE-US-00005 TABLE 5 Example 45 Example 46 Example 47
Pretreatment UDMA 40 40 40 material GDMA 5 5 5 composition HEMA 5 5
5 (second pack) MDP 20 20 -- 4-MET -- -- 20 CuCl.sub.2 1 1 1 BHT
0.05 0.05 0.05 EtOH 15 15 15 H.sub.2O 15 15 15 Filler UDMA 80 80 80
composition TEGDMA 20 20 20 (first pack) CQ 0.3 0.3 0.3 DMABAE 0.3
0.3 0.3 BHT 0.2 0.2 0.2 MEHQ 0.1 0.1 0.1 PBZ 3 3 3 tBPB 4 -- 4
p-TSS 5 5 5 GM27884 185 185 185 Adhesion to tooth Bovine tooth
enamel 15.4 MPa 14.8 MPa 12.0 MPa SD 4.1 0.9 0.8
[0224] From the above, it was shown that the polymerization
initiator systems containing PBZ shown in Tables 4 and 5 can be
used as chemical polymerization initiator systems, and the curable
composition containing the polymerization initiator system also has
sufficient adhesion to tooth.
[0225] When the value of adhesive strength to tooth is 10 MPa or
more, it can be determined that the curable composition containing
the polymerization initiator of the present invention has
sufficient adhesive strength.
* * * * *