U.S. patent application number 12/523554 was filed with the patent office on 2010-05-27 for polymerizable monomer, polymerizable composition, and dental material.
This patent application is currently assigned to Kuraray Medical Inc.. Invention is credited to Ai Hinamoto, Hiroshige Ishino, Naoki Nishigaki, Koichi Okada, Takahiro Sekiguchi, Mitsuru Takei.
Application Number | 20100130682 12/523554 |
Document ID | / |
Family ID | 39635983 |
Filed Date | 2010-05-27 |
United States Patent
Application |
20100130682 |
Kind Code |
A1 |
Hinamoto; Ai ; et
al. |
May 27, 2010 |
POLYMERIZABLE MONOMER, POLYMERIZABLE COMPOSITION, AND DENTAL
MATERIAL
Abstract
The present invention provides a polymerizable composition that
exhibits excellent adhesive properties to a tooth structure
(particularly dentin) when applied as a dental material, and a
polymerizable monomer that is used as a component of the
polymerizable composition. The present invention is a polymerizable
monomer (A) that is a compound having at least two polymerizable
groups. The polymerizable monomer (A) has a retention time of 7
minutes to 30 minutes in a high-performance liquid chromatography
(HPLC) measurement conducted under a condition in which a column
with an inner diameter of 3.9 mm and a length of 300 mm, packed
with a C18 packing material having been crushed to have an average
particle size of 10 .mu.m and a pore size of 125 angstroms, is
used, an eluent is a mixed solvent of methanol and water contained
at a ratio of 3:7, a flow rate is 1.0 mL/minute, a measurement
temperature is 50.degree. C., a sample injection volume is 10
.mu.L, and a dead volume from a sample inlet to a detection point
excluding the column is 87 .mu.L. The present invention also is a
composition containing the polymerizable monomer (A).
Inventors: |
Hinamoto; Ai; (Okayama,
JP) ; Ishino; Hiroshige; (Okayama, JP) ;
Sekiguchi; Takahiro; (Okayama, JP) ; Okada;
Koichi; (Okayama, JP) ; Takei; Mitsuru;
(Okayama, JP) ; Nishigaki; Naoki; (Okayama,
JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, L.L.P.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Kuraray Medical Inc.
Okayama
JP
|
Family ID: |
39635983 |
Appl. No.: |
12/523554 |
Filed: |
January 16, 2008 |
PCT Filed: |
January 16, 2008 |
PCT NO: |
PCT/JP2008/050435 |
371 Date: |
October 23, 2009 |
Current U.S.
Class: |
524/854 ;
526/277; 560/181 |
Current CPC
Class: |
A61K 6/30 20200101; C08F
20/10 20130101; A61K 6/887 20200101; A61K 6/887 20200101; A61K
6/887 20200101; A61K 6/887 20200101; A61K 6/30 20200101; A61K 6/30
20200101; C08F 20/28 20130101; A61K 6/887 20200101; A61K 6/30
20200101; C08F 220/26 20130101; C08L 33/26 20130101; C08L 33/26
20130101; C08L 33/04 20130101; C08L 33/04 20130101; C08L 33/26
20130101; C08L 33/04 20130101; C08L 33/04 20130101; C08L 33/26
20130101; A61K 6/30 20200101 |
Class at
Publication: |
524/854 ;
560/181; 526/277 |
International
Class: |
C08L 33/10 20060101
C08L033/10; C07C 69/73 20060101 C07C069/73; C08F 230/02 20060101
C08F230/02 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 17, 2007 |
JP |
2007-008420 |
Jan 17, 2007 |
JP |
2007-008421 |
Mar 20, 2007 |
JP |
2007-073603 |
Claims
1. A polymerizable monomer (A) having at least two polymerizable
groups, wherein the polymerizable monomer (A) has a retention time
of 7 minutes to 30 minutes in a high-performance liquid
chromatography (HPLC) measurement conducted under a condition
wherein a column with an inner diameter of 3.9 mm and a length of
300 mm, packed with a C18 packing material which is crushed to have
an average particle size of 10 .mu.m and a pore size of 125
angstroms, is used, an eluent is a mixed solvent of methanol and
water at a ratio of 3:7, a flow rate is 1.0 mL/minute, a
measurement temperature is 50.degree. C., a sample injection volume
is 10 .mu., and a dead volume from a sample inlet to a detection
point excluding the column is 87 .mu.L.
2. The polymerizable monomer (A) according to claim 1, having at
least two hydroxyl groups.
3. The polymerizable monomer (A) according to claim 1, having at
least three hydroxyl groups.
4. The hydrophilic monomer (A) according to claim 1, wherein each
of the polymerizable groups is a group represented by formula (1),
formula (2), or formula (3): ##STR00009## where R.sup.1, R.sup.2,
and R.sup.3 each denote a hydrogen atom or an aliphatic hydrocarbon
group having 1 to 10 carbon atoms and "*" denotes a bond.
5. The polymerizable monomer (A) according to claim 4, wherein each
of the R.sup.1, R.sup.2, and R.sup.3 is a hydrogen atom or a methyl
group.
6. The polymerizable monomer (A) according to claim 1, wherein the
polymerizable monomer (A) is a compound represented by formula (4):
##STR00010## where Gs are hydroxyl groups or polymerizable groups,
n is an integer of 3 or more, at least three of the Gs are hydroxyl
groups, and at least two of the Gs are polymerizable groups.
7. A composition, comprising the polymerizable monomer (A)
according to claim 1.
8. The composition according to claim 7, further comprising, as a
polymerizable monomer component, at least one polymerizable monomer
selected from the group consisting of a polymerizable monomer (B)
having one polymerizable functional group and at least one hydroxyl
group, a polymerizable monomer (C) having an acidic group, and a
crosslinkable polymerizable monomer (D).
9. The composition according to claim 7, comprising a solvent
(E).
10. The composition according to according to claim 7, comprising a
polymerization initiator (F).
11. The composition according to according to claim 7, comprising a
polymerization accelerator (G).
12. The composition according to according to claim 7, comprising a
filler (H).
13. The composition according to claim 7, for a dental
application.
14. A primer comprising the composition according to claim 7.
15. A bonding material comprising the composition according to
claim 7.
16. A composite resin comprising the composition according to claim
7.
17. A cement comprising the composition according to claim 7.
Description
TECHNICAL FIELD
[0001] The present invention relates to a hydrophilic polymerizable
monomer that is used mainly for dental materials and that has a
plurality of polymerizable groups. The present invention also
relates to a polymerizable composition containing the polymerizable
monomer. The present invention also relates to dental materials
using the composition, such as dental primers, bonding materials,
cements, and composite resins.
BACKGROUND ART
[0002] When a lost part of a tooth is filled or covered with a
restorative material, generally a dental adhesive is used. A known
dental adhesive is one containing a polymerizable monomer having a
polymerizable group and a hydroxyl group.
[0003] For example, WO 2004/047773 describes a dental adhesive
composition characterized by containing a polyfunctional
polymerizable monomer that is an ester compound of polyhydric
alcohol having 3 to 6 carbon atoms and a plurality of (meth)acrylic
acids and that has one to two hydroxyl groups, a monofunctional
(meth)acrylate having no hydroxyl group in the molecule, a
polymerizable monomer having an acidic group in the molecule, an
organoboron compound as a curing agent, and a filling material.
This describes that the addition of a small amount of the above
polyfunctional polymerizable monomer to the composition can improve
the cure rate considerably almost without affecting the adhesive
properties of the composition, physical properties of the cured
product, or operable time. This composition is, however, not
necessarily excellent in penetrability into a collagen layer of
dentin and may cause a reduction in bond strength, and therefore
improvement in this respect has been desired.
[0004] When such a dental adhesive is allowed to act on dentin, it
is important for the dental adhesive to have an decalcifying effect
that allows a dentin surface to be dissolved with an acidic
component, a penetration effect that allows a monomer component to
penetrate into a collagen layer of dentin, and a curing effect that
allows the monomer component thus penetrated to solidify to form a
hybrid layer (hereinafter also referred to as a "resin-impregnated
layer") with collagen.
[0005] It has been studied so far to simplify the form of
application of the dental adhesive from a three-component
three-step type in which the aforementioned decalcifying effect,
penetration effect, and curing effect are applied sequentially, to
a two-component two-step type in which the decalcifying effect and
the penetration effect are integrated, and further to a
one-component one-step type in which the decalcifying effect,
penetration effect, and curing effect are all combined together.
All the forms of application require compositions that can be used
for dental adhesives that are excellent in adhesive properties.
Therefore, there is a demand for a polymerizable monomer that is
used as a component of the composition and that imparts the
excellent adhesive properties.
DISCLOSURE OF INVENTION
[0006] The present invention is intended to provide a polymerizable
composition that exhibits excellent adhesive properties to a tooth
structure (particularly dentin) when it is applied as a dental
material, and a polymerizable monomer that is used as a component
of the polymerizable composition. The present invention also is
intended to provide a dental material that is excellent in adhesive
properties to a tooth structure (particularly dentin).
[0007] The present invention is a polymerizable monomer (A) that is
a compound having at least two polymerizable groups. The
polymerizable monomer (A) has a retention time of 7 minutes to 30
minutes in a high-performance liquid chromatography (HPLC)
measurement conducted under a condition in which a column with an
inner diameter of 3.9 mm and a length of 300 mm, packed with a C18
packing material having been crushed to have an average particle
size of 10 .mu.m and a pore size of 125 angstroms, is used, an
eluent is a mixed solvent of methanol and water contained at a
ratio of 3:7, a flow rate is 1.0 mL/minute, a measurement
temperature is 50.degree. C., a sample injection volume is 10
.mu.L, and a dead volume from a sample inlet to a detection point
excluding the column is 87 .mu.L.
[0008] Preferably, the polymerizable monomer (A) of the present
invention has at least two hydroxyl groups, and more preferably has
at least three hydroxyl groups.
[0009] The polymerizable group of the polymerizable monomer (A)
preferably is a group represented by the following formula (1),
formula (2), or formula (3):
##STR00001##
[0010] where R.sup.1, R.sup.2, and R.sup.3 each indicate a hydrogen
atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms
and "*" indicates a bond.
[0011] Preferably, R.sup.1, R.sup.2, and R.sup.3 each are a
hydrogen atom or a methyl group.
[0012] Preferably, the polymerizable monomer (A) is a compound
represented by formula (4):
##STR00002##
[0013] where Gs are hydroxyl groups or polymerizable groups, n is
an integer of 3 or more, at least three of the Gs are hydroxyl
groups, and at least two of the Gs are polymerizable groups.
[0014] In another aspect, the present invention is a composition
containing the polymerizable monomer (A).
[0015] Preferably, the composition of the present invention further
contains, as a polymerizable monomer component, at least one
polymerizable monomer selected from the group consisting of a
polymerizable monomer (B) having one polymerizable functional group
and at least one hydroxyl group, a polymerizable monomer (C) having
an acidic group, and a crosslinkable polymerizable monomer (D).
Preferably, the composition of the present invention contains a
solvent (E). Preferably, the composition of the present invention
contains a polymerization initiator (F). Preferably, the
composition of the present invention contains a polymerization
accelerator (G). Preferably, the composition of the present
invention contains a filler (H).
[0016] Preferably, the composition of the present invention is a
dental composition.
[0017] In yet another aspect, the present invention is a primer, a
bonding material, a composite resin, and a cement each using the
dental composition.
[0018] The polymerizable monomer (A) of the present invention is a
hydrophilic compound having a plurality of polymerizable groups.
Thus, the polymerizable monomer (A) of the present invention is
useful for applications that require the polymerizable monomer (A)
to be curable and applications that require a polymer of the
polymerizable monomer (A) to be hydrophilic. The composition
containing the polymerizable monomer (A) of the present invention
is useful for various applications including dental applications.
Especially, the dental materials, such as a dental primer, bonding
material, cement, and composite resin, using the composition have
excellent adhesive properties to a tooth structure (particularly
dentin).
BEST MODE FOR CARRYING OUT THE INVENTION
[0019] First, the polymerizable monomer (A) of the present
invention is described.
[0020] Polymerizable Monomer (A)
[0021] The polymerizable monomer (A) has at least two polymerizable
groups. When a composition containing the polymerizable monomer (A)
is used for a dental application, these polymerizable groups are
polymerized and thereby the composition is cured to be able to
function as dental materials such as a primer, bonding material,
composite resin, and cement. Furthermore, since the number of the
polymerizable groups is two or more, the polymerizable monomer (A)
has crosslinkability. Accordingly, the composition containing the
polymerizable monomer (A) has high curability and the cured product
has high mechanical strength. The number of the polymerizable
groups preferably is six or less because an excessive amount of the
polymerizable groups makes it difficult to attain an appropriate
hydrophilicity in some cases.
[0022] With respect to the polymerizable monomer (A), the
polymerizable group denotes a group including a radical
polymerizable functional group and examples thereof include a group
including a vinyl group. Particularly, from the viewpoint of
polymerization reactivity, the group represented by the following
formula (1), (2), or (3) is preferable as the polymerizable group.
Among these, from the viewpoint of ease of introduction into the
polymerizable monomer (A), a group represented by formula (1) is
most preferable.
##STR00003##
[0023] In the above formulae, R.sup.1, R.sup.2, and R.sup.3 each
indicate a hydrogen atom or an aliphatic hydrocarbon group having 1
to 10 carbon atoms and "*" indicates a bond. Examples of the
aliphatic hydrocarbon group having 1 to 10 carbon atoms include an
alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2
to 10 carbon atoms, and an alkynyl group having 2 to 10 carbon
atoms.
[0024] The alkyl group having 1 to 10 carbon atoms may be any one
of linear, branched, and cyclic, and examples thereof include a
methyl group, ethyl group, n-propyl group, isopropyl group,
cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group,
tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl
group, neopentyl group, tert-pentyl group, cyclopentyl group,
n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group,
cycloheptanyl group, n-octyl group, 2-ethylhexyl group,
cyclooctanyl group, n-nonyl group, cyclononanyl group, and n-decyl
group.
[0025] The alkenyl group having 2 to 10 carbon atoms may be any one
of linear, branched, and cyclic, and examples thereof include a
vinyl group, allyl group, methylvinyl group, propenyl group,
butenyl group, pentenyl group, hexenyl group, cyclopropenyl group,
cyclobutenyl group, cyclopentenyl group, and cyclohexenyl
group.
[0026] The alkynyl group having 2 to 10 carbon atoms may be any one
of linear, branched, and cyclic, and examples thereof include
ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl,
2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl,
3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl,
2-methyl-3-butynyl, 1-hexynyl, 2-hexynyl, 1-ethyl-2-butynyl,
3-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl,
4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, and
1-ethyl-3-butynyl.
[0027] When the polymerizable monomer (A) is used in, for example,
dental applications, radical polymerization is performed.
Accordingly, it is preferable from the viewpoint of radical
polymerization reactivity that R.sup.1, R.sup.2, and R.sup.3 each
be a hydrogen atom or a methyl group. Furthermore, when the
polymerizable monomer (A) is used for a dental composition, the
polymerizable group may be detached from the polymerizable monomer
(A) by, for example, hydrolysis. When the stimulativeness of the
detached polymerizable group to a biological body is taken into
account, it is preferable that the polymerizable group include a
methacryloyloxy group. Therefore, it is more preferable that
R.sup.1, R.sup.2, and R.sup.3 each be a methyl group.
[0028] The polymerizable monomer (A) includes at least two
polymerizable groups, and the at least two polymerizable groups may
be identical to or different from each other.
[0029] The polymerizable monomer (A) is characterized in that it
has a retention time of 7 minutes to 30 minutes in a
high-performance liquid chromatography (HPLC) measurement conducted
under a condition in which a column with an inner diameter of 3.9
mm and a length of 300 mm, packed with a C18 packing material
having been crushed to have an average particle size of 10 .mu.m
and a pore size of 125 angstroms, is used, an eluent is a mixed
solvent of methanol and water contained at a ratio of 3:7, a flow
rate is 1.0 mL/minute, a measurement temperature is 50.degree. C.,
a sample injection volume is 10 .mu.L, and a dead volume from a
sample inlet to a detection point excluding the column is 87
.mu.L.
[0030] When bonding a dental material using a dental composition to
a tooth structure, the dental material will be bonded to a collagen
layer of dentin exposed by decalcifying. Accordingly, in order to
achieve a high bond strength, penetrability of the dental material
into the collagen layer, and the strength of a layer (hereinafter
referred to as a resin-impregnated layer) formed of the collagen
layer and the dental material integrated with each other are
important. Thus, the hydrophilic degree of the polymerizable
monomer contained in the dental material is important. The present
inventors have found that a retention time obtained from an HPLC
measurement under a particular condition can define the hydrophilic
degree of the polymerizable monomer that can provide the dental
material with excellent adhesive properties to a tooth structure,
resulting in the achievement of the present invention.
[0031] As the column with an inner diameter of 3.9 mm and a length
of 300 mm, packed with the C18 packing material having been crushed
to have an average particle size of 10 .mu.m and a pore size of 125
angstroms, there can be used, for example, .mu.Bondapak ("Micro
Bondapak" (registered trademark)) C.sub.18 analytical column (C18
packing material (crushed type) with an average particle size of 10
micrometers and a pore size of 125 angstroms, the column size 3.9
mm.times.300 mm), manufactured by Waters Corp.
[0032] In order to meet the requirement that the dead volume from
the sample inlet to the detection point excluding the column be 87
.mu.L, it is recommended to use, in the HPLC, CBM-20A, manufactured
by Shimadzu Corp., as a system controller, SIL-20A, manufactured by
Shimadzu Corp., as an autosampler, and SPD-M20A, manufactured by
Shimadzu Corp., as a detector.
[0033] For detection, it is recommended to use an ultraviolet ray
with a wavelength of 254 nm and a band width of 4 nm.
[0034] The polymerizable monomer (A) of the present invention has a
retention time of 7 minutes to 30 minutes when being subject to an
HPLC measurement under the aforementioned measurement condition.
The inside of an oral cavity has a humid environment, and the
temperature thereof is subject to change according to the
temperatures of food and drink. Thus, the cured product may absorb
water and be hydrolyzed. Since polymerizable monomers with a
retention time shorter than 7 minutes have an excessively high
hydrophilicity, the cured product may absorb water and be
hydrolyzed, deteriorating the mechanical strength of an adhesive
layer. Moreover, a small amount of the polymerizable monomer
remaining uncured may be eluted from the dental material. In
contrast, polymerizable monomers with a retention time of longer
than 30 minutes have an excessively poor hydrophilicity, and cannot
penetrate sufficiently into a collagen layer of dentin, making it
difficult to provide the composition with high adhesive properties
to a tooth structure. Preferably, the retention time is 10 minutes
or longer, and 25 minutes or shorter.
[0035] In selecting a polymerizable monomer with a retention time
of 7 minutes to 30 minutes when being subject to an HPLC
measurement under the aforementioned measurement condition, the
selection should be done considering the molecular size of the
polymerizable monomer as well as the type and number of hydrophilic
group. When two polymerizable monomers have the same type and the
same number of hydrophilic group, the one with a larger molecular
size tends to show a longer retention time. On the other hand, when
two polymerizable monomers have the same type of hydrophilic group
and the same molecular size, the one having more hydrophilic groups
tends to show a shorter retention time. When two polymerizable
monomers have the same number of hydrophilic group and the same
molecular size, the one having the hydrophilic group with higher
hydrophilicity tends to show a shorter retention time. Moreover,
the retention time becomes shorter when the hydrophilic group is
located at a position where steric hindrance is smaller, like a
position closer to an end of a molecular chain than to a side
chain. As the polymerizable monomer with a retention time of 7
minutes to 30 minutes, there can be mentioned, for example, a
compound represented by the following formulas (5) to (8)
(erythritol dimethacrylate, xylitol dimethacrylate, sorbitol
dimethacrylate, mannitol dimethacrylate, etc.) Their retention
times are shown in Examples. Several kinds of polymerizable
monomers and their retention times are shown in Comparative
Examples to be described later. Based on the above-mentioned
tendencies and the retention times described in the Examples and
the Comparative Examples, it is possible to select efficiently a
polymerizable monomer with a retention time of 7 minutes to 30
minutes.
##STR00004##
[0036] Preferably, the polymerizable monomer (A) has two or more
hydroxyl groups. By having two or more hydroxyl groups, the
polymerizable monomer (A) is given a high hydrophilicity and an
excellent penetrability into a collagen layer of dentin. Thereby,
excellent adhesive properties to a tooth structure (particularly
dentin) can be given to the dental composition. From the viewpoint
of achieving higher adhesive properties, the number of hydroxyl
groups preferably is three or more. On the other hand, since an
excessive amount of hydroxyl groups may make it difficult to ensure
an appropriate hydrophilicity, the number of hydroxyl groups
preferably is six or less.
[0037] The molecular structure constituting the polymerizable
monomer (A), other than the polymerizable groups, is not
particularly limited. The polymerizable groups, and the hydrophilic
group such as a hydroxyl group preferably are bonded to a
hydrocarbon chain.
[0038] The polymerizable monomer (A) preferably is a compound
represented by the following formula (4).
##STR00005##
[0039] In the above formula, Gs are hydroxyl groups or
polymerizable groups, n is an integer of 3 or more, at least three
of the Gs are hydroxyl groups, and at least two of the Gs are
polymerizable groups.
[0040] In this structure, the polymerizable group or the hydroxyl
group is bonded to each carbon atom of the carbon chain, and
therefore the polymerizable groups and hydroxyl groups are
closely-located with a high density. Accordingly, when a
composition containing this polymerizable monomer (A) is applied as
a dental material, it exhibits excellent curability and adhesive
properties. Furthermore, it also has an advantage that it can be
produced easily using sugar alcohol.
[0041] From the viewpoints of curability and adhesive properties to
a tooth structure as well as availability of raw materials, n is
preferably an integer of 3 to 10, more preferably an integer of 3
to 8, and most preferably an integer of 3 or 4.
[0042] When adhesive properties to a tooth structure is considered
important, the polymerizable monomer (A) is preferably a compound
represented by the following formula (9).
##STR00006##
[0043] In the above formula, R.sup.1 denotes the same as described
above, m denotes an integer of 2 or more, k denotes an integer of 1
or more, and the sequence order of m units having an ester group
and k units having a hydroxyl group is arbitrary.
[0044] From the viewpoints of curability and adhesive properties to
a tooth structure as well as availability of raw materials, m is
preferably 2 to 5, more preferably 2 to 4, and most preferably 2.
Furthermore, k is preferably 1 to 5, more preferably 2 to 4, and
most preferably 2. The total of m and k is preferably 3 to 10, more
preferably 3 to 8, further preferably 4 to 6, and most preferably
4.
[0045] The compound represented by formula (9) has at least three
hydroxyl groups, two of which are primary hydroxyl groups. These
primary hydroxyl groups are highly advantageous for interaction
with a tooth structure (particularly dentin). Accordingly, when a
composition containing a compound represented by formula (9) is
applied as dental applications, a composition with particularly
high adhesive properties to a tooth structure (particularly dentin)
is obtained. Moreover, since at least two groups represented by
formula (1) are included as polymerizable groups, curability also
is excellent.
[0046] Furthermore, among the compounds represented by formula (9),
compounds represented by formulas (8) and (10) are preferable from
the viewpoints of curability and adhesive properties to a tooth
structure.
##STR00007##
[0047] On the other hand, when curability is considered important,
the polymerizable monomer (A) is preferably a compound represented
by the following formula (11).
##STR00008##
[0048] In the above formula, R.sup.1 denotes the same as described
above, and p denotes an integer of 3 or more.
[0049] The compound represented by formula (11) has polymerizable
groups represented by formula (1) at the both ends of an
unconjugated carbon chain with at least four carbon atoms bonded
continuously and has particularly high polymerization performance
due to a steric factor. Accordingly, when a composition containing
the compound represented by formula (11) is applied as a dental
application, it serves as a composition with particularly high
curability. Moreover, since it has at least three of hydroxyl
groups, it has excellent penetrability into a collagen layer of
dentin as well as excellent adhesive properties to a tooth
structure.
[0050] p is preferably 3 or 4. This is because when a decomposition
product is produced by an action such as hydrolysis inside an oral
cavity, the decomposition product is a highly safe compound such as
xylitol, sorbitol, or mannitol. Examples of compounds in which p is
an integer of 3 or 4 include xylitol di(meth)acrylate, and sorbitol
di(meth)acrylate.
[0051] The polymerizable monomer (A) can be obtained through
production by a known method. Specifically, for example, a
carboxylic acid having a polymerizable group (for instance, a
carboxylic acid in which a hydrogen atom is bonded to a bond of a
group represented by formula (1)) or a derivative thereof, and a
chain polyhydric alcohol compound (a sugar alcohol compound) such
as xylitol, sorbitol, and mannitol may be allowed to undergo an
esterification reaction according to a conventional method and this
may then be purified by a separation means such as chromatography.
In order to improve the yield, the esterification reaction may be
carried out after the carboxylic acid having a polymerizable group
is converted into a derivative such as an acid halide.
[0052] When the polymerizable monomer (A) is particularly a
compound represented by formula (9), especially a compound
represented by formula (8) or (10), it is preferable that the
polymerizable monomer (A) be produced by performing a step (a)
where using a compound in which primary hydroxyl groups of a chain
polyhydric alcohol compound such as mannitol are protected
beforehand, as a raw material, the compound and carboxylic acid
having a polymerizable group (in this case, carboxylic acid in
which a hydrogen atom is bonded to a bond of a group represented by
formula (1)) or a derivative thereof are esterified, and a step (b)
where the protecting groups of the primary hydroxyl groups of the
resultant ester compound are deprotected. The derivative of the
carboxylic acid having a polymerizable group is not particularly
limited but an acid halide or acid anhydride is used preferably.
When the reactivity with the alcohol compound is taken into
account, an acid halide is used more preferably. Furthermore, among
the acid halides, acid chloride is used particularly preferably
when availability and storage stability of the compound are taken
into account. The production process including these steps allows a
polymerizable monomer to be obtained with high yield and therefore
is suitable for industrial production.
[0053] The compound in which primary hydroxyl groups of the alcohol
compound are protected beforehand can be obtained as a commercially
available product, for example,
1,2:5,6-di-O-isopropylidene-D-mannitol and
1,3:4,6-di-O-benzylidene-D-mannitol. Furthermore, it also can be
produced by carrying out a step of protecting the primary hydroxyl
groups of the alcohol compound. In a compound in which primary
hydroxyl groups of the alcohol compound are protected beforehand,
it is preferable that a part of hydroxyl groups other than the
primary hydroxyl groups be protected while a plurality of hydroxyl
groups are allowed to remain. In this manner, a structure having at
least three hydroxyl groups is obtained easily.
[0054] The step of protecting the primary hydroxyl groups of the
alcohol compound can be carried out by performing a known reaction
for introducing protecting groups.
[0055] It is advantageous to select a group that is introduced
preferentially into a primary hydroxyl group, as a protecting group
for the primary hydroxyl groups of the alcohol compound.
Furthermore, for the protecting group, it is advantageous to select
one that tends not to undergo a deprotection reaction during the
esterification reaction and tends not to allow the ester bond to be
cleaved during the deprotection reaction. From these viewpoints,
protecting groups that are used preferably are ether protecting
groups, silyl ether protecting groups, and acetal protecting
groups. Ether protecting groups that are used more preferably are a
1-ethoxyethyl ether group and triphenylmethyl ether group. Silyl
ether protecting groups that are used more preferably are a
triisopropylsilyl ether group, t-butyldimethylsilyl ether group,
and t-butyldiphenylsilyl ether group. Each of these protecting
groups can be introduced preferentially into a primary hydroxyl
group and can be deprotected under a mild acidic condition, and
therefore it has an advantage that deprotection can be achieved
without cleaving the ester bond. On the other hand, acetal
protecting groups that are used more preferably are an
isopropylidene group, cycloheptylidene group, benzylidene group,
and p-methoxybenzylidene group. When using an acetal protecting
group, it not only can be introduced preferentially into a primary
hydroxyl group but also can protect two or more hydroxyl groups
including the primary hydroxyl group at the same time. Accordingly,
the acetal protecting group is especially suitable for synthesis of
the polymerizable monomer (A). Therefore, among the ether
protecting groups, silyl ether protecting groups, and acetal
protecting groups, the acetal protecting groups are used further
preferably. Moreover, from the viewpoints that deprotection is
possible under a particularly mild acidic condition and a byproduct
produced at the time of deprotection can be removed easily, an
isopropylidene group is used particularly preferably.
[0056] The step of esterifying a compound in which primary hydroxyl
groups of the alcohol compound are protected beforehand and a
carboxylic acid having a polymerizable group or a derivative
thereof can be carried out according to a known method. For the
esterification reaction, it is important to select suitable
reaction conditions (particularly, the temperature condition and
the type of catalyst) under which a deprotection reaction tends not
to occur, with consideration given to the type of the protecting
group. Furthermore, it is important to select the reaction
conditions (particularly, the amounts of the compound in which
primary hydroxyl groups of the alcohol compound are protected
beforehand and the carboxylic acid having a polymerizable group or
a derivative thereof to be used) so that after the esterification
reaction, a plurality of ester bonds are formed and the total
number of the protected hydroxyl groups and unreacted hydroxyl
groups is at least three, in one molecule.
[0057] The step of deprotecting the protecting groups of the
primary hydroxyl groups of the resultant ester compound may be
carried out according to a known method depending on the type of
the protecting group. In this case, it is important to select
reaction conditions (particularly, the temperature condition and
the type of catalyst) under which the ester bond tends not to be
cleaved. As described above, when the ether protecting groups,
silyl ether protecting groups and acetal protecting groups that are
preferable as the protecting group of the primary hydroxyl group
are used, all of them can be deprotected under mild acidic
conditions and therefore deprotection can be performed without
allowing the ester bond to be cleaved. Furthermore, the silyl ether
protecting groups can be deprotected with extremely high
selectivity by the use of a fluorine-containing compound such as
TBAF (tetrabutylammonium fluoride) and thus are highly useful. In
the case of deprotection under an acidic condition, for example,
mineral acids such as hydrochloric acid and sulfuric acid and
aqueous solutions thereof, organic acids such as formic acid,
acetic acid, and trifluoroacetic acid and aqueous solutions
thereof; and cation exchange resin are used preferably. Among
these, since the acidity is suitable and deprotection can be
performed with cleavage of the ester bond being prevented
efficiently, organic acids such as formic acid, acetic acid, and
trifluoroacetic acid and aqueous solutions thereof are more
preferable, and formic acid, acetic acid, and aqueous solutions
thereof are further preferable.
[0058] Since the polymerizable monomer (A) has a plurality of
polymerizable groups and is hydrophilic, it is excellent in
crosslinking reactivity and can interact strongly with a compound
having a hydrophilic group. Accordingly, when the polymerizable
monomer is mixed with a suitable component into a composition, the
composition thus obtained exhibits excellent curability and
adhesive properties in various applications including dental
applications. The polymerizable monomers (A) can be used
independently or two or more of them can be used in combination.
From the viewpoint of obtaining both curability and adhesive
properties to a tooth structure of the composition in a balanced
manner, compounds represented by the aforementioned formulae (9)
and (11) can be used in combination.
[0059] Next, the composition of the present invention is described.
The composition of the present invention is a composition
containing the polymerizable monomer (A). A component other than
the polymerizable monomer (A) appropriately can be selected
depending on the application of the composition. For example, the
composition can be obtained from a composition containing a known
crosslinkable polymerizable monomer by replacing the crosslinkable
polymerizable monomer with the polymerizable monomer (A).
[0060] As the component that the composition of the present
invention contains besides the polymerizable monomer (A), there can
be mentioned, for example, polymerizable monomer components such as
a polymerizable monomer (B) having one polymerizable functional
group and at least one hydroxyl group, a polymerizable monomer (C)
having an acidic group, and a crosslinkable polymerizable monomer
(D), a solvent (E), a polymerization initiator (F), a
polymerization accelerator (G), and a filler (H).
[0061] In the present invention, the phrase "the whole amount of
polymerizable monomer components" denotes the total amount of the
polymerizable monomers (A) to (D).
[0062] The amount of polymerizable monomer (A) to be added may be
determined appropriately according to the application of the
composition. Generally, it is preferable that 1 to 99 parts by mass
of polymerizable monomer (A) be contained in 100 parts by mass of
the whole amount of polymerizable monomer components. When a
composition in which the amount of polymerizable monomer (A) to be
added is in such a range is used as a dental composition, there are
advantages that penetrability into a collagen layer of dentin is
excellent and bond strength is high. When the amount of
polymerizable monomer (A) to be added is less than 1 part by mass,
bond strength may be reduced and bond durability also may be
reduced. Therefore, the amount is more preferably at least 2 parts
by mass and further preferably at least 5 parts by mass. On the
other hand, the amount of polymerizable monomer (A) to be added
exceeding 99 parts by mass results in insufficient decalcification
and sufficiently high bond strength may not be obtained. Therefore
the amount is more preferably 98 parts by mass or less and further
preferably 95 parts by mass or less.
[0063] In the following description, terms "monofunctional",
"bifunctional", and "trifunctional" are used and the terms
"monofunctional", "bifunctional", and "trifunctional" indicate that
one, two, and three polymerizable groups each are contained in one
molecule. Preferably, these polymerizable groups are groups that
are radical-copolymerizable with polymerizable groups of the
polymerizable monomer (A).
[0064] Polymerizable Monomer (B) Having One Polymerizable Group and
at Least One Hydroxyl Group
[0065] Preferably, the composition containing the polymerizable
monomer (A) of the present invention contains the polymerizable
monomer (B) having one polymerizable group and at least one
hydroxyl group. When the composition contains the polymerizable
monomer (B), particularly when it is used as a dental composition,
excellent bond strength is obtained. Since the polymerizable
monomer (B) has a polymerizable group, not only radical
polymerization can occur but also copolymerization with another
monomer can occur. The polymerizable monomer (B) having one
polymerizable group and at least one hydroxyl group is not
particularly limited. The polymerizable group of the polymerizable
monomer (B) is preferably a group that is radical-copolymerizable
with a polymerizable group of the polymerizable monomer (A). From
the viewpoint of ease of radical polymerization, the polymerizable
group preferably is a (meth)acrylic group or (meth)acrylamide
group. The polymerizable monomer (B) is used preferably as a
component of a dental composition. However, since the inside of an
oral cavity has a humid environment, the polymerizable group may be
detached by, for example, hydrolysis. When consideration is given
to stimulativeness of a detached polymerizable group to a
biological body, the polymerizable group is preferably a
methacrylic group or methacrylamide group.
[0066] The polymerizable monomer (B) has at least one hydroxyl
group and therefore has excellent hydrophilicity, and it is a
monofunctional polymer monomer having one polymerizable group.
Accordingly, when a composition containing the polymerizable
monomer (A) and the polymerizable monomer (B) is used as a dental
composition, an effect that the penetrability into a collagen layer
of dentin is further excellent also is obtained.
[0067] The polymerizable monomers (B) can be used independently or
two or more of them can be used in suitable combination. Examples
of the polymerizable monomer (B) include
2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate,
4-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, and
N,N-(dihydroxyethyl)(meth)acrylamide. Among these, from the
viewpoint of improving the penetrability into a collagen layer of
dentin, 2-hydroxyethyl(meth)acrylate,
3-hydroxypropyl(meth)acrylate, glycerol mono(meth)acrylate, and
erythritol mono(meth)acrylate are preferable and
2-hydroxyethylmethacrylate is particularly preferable.
[0068] The amount of polymerizable monomer (B) to be added is not
particularly limited, but it is preferable that 1 to 90 parts by
mass of polymerizable monomer (B) be contained in 100 parts by mass
of the whole amount of polymerizable monomer components. When a
composition in which the amount of polymerizable monomer (B) to be
added is in such a range is used as a dental composition, both
excellent penetrability into a collagen layer of dentin and
excellent bond strength are obtained and it thus is preferable.
When the amount of polymerizable monomer (B) to be added is less
than 1 part by mass, contribution of the polymerizable monomer (B)
to penetration into a collagen layer of dentin may not be obtained
and the bond strength may be reduced. The amount of polymerizable
monomer (B) to be added is more preferably at least 3 parts by
mass, further preferably at least 5 parts by mass, and particularly
preferably at least 7 parts by mass. On the other hand, when the
amount of polymerizable monomer (B) to be added exceeds 90 parts by
mass, sufficiently high curability cannot be obtained and therefore
the mechanical strength of the cured product may be reduced.
Accordingly, the bond strength may be reduced. The amount of
polymerizable monomer (B) to be added is more preferably 80 parts
by mass or less, further preferably 75 parts by mass or less, and
particularly preferably 70 parts by mass or less.
[0069] Polymerizable Monomer (C) Having Acidic Group
[0070] Preferably, the composition of the present invention
contains a polymerizable monomer (C) having an acidic group. When a
composition containing the polymerizable monomer (C) having an
acidic group is used, the polymerizable monomer (C) itself that has
an acidic group has an acid-etching effect and a primer treatment
effect. Therefore, it has advantages that, for example,
pretreatments such as an acid etching treatment and a primer
treatment are not necessary. Accordingly, a combination with the
polymerizable monomer (C) having an acidic group makes it possible
to obtain a composition suitable for self-etching primers and
one-component bonding materials.
[0071] The polymerizable monomers (C) having an acidic group can be
used independently or two or more of them can be used in suitable
combination. The polymerizable monomer (C) having an acidic group
is not particularly limited. Examples thereof include a
monofunctional polymerizable monomer having one carboxyl group or
an acid anhydride group thereof in the molecule, a monofunctional
polymerizable monomer having a plurality of carboxyl groups or an
acid anhydride group thereof in the molecule, and a monofunctional
polymerizable monomer having a phosphinyloxy group or phosphonooxy
group in the molecule (also referred to as a monofunctional radical
polymerizable phosphoric acid ester).
[0072] Examples of the monofunctional polymerizable monomer having
one carboxyl group or an acid anhydride group thereof in the
molecule include (meth)acrylic acid, N-(meth)acryloylglycine,
N-(meth)acryloylaspartic acid, N-(meth)acryloyl-5-aminosalicylic
acid, 2-(meth)acryloyloxyethyl hydrogen succinate,
2-(meth)acryloyloxyethyl hydrogen phthalate,
2-(meth)acryloyloxyethyl hydrogen malate, 6-(meth)acryloyloxyethyl
naphthalene-1,2,6-tricarboxylic acid, O-(meth)acryloyltyrosine,
N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine,
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-4-aminosalicylic
acid, and compounds obtained by converting the carboxyl group of
these compounds into an acid anhydride group.
[0073] Examples of the monofunctional polymerizable monomer having
a plurality of carboxyl groups or an acid anhydride group thereof
in the molecule include
11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid,
10-(meth)acryloyloxydecane-1,1-dicarboxylic acid,
12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid,
6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid,
2-(meth)acryloyloxyethyl-3'-methacryloyloxy-2'-(3,4-dicarboxybenzoyloxy)--
propyl succinate, 4-(2-(meth)acryloyloxyethyl)trimeritate
anhydride, 4-(2-(meth)acryloyloxyethyl)trimeritate,
4-(meth)acryloyloxyethyl trimeritate, 4-(meth)acryloyloxybutyl
trimeritate, 4-(meth)acryloyloxyhexyl trimeritate,
4-(meth)acryloyloxydecyl trimeritate,
6-(meth)acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid
anhydride, 6-(meth)acryloyloxyethylnaphthalene-2,3,6-tricarboxylic
acid anhydride,
4-(meth)acryloyloxyethylcarbonylpropionoyl-1,8-naphthalic acid
anhydride, 4-(meth)acryloyloxyethylnaphthalene-1,8-tricarboxylic
acid anhydride, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid,
13-(meth)acryloyloxytridecane-1,1-dicarboxylic acid, and
11-(meth)acrylamideundecane-1,1-dicarboxylic acid.
[0074] Examples of the monofunctional polymerizable monomer having
a phosphinyloxy group or phosphonooxy group in the molecule (also
referred to as a monofunctional radical polymerizable phosphoric
acid ester) include 2-(meth)acryloyloxyethyl dihydrogenphosphate,
2-(meth)acryloyloxyethylphenyl hydrogenphosphate,
10-(meth)acryloyloxydecyl dihydrogenphosphate,
6-(meth)acryloyloxyhexyl dihydrogenphosphate,
2-(meth)acryloyloxyethyl-2-bromoethyl hydrogenphosphate, and
2-(meth)acrylamideethyl dihydrogenphosphate.
[0075] Examples of other monofunctional polymerizable monomer
having an acidic group include a monofunctional polymerizable
monomer having a sulfo group in the molecule such as
2-(meth)acrylamide-2-methylpropanesulfonic acid and
10-sulfodecyl(meth)acrylate.
[0076] The amount of polymerizable monomer (C) having an acidic
group to be added is not particularly limited. Generally, it is
preferable that 1 to 90 parts by mass of polymerizable monomer (C)
having an acidic group be contained in 100 parts by mass of the
whole amount of polymerizable monomer components. When the amount
of polymerizable monomer (C) having an acidic group to be added is
less than 1 part by mass, the acid-etching effect may not be
obtained. Therefore, the amount is more preferably at least 2 parts
by mass and further preferably at least 5 parts by mass. On the
other hand, when the amount of polymerizable monomer (C) having an
acidic group to be added exceeds 90 parts by mass, sufficiently
high curability may not be obtained and therefore the adhesive
properties may be deteriorated. Accordingly, the amount is more
preferably 80 parts by mass or less and further preferably 70 parts
by mass or less.
[0077] Crosslinkable Polymerizable Monomer (D)
[0078] Preferably, the composition of the present invention
contains a crosslinkable polymerizable monomer (D). When a
composition containing the crosslinkable polymerizable monomer (D)
is used as a dental composition, it has advantages such as a
further improvement in bond strength.
[0079] The crosslinkable polymerizable monomers (D) can be used
independently or two or more of them can be used in suitable
combination. The crosslinkable polymerizable monomer (D) is not
particularly limited. Examples thereof include an aromatic
compound-based bifunctional polymerizable monomer, an aliphatic
compound-based bifunctional polymerizable monomer, and
trifunctional or higher polymerizable monomers.
[0080] Examples of the aromatic compound-based bifunctional
polymerizable monomer include
2,2-bis((meth)acryloyloxyphenyl)propane,
2,2-bis[4-(3-(meth)acryloyloxy)-2-hydroxypropoxyphenyl]propane
(commonly known as "Bis-GMA"),
2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane,
2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)-
-propane,
2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytrie-
thoxy-phenyl)propane,
2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxy-ph-
enyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane,
2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane, and
1,4-bis(2-(meth)acryloyloxyethyl)pyromeritate.
[0081] Examples of the aliphatic compound-based bifunctional
polymerizable monomer include ethylene glycol di(meth)acrylate,
diethylene glycol 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, and
2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate
(commonly known as "UDMA").
[0082] Examples of the trifunctional or higher polymerizable
monomers include trimethylolpropane tri(meth)acrylate,
trimethylolethane tri(meth)acrylate, trimethylolmethane
tri(meth)acrylate, pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, dipentaerythritol
tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,
dipentaerythritol hexa(meth)acrylate,
N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]te-
tramethacrylate, and
1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane.
[0083] The amount of crosslinkable polymerizable monomer (D) to be
added is not particularly limited. Generally, it is preferable that
1 to 90 parts by mass of crosslinkable polymerizable monomer (D) be
contained in 100 parts by mass of the whole amount of polymerizable
monomer components. When the amount of crosslinkable polymerizable
monomer (D) to be added is less than 1 part by mass, sufficiently
high bond strength may not be obtained. Therefore, the amount is
more preferably at least 2 parts by mass and further preferably at
least 5 parts by mass. On the other hand, when the amount of
crosslinkable polymerizable monomer (D) to be added exceeds 90
parts by mass, the composition may not penetrate sufficiently into
a collagen layer of dentin and thereby high bond strength may not
be obtained. Therefore, the amount is more preferably 80 parts by
mass or less and further preferably 70 parts by mass or less.
[0084] The composition of the present invention may contain a
polymerizable monomer other than the aforementioned (A), (B), (C),
and (D) as required.
[0085] Solvent (E)
[0086] Preferably, the composition of the present invention
contains a solvent (E) depending on the specific embodiment.
Examples of the solvent include water (I), an organic solvent (J),
and a mixed solvent thereof.
[0087] Examples of the organic solvent (J) include methanol,
ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol,
acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether,
diisopropyl ether, hexane, toluene, chloroform, ethyl acetate, and
butyl acetate. Particularly, when both safety to biological bodies
and easy removal based on volatility are taken into consideration,
the organic solvent (J) is preferably a water-soluble organic
solvent. Specifically, ethanol, 2-propanol, 2-methyl-2-propanol,
acetone, and tetrahydrofuran can be used preferably.
[0088] When the composition of the present invention contains the
water (I), it exhibits both excellent bond strength and excellent
bond durability. Preferably, the water (I) is free of impurities
that have adverse effects, and distilled water or ion exchanged
water is preferable.
[0089] Moreover, the solvent (E) may not need to be added depending
on the embodiment. In an embodiment using the solvent, it is
preferable that the composition contains 1 to 4000 parts by mass of
solvent (E) with respect to 100 parts by mass of the whole amount
of polymerizable monomer components. When the solvent is the water
(I), or a mixed solvent of the water (I) and the organic solvent
(J), it is preferable that the amount of water (I) to be added is 6
to 2000 parts by mass with respect to 100 parts by mass of the
whole amount of polymerizable monomer components. When the content
of water (I) is less than 6 parts by mass, the monomer may not
penetrate sufficiently into a collagen layer and the bond strength
may be reduced. On the other hand, when the content of water (I)
exceeds 2000 parts by mass, the polymerizability of the monomer may
be deteriorated and both the bond strength and bond durability may
be reduced. The content of water (I) is more preferably at least 7
parts by mass and further preferably at least 10 parts by mass.
Furthermore, the content of water (I) is more preferably 1500 parts
by mass or less. The preferable amount of the solvent (E) to be
added varies considerably depending on the embodiment in which it
is used. Therefore, preferable amounts of organic solvents (E) to
be added according to respective embodiments are indicated together
with description of specific embodiments of the composition of the
present invention described later.
[0090] Polymerization Initiator (F)
[0091] A polymerization initiator (F) used in the present invention
can be selected from polymerization initiators commonly used in the
industrial field. Among them, polymerization initiators used for
dental applications are used preferably. Particularly,
photopolymerization initiators and chemical polymerization
initiators are used independently or two or more of them are used
in suitable combination.
[0092] Examples of the photopolymerization initiator include
(bis)acylphosphine oxides, water-soluble acylphosphine oxides,
thioxanthones or the quaternary ammonium salts of thioxanthones,
ketals, alpha-diketones, coumarins, anthraquinones, benzoin alkyl
ether compounds, and alpha-amino ketone compounds.
[0093] Among (bis)acylphosphine oxides used as the
photopolymerization initiator, examples of acylphosphine oxides
include 2,4,6-trimethylbenzoyldiphenylphosphine oxide,
2,6-dimethoxybenzoyldiphenylphosphine oxide,
2,6-dichlorobenzoyldiphenylphosphine oxide,
2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide,
2,4,6-trimethylbenzoylethoxyphenylphosphine oxide,
2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyl
di-(2,6-dimethylphenyl)phosphonate. Examples of bisacylphosphine
oxides include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide,
bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide,
bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide,
bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide,
bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide,
bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide,
bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide,
bis-(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and
(2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide.
[0094] Preferably, the water-soluble acylphosphine oxides used as
the photopolymerization initiator have alkali metal ions, alkaline
earth metal ions, pyridinium ions, or ammonium ions in the
acylphosphine oxide molecules. For instance, the water-soluble
acylphosphine oxides can be synthesized by the method disclosed in
EP 0009348 B1 or JP 57(1982)-197289 A.
[0095] Specific examples of the aforementioned water-soluble
acylphosphine oxides include sodium monomethylacetylphosphonate,
sodium monomethyl(1-oxopropyl)phosphonate, sodium
monomethylbenzoylphosphonate, sodium
monomethyl(1-oxobutyl)phosphonate, sodium
monomethyl(2-methyl-1-oxopropyl)phosphonate, sodium
acetylphosphonate, sodium monomethylacetylphosphonate, sodium
acetylmethylphosphonate,
methyl-4-(hydroxymethoxyphosphinyl)-4-oxobutanoate sodium salt,
methyl-4-oxophosphonobutanoate monosodium salt,
acetylphenylphosphinate sodium salt, sodium
(1-oxopropyl)pentylphosphinate,
methyl-4-(hydroxypentylphosphinyl)-4-oxobutanoate sodium salt,
sodium acetylpentylphosphinate, sodium acetylethylphosphinate,
sodium methyl(1,1-dimethyl)methylphosphinate, sodium
(1,1-diethoxyethyl)methylphosphinate, sodium
(1,1-diethoxyethyl)methylphosphinate,
methyl-4-(hydroxymethylphosphinyl)-4-oxobutanoate lithium salt,
4-(hydroxymethylphosphinyl)-4-oxobutanoic acid dilithium salt,
methyl(2-methyl-1,3-dioxolan-2-yl)phosphinate sodium salt,
methyl(2-methyl-1,3-thiazolidin-2-yl)phosphonite sodium salt,
(2-methylperhydro-1,3-diazin-2-yl)phosphonite sodium salt,
acetylphosphinate sodium salt, (1,1-diethoxyethyl)phosphonite
sodium salt, (1,1-diethoxyethyl)methylphosphonite sodium salt,
methyl(2-methyloxathiolane-2-yl)phosphinate sodium salt,
methyl(2,4,5-trimethyl-1,3-dioxolan-2-yl)phosphinate sodium salt,
methyl(1,1-propoxyethyl)phosphinate sodium salt,
(1-methoxyvinyl)methylphosphinate sodium salt,
(1-ethylthiovinyl)methylphosphinate sodium salt,
methyl(2-methylperhydro-1,3-diazin-2-yl)phosphinate sodium salt,
methyl(2-methylperhydro-1,3-thiazin-2-yl)phosphinate sodium salt,
methyl(2-methyl-1,3-diazolidin-2-yl)phosphinate sodium salt,
methyl(2-methyl-1,3-thiazolidin-2-yl)phosphinate sodium salt,
(2,2-dicyano-1-methylethynyl)phosphinate sodium salt,
acetylmethylphosphinate oxime sodium salt,
acetylmethylphosphinate-O-benzyloxime sodium salt,
1-[(N-ethoxyimino)ethyl]methylphosphinate sodium salt,
methyl(1-phenyliminoethyl)phosphinate sodium salt,
methyl(1-phenylhydrazone ethyl)phosphinate sodium salt,
[1-(2,4-dinitrophenylhydrazono)ethyl]methylphosphinate sodium salt,
acetylmethylphosphinate semicarbazone sodium salt,
(1-cyano-1-hydroxyethyl)methylphosphinate sodium salt,
(dimethoxymethyl)methyl phosphinate sodium salt,
formylmethylphosphinate sodium salt,
(1,1-dimethoxypropyl)methylphosphinate sodium salt,
methyl(1-oxopropyl)phosphinate sodium salt, dodecylguanidine salt
of (1,1-dimethoxypropyl)methylphosphinate, isopropylamine salt of
(1,1-dimethoxypropyl)methylphosphinate, acetylmethylphosphinate
thiosemicarbazone sodium salt,
1,3,5-tributyl-4-methylamino-1,2,4-triazolium
(1,1-dimethoxyethyl)-methylphosphinate,
1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium
(1,1-dimethoxyethyl)-methylphosphinate,
2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt,
2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, and
ammonium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide.
Furthermore, examples thereof also include compounds described in
JP 2000-159621 A.
[0096] Among these (bis)acylphosphine oxides and water-soluble
acylphosphine oxides, particularly preferable ones are
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide,
bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and
2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt.
[0097] Examples of thioxanthones or the quaternary ammonium salts
of thioxanthones that are used as the above-mentioned
photopolymerization initiators include thioxanthone,
2-chlorothioxanthen-9-one,
2-hydroxy-3-(9-oxy-9H-thioxanthen-4-yloxy)-N,N,N-trimethyl-propaneaminium
chloride,
2-hydroxy-3-(1-methyl-9-oxy-9H-thioxanthen-4-yloxy)-N,N,N-trime-
thyl-propaneaminium chloride,
2-hydroxy-3-(9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-propaneaminium
chloride,
2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-t-
rimethyl-1-propaneaminium chloride,
2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propa-
neaminium chloride, and
2-hydroxy-3-(1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethy-
l-1-propaneaminium chloride.
[0098] Among the thioxanthones or the quaternary ammonium salts of
thioxanthones, a particularly preferable thioxanthone is
2-chlorothioxanthen-9-one, and a particularly preferable quaternary
ammonium salt of thioxanthone is
2-hydroxy-3-(3,4-dimethyl-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propa-
neaminium chloride.
[0099] Examples of ketals used as the photopolymerization initiator
include benzyl dimethyl ketal and benzyl diethyl ketal.
[0100] Examples of the alpha-diketones used as the
photopolymerization initiator include diacetyl, dibenzyl,
camphorquinone, 2,3-pentadione, 2,3-octadione,
9,10-phenanthrenequinone, 4,4'-oxybenzyl, and acenaphthenequinone.
Among these, camphorquinone is particularly preferable from the
viewpoint of having the maximum absorption wavelength in the
visible light range.
[0101] Examples of the coumarin compound used as the aforementioned
photopolymerization initiator include compounds described in JP
9(1997)-3109 A and JP 10(1998)-245525 A such as
3,3'-carbonylbis(7-diethylamino)coumarin,
3-(4-methoxybenzoyl)coumarin, 3-thienoyl coumarin,
3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-7-methoxycoumarin,
3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin,
3-benzoylcoumarin, 7-methoxy-3-(p-nitrobenzoyl)coumarin,
3-(p-nitrobenzoyl)coumarin 3,5-carbonylbis(7-methoxycoumarin),
3-benzoyl-6-bromocoumarin, 3,3'-carbonylbiscoumarin,
3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo[f]coumarin,
3-carboxycoumarin, 3-carboxy-7-methoxycoumarin,
3-ethoxycarbonyl-6-methoxycoumarin,
3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo[f]coumarin,
7-methoxy-3-(p-nitrobenzoyl)coumarin, 3-(p-nitrobenzoyl)coumarin,
3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin,
7-dimethylamino-3-(4-methoxybenzoyl)coumarin,
7-diethylamino-3-(4-methoxybenzoyl)coumarin,
7-diethylamino-3-(4-diethylamino)coumarin,
7-methoxy-3-(4-methoxybenzoyl)coumarin,
3-(4-nitrobenzoyl)benzo[f]coumarin,
3-(4-ethoxycinnamoyl)-7-methoxycoumarin,
3-(4-dimethylaminocinnamoyl)coumarin,
3-(4-diphenylaminocinnamoyl)coumarin,
3-[(3-dimethylbenzothiazole-2-ilidene)acetyl]coumarin,
3-[(1-methylnaphtho[1,2-d]thiazole-2-ilidene)acetyl]coumarin,
3,3'-carbonylbis(6-methoxycoumarin),
3,3'-carbonylbis(7-acetoxycoumarin),
3,3'-carbonylbis(7-dimethylaminocoumarin),
3-(2-benzothiazoyl)-7-(diethylamino)coumarin,
3-(2-benzothiazoyl)-7-(dibutylamino)coumarin,
3-(2-benzimidazoyl)-7-(diethylamino)coumarin,
3-(2-benzothiazoyl)-7-(dioctylamino)coumarin,
3-acetyl-7-(dimethylamino)coumarin,
3,3'-carbonylbis(7-dibutylaminocoumarin),
3,3'-carbonyl-7-diethylaminocoumarin-7'-bis(butoxyethyl)aminocoumarin,
10-[3-[4-(dimethylamino)phenyl]-1-oxo-2-propenyl]-2,3,6,7-1,1,7,7-tetrame-
thyl1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolizine-11-one, and
10-(2-benzothiazoyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl1H,5H,11H-[1]--
benzopyrano[6,7,8-ij]quinolizin-11-one.
[0102] Among the above-mentioned coumarin compounds, particularly
3,3'-carbonylbis(7-diethylaminocoumarin) and
3,3'-carbonylbis(7-dibutylaminocoumarin) are suitable.
[0103] Examples of the anthraquinones used as the aforementioned
photopolymerization initiator include anthraquinone,
1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone,
1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone,
and 1-hydroxyanthraquinone.
[0104] Examples of the benzoin alkyl ethers used as the
aforementioned photopolymerization initiator include benzoin methyl
ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin
isobutyl ether.
[0105] Examples of the alpha-aminoketones used as the
aforementioned photopolymerization initiator include
2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.
[0106] Preferably, among these photopolymerization initiators, at
least one selected from the group consisting of (bis)acylphosphine
oxides, salts thereof, alpha-diketones, and coumarin compounds is
used. This makes it possible to obtain a composition that has
excellent photocurability in visible and near-ultraviolet ranges
and sufficiently high photocurability regardless of which light
source among a halogen lamp, light-emitting diode (LED), and xenon
lamp is used.
[0107] Among the polymerization initiators (F) used in the present
invention, a chemical polymerization initiator that is used
preferably is organic peroxide. The organic peroxide used as the
chemical polymerization initiator is not particularly limited and a
known one can be used. Examples of typical organic peroxides
include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl
peroxide, peroxyketal, peroxyester, and peroxydicarbonate.
[0108] Examples of ketone peroxide used as the chemical
polymerization initiator include methyl ethyl ketone peroxide,
methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and
cyclohexanone peroxide.
[0109] Examples of hydroperoxide used as the chemical
polymerization initiator include
2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene
hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and
1,1,3,3-tetramethylbutyl hydroperoxide.
[0110] Examples of diacyl peroxide used as the chemical
polymerization initiator include acetyl peroxide, isobutyryl
peroxide, benzoyl peroxide, decanoyl peroxide,
3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and
lauroyl peroxide.
[0111] Examples of dialkyl peroxide used as the chemical
polymerization initiator include di-t-butyl peroxide, dicumyl
peroxide, t-butylcumyl peroxide,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
1,3-bis(t-butylperoxyisopropyl)benzene, and
2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne.
[0112] Examples of peroxyketal used as the chemical polymerization
initiator include
1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,
1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane,
2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)valeric
acid-n-butyl ester.
[0113] Examples of peroxyester used as the chemical polymerization
initiator include alpha-cumyl peroxyneodecanoate, t-butyl
peroxyneodecanoate, t-butyl peroxypivarate,
2,2,4-trimethylpentylperoxy-2-ethyl hexanoate, t-amylperoxy-2-ethyl
hexanoate, t-butylperoxy-2-ethyl hexanoate, di-t-butylperoxy
isophthalate, di-t-butylperoxy hexahydroterephthalate,
t-butylperoxy-3,3,5-trimethyl hexanoate, t-butylperoxy acetate,
t-butylperoxy benzoate, and t-butylperoxymaleic acid.
[0114] Examples of peroxydicarbonate used as the chemical
polymerization initiator include di-3-methoxy peroxydicarbonate,
di-2-ethylhexyl peroxydicarbonate,
bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl
peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl
peroxydicarbonate, and diallyl peroxydicarbonate.
[0115] Among these organic peroxides, diacyl peroxide is used
preferably from the viewpoint of a comprehensive balance of safety,
storage stability, and radical production ability, and among these,
benzoyl peroxide is used particularly preferably.
[0116] The amount of polymerization initiator (F) to be added in
the present invention is not particularly limited. However, from
the viewpoint of, for example, curability of the resultant
composition, it is preferable that 0.001 to 30 parts by mass of
polymerization initiator (F) be contained with respect to 100 parts
by mass of the whole amount of polymerizable monomer components.
When the amount of polymerization initiator (F) to be added is less
than 0.001 part by mass, polymerization may not proceed
sufficiently and thereby bond strength may be reduced. Therefore,
the amount is more preferably at least 0.05 part by mass and
further preferably at least 0.1 part by mass. On the other hand,
when the amount of polymerization initiator (F) to be added exceeds
30 parts by mass, in the case where the polymerization initiator
itself has low polymerization performance, sufficiently high bond
strength may not be obtained and further precipitation from the
composition may occur. Therefore, the amount is more preferably 20
parts by mass or less, further preferably 15 parts by mass or less,
and most preferably 10 parts by mass or less.
[0117] Polymerization Accelerator (G)
[0118] Preferably, the composition of the present invention
contains a polymerization accelerator (G). Examples of the
polymerization accelerator (G) used in the present invention
include amines, sulfinic acids and salts thereof, borate compounds,
barbituric acid derivatives, triazine compounds, copper compounds,
tin compounds, vanadium compounds, halogen compounds, aldehydes,
thiol compounds, sulfite, bisulfite, and thiourea compounds.
[0119] Amines used as the polymerization accelerator (G) can be
divided into aliphatic amines and aromatic amines. Examples of
aliphatic amines include: primary aliphatic amines such as
n-butylamine, n-hexylamine, and n-octylamine; secondary aliphatic
amines such as diisopropylamine, dibutylamine, and
N-methylethanolamine; and tertiary aliphatic amines such as
N-methyldiethanolamine, N-ethyldiethanolamine,
N-n-butyldiethanolamine, N-lauryldiethanolamine,
2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine
dimethacrylate, N-ethyldiethanolamine dimethacrylate,
triethanolamine monomethacrylate, triethanolamine dimethacrylate,
triethanolamine trimethacrylate, triethanolamine, trimethylamine,
triethylamine, and tributylamine. Among these, tertiary aliphatic
amines are preferable from the viewpoint of curability and storage
stability of the composition, and particularly,
N-methyldiethanolamine and triethanolamine are used more
preferably.
[0120] Examples of aromatic amine include
N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline,
N,N-di(2-hydroxyethyl)-p-toluidine,
N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline,
N,N-bis(2-hydroxyethyl)-4-ethylaniline,
N,N-bis(2-hydroxyethyl)-4-isopropylaniline,
N,N-bis(2-hydroxyethyl)-4-t-butylaniline,
N,N-bis(2-hydroxyethyl)-3,5-di-isopropylaniline,
N,N-bis(2-hydroxyethyl)-3,5-di-t-butylaniline, N,N-dimethylaniline,
N,N-dimethyl-p-toluidine, N,N-dimethyl-m-toluidine,
N,N-diethyl-p-toluidine, N,N-dimethyl-3,5-dimethylaniline,
N,N-dimethyl-3,4-dimethylaniline, N,N-dimethyl-4-ethylaniline,
N,N-dimethyl-4-isopropylaniline, N,N-dimethyl-4-t-butylaniline,
N,N-dimethyl-3,5-di-t-butylaniline, 4-N,N-dimethylaminobenzoic acid
ethyl ester, 4-N,N-dimethylaminobenzoic acid methyl ester,
N,N-dimethylaminobenzoic acid n-butoxyethyl ester,
4-N,N-dimethylaminobenzoic acid 2-(methacryloyloxy)ethyl ester,
4-N,N-dimethylaminobenzophenone, and butyl 4-dimethylaminobenzoate.
Among these, at least one selected from the group consisting of
N,N-di(2-hydroxyethyl)-p-toluidine, 4-N,N-dimethylaminobenzoic acid
ethyl ester, N,N-dimethylaminobenzoic acid n-butoxyethyl ester, and
4-N,N-dimethylaminobenzophenone is used preferably from the
viewpoint of being capable of providing the composition with
excellent curability.
[0121] Examples of sulfinic acid and salt thereof used as the
polymerization accelerator (G) include p-toluenesulfinic acid,
sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium
p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic
acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium
benzenesulfinate, calcium benzenesulfinate,
2,4,6-trimethylbenzenesulfinic acid, sodium
2,4,6-trimethylbenzenesulfinate, potassium
2,4,6-trimethylbenzenesulfinate, lithium
2,4,6-trimethylbenzenesulfinate, calcium
2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinic
acid, sodium 2,4,6-triethylbenzenesulfinate, potassium
2,4,6-triethylbenzenesulfinate, lithium
2,4,6-triethylbenzenesulfinate, calcium
2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic
acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium
2,4,6-triisopropylbenzenesulfinate, lithium
2,4,6-triisopropylbenzenesulfinate, and calcium
2,4,6-triisopropylbenzenesulfinate. Sodium benzenesulfinate, sodium
p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate
are particularly preferable.
[0122] The borate compound used as the polymerization accelerator
(G) is preferably an arylborate compound. Specific examples of
arylborate compounds that are used preferably include, as a borate
compound having one aryl group in one molecule, sodium salt,
lithium salt, potassium salt, magnesium salt, tetrabutylammonium
salt, tetramethylammonium salt, tetraethylammonium salt,
methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt,
methylquinolinium salt, ethylquinolinium salt, and butylquinolinium
salt of trialkylphenylboron, trialkyl(p-chlorophenyl)boron,
trialkyl(p-fluorophenyl)boron,
trialkyl(3,5-bistrifluoromethyl)phenylboron,
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 (each alkyl group is at least one
selected from the group consisting of, for example, an n-butyl
group, an n-octyl group, and an n-dodecyl group).
[0123] Examples of the borate compound having two aryl groups in
one molecule include sodium salt, lithium salt, potassium salt,
magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
tetraethylammonium salt, methylpyridinium salt, ethylpyridinium
salt, butylpyridinium salt, methylquinolinium salt,
ethylquinolinium salt, and butylquinolinium salt of
dialkyldiphenylboron, dialkyldi(p-chlorophenyl)boron,
dialkyldi(p-fluorophenyl)boron,
dialkyldi(3,5-bistrifluoromethyl)phenylboron,
dialkyldi[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,
dialkyldi(p-nitrophenyl)boron, dialkyldi(m-nitrophenyl)boron,
dialkyldi(p-butylphenyl)boron, dialkyldi(m-butylphenyl)boron,
dialkyldi(p-butyloxyphenyl)boron, dialkyldi(m-butyloxyphenyl)boron,
dialkyldi(p-octyloxyphenyl)boron, and
dialkyldi(m-octyloxyphenyl)boron (each alkyl group is at least one
selected from the group consisting of, for example, an n-butyl
group, an n-octyl group, and an n-dodecyl group).
[0124] Examples of the borate compound having three aryl groups in
one molecule include sodium salt, lithium salt, potassium salt,
magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
tetraethylammonium salt, methylpyridinium salt, ethylpyridinium
salt, butylpyridinium salt, methylquinolinium salt,
ethylquinolinium salt, and butylquinolinium salt of
monoalkyltriphenylboron, monoalkyltri(p-chlorophenyl)boron,
monoalkyltri(p-fluorophenyl)boron,
monoalkyltri(3,5-bistrifluoromethyl)phenylboron,
monoalkyltri[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]bor-
on, monoalkyltri(p-nitrophenyl)boron,
monoalkyltri(m-nitrophenyl)boron, monoalkyltri(p-butylphenyl)boron,
monoalkyltri(m-butylphenyl)boron,
monoalkyltri(p-butyloxyphenyl)boron,
monoalkyltri(m-butyloxyphenyl)boron,
monoalkyltri(p-octyloxyphenyl)boron, and
monoalkyltri(m-octyloxyphenyl)boron (each alkyl group is one
selected from, for example, an n-butyl group, an n-octyl group, and
an n-dodecyl group).
[0125] Furthermore, examples of the borate compound having four
aryl groups in one molecule include sodium salt, lithium salt,
potassium salt, magnesium salt, tetrabutylammonium salt,
tetramethylammonium salt, tetraethylammonium salt, methylpyridinium
salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium
salt, ethylquinolinium salt, and butylquinolinium salt of
tetraphenylboron, tetrakis(p-chlorophenyl)boron,
tetrakis(p-fluorophenyl)boron,
tetrakis(3,5-bistrifluoromethyl)phenylboron,
tetrakis[3,5-bis(1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl)phenyl]boron,
tetrakis(p-nitrophenyl)boron, tetrakis(m-nitrophenyl)boron,
tetrakis(p-butylphenyl)boron, tetrakis(m-butylphenyl)boron,
tetrakis(p-butyloxyphenyl)boron, tetrakis(m-butyloxyphenyl)boron,
tetrakis(p-octyloxyphenyl)boron, tetrakis(m-octyloxyphenyl)boron,
(p-fluorophenyl)triphenylboron,
(3,5-bistrifluoromethyl)phenyltriphenylboron,
(p-nitrophenyl)triphenylboron, (m-butyloxyphenyl)triphenylboron,
(p-butyloxyphenyl)triphenylboron, (m-octyloxyphenyl)triphenylboron,
and (p-octyloxyphenyl)triphenylboron.
[0126] More preferably, from the viewpoint of storage stability,
among these arylborate compounds, a borate compound having three or
four aryl groups in one molecule is used. Furthermore, one of these
arylborate compounds can be used or two or more of them can be used
in mixture.
[0127] Examples of a barbituric acid derivative used as the
polymerization accelerator (G) include barbituric acid,
1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid,
1,5-dimethylbarbituric acid, 5-butylbarbituric acid,
5-ethylbarbituric acid, 5-isopropylbarbituric acid,
5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid,
1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric
acid, 1,3-dimethyl-5-isobutylbarbituric acid,
1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric
acid, 1,3-dimethyl-5-cyclohexylbarbituric acid,
1,3-dimethyl-5-phenylbarbituric acid,
1-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric
acid, 5-methylbarbituric acid, 5-propylbarbituric acid,
1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid,
1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric
acid, 1-cyclohexyl-5-methylbarbituric acid,
1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric
acid, 1-cyclohexyl-5-hexylbarbituric acid,
5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric
acid, and thiobarbituric acids, as well as salts thereof
(particularly, alkali metals or alkaline earth metals are
preferable). Examples of salts of these barbituric acids include
sodium 5-butylbarbiturate, sodium 1,3,5-trimethylbarbiturate, and
sodium 1-cyclohexyl-5-ethylbarbiturate.
[0128] Examples of particularly preferable barbituric acid
derivatives include 5-butylbarbituric acid,
1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric
acid, 1-benzyl-5-phenylbarbituric acid, and sodium salts of these
barbituric acids.
[0129] Examples of the triazine compound used as the polymerization
accelerator
[0130] (G) include 2,4,6-tris(trichloromethyl)-s-triazine,
2,4,6-tris(tribromomethyl)-s-triazine,
2-methyl-4,6-bis(trichloromethyl)-s-triazine,
2-methyl-4,6-bis(tribromomethyl)-s-triazine,
2-phenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(2,4-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine,
2-n-propyl-4,6-bis(trichloromethyl)-s-triazine,
2-(.alpha.,.alpha.,.beta.-trichloroethyl)-4,6-bis(trichloromethyl)-s-tria-
zine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(p-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(o-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(p-butoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,
2-[2-(3,4,5-trimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine-
, 2-(1-naphthyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine,
2-[2-{N,N-bis(2-hydroxyethyl)amino}ethoxy]-4,6-bis(trichloromethyl)-s-tri-
azine,
2-[2-{N-hydroxyethyl-N-ethylamino}ethoxy]-4,6-bis(trichloromethyl)--
s-triazine,
2-[2-{N-hydroxyethyl-N-methylamino}ethoxy]-4,6-bis(trichloromethyl)-s-tri-
azine, and
2-[2-{N,N-diallylamino}ethoxy]-4,6-bis(trichloromethyl)-s-triaz-
ine.
[0131] Particularly preferable ones among the triazine compounds
described above as examples are
2,4,6-tris(trichloromethyl)-s-triazine in terms of polymerization
activity and 2-phenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, and
2-(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine in terms of
storage stability. One of the above-mentioned triazine compounds
may be used or two or more of them may be used in mixture.
[0132] Examples of the copper compound used preferably as the
polymerization accelerator (G) include copper acetylacetonate,
copper (II) acetate, copper oleate, copper (II) chloride, and
copper (II) bromide.
[0133] Examples of the tin compound used as the polymerization
accelerator (G) include di-n-butyltin dimalate, di-n-octyltin
dimalate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate.
Particularly preferable tin compounds are di-n-octyltin dilaurate
and di-n-butyltin dilaurate.
[0134] The vanadium compound used as the polymerization accelerator
(G) is preferably one of tetravalent and/or pentavalent vanadium
compounds. Examples of the tetravalent and/or pentavalent vanadium
compounds include compounds described in JP 2003-96122 A such as
divanadium (IV) tetroxide, vanadyl (IV) acetylacetonate, vanadyl
(IV) oxalate, vanadyl (IV) sulfate,
oxobis(1-phenyl-1,3-butanedionate)vanadium (IV),
bis(maltolato)oxovanadium (IV), vanadium (V) pentoxide, sodium
metavanadate (V), and ammonium metavanadate (V).
[0135] Examples of the halogen compound used preferably as the
polymerization accelerator (G) include
dilauryldimethylammoniumchloride,
lauryldimethylbenzylammoniumchloride,
benzyltrimethylammoniumchloride, tetramethylammoniumchloride,
benzyldimethylcetylammoniumchloride, and
dilauryldimethylammoniumbromide.
[0136] Examples of aldehydes used as the polymerization accelerator
(G) include terephthalaldehyde and a benzaldehyde derivative.
Examples of the benzaldehyde derivative include
dimethylaminobenzaldehyde, p-methyloxybenzaldehyde,
p-ethyloxybenzaldehyde, and p-n-octyloxybenzaldehyde. Among these,
from the viewpoint of curability, p-n-octyloxybenzaldehyde is used
preferably.
[0137] Examples of the thiol compound used as the polymerization
accelerator (G) include 3-mercaptopropyltrimethoxysilane,
2-mercaptobenzooxazol, decanethiol, and thiobenzoic acid.
[0138] Examples of sulfite used as the polymerization accelerator
(G) include sodium sulfite, potassium sulfite, calcium sulfite, and
ammonium sulfite.
[0139] Examples of bisulfate used as the polymerization accelerator
(G) include sodium bisulfate and potassium bisulfate.
[0140] Examples of the thiourea compound used as the polymerization
accelerator (G) include 1-(2-pyridyl)-2-thiourea, thiourea,
methylthiourea, ethylthiourea, N,N'-dimethylthiourea,
N,N'-diethylthiourea, N,N'-di-n-propylthiourea,
N,N'-dicyclohexylthiourea, trimethylthiourea, triethylthiourea,
tri-n-propylthiourea, tricyclohexylthiourea, tetramethylthiourea,
tetraethylthiourea, tetra-n-propylthiourea, and
tetracyclohexylthiourea.
[0141] The amount of polymerization accelerator (G) to be added in
the present invention is not particularly limited. However, from
the viewpoints of, for example, curability of the resultant
composition, it is preferable that 0.001 to 30 parts by mass of
polymerization accelerator (G) be contained with respect to 100
parts by mass of the whole amount of polymerizable monomer
components. When the amount of polymerization accelerator (G) to be
added is less than 0.001 part by mass, polymerization may not
proceed sufficiently and bond strength may be reduced. Therefore,
the amount is more preferably at least 0.05 part by mass and
further preferably at least 0.1 part by mass. On the other hand,
when the amount of polymerization accelerator (G) to be added
exceeds 30 parts by mass, in the case where the polymerization
initiator itself has low polymerization performance, sufficiently
high bond strength may not be obtained and further precipitation
from the composition may occur. Therefore, the amount is more
preferably 20 parts by mass or less and further preferably 10 parts
by mass or less.
[0142] Filler (H)
[0143] Preferably, a filler (H) further is mixed into a composition
of the present invention depending on the embodiment. Generally,
such fillers are divided roughly into organic fillers, inorganic
fillers, and organic-inorganic composite fillers. Examples of
materials for the organic fillers include polymethylmethacrylate,
polyethylmethacrylate, a methylmethacrylate-ethylmethacrylate
copolymer, cross-linked polymethylmethacrylate, cross-linked
polyethylmethacrylate, polyamide, polyvinyl chloride, polystyrene,
chloroprene rubber, nitrile rubber, an ethylene-vinyl acetate
copolymer, a styrene-butadiene copolymer, an acrylonitrile-styrene
copolymer, and an acrylonitrile-styrene-butadiene copolymer. These
may be used independently or a mixture of two or more of them may
be used. The shapes of the organic fillers are not particularly
limited, and particle sizes of the fillers to be used can be
selected appropriately. From the viewpoints of, for example,
handling ability and mechanical strength of the resultant
composition, the mean particle size of the organic fillers is
preferably 0.001 to 50 .mu.m and more preferably 0.001 to 10
.mu.m.
[0144] Examples of materials for the inorganic fillers include
quartz, silica, alumina, silica-titania, silica-titania-barium
oxide, silica-zirconia, silica-alumina, lanthanum glass,
borosilicate glass, soda glass, barium glass, strontium glass,
glass ceramics, aluminosilicate glass, barium boroaluminosilicate
glass, strontium boroaluminosilicate glass, fluoroaluminosilicate
glass, calcium fluoroaluminosilicate glass, strontium
fluoroaluminosilicate glass, barium fluoroaluminosilicate glass,
and strontium calcium fluoroaluminosilicate glass. Similarly, these
can be used independently or two or more of them can be used in
mixture. The shapes of the inorganic fillers are not particularly
limited and particle sizes of the fillers to be used can be
selected appropriately. From the viewpoints of, for example,
handling ability and mechanical strength of the resultant
composition, the mean particle size of the inorganic fillers is
preferably 0.001 to 50 .mu.m and more preferably 0.001 to 10
.mu.m.
[0145] Examples of the shapes of the inorganic fillers include
amorphous fillers and spherical fillers. From the viewpoint of
improving the mechanical strength of a composition, it is
preferable that spherical fillers be used as the inorganic fillers.
Furthermore, in the case of using the spherical fillers, when a
composition of the present invention is used as a dental composite
resin, there also is an advantage that a composition resin with
excellent surface smoothness is obtained. In this case, the
spherical fillers are fillers in which when a photograph thereof is
taken with a scanning electron microscope (hereinafter abbreviated
as SEM), particles observed within a unit field of view are rounded
and the mean uniformity obtained by dividing the particle size in
the direction orthogonal to the maximum diameter by the maximum
diameter is at least 0.6. The mean particle size of the spherical
fillers is preferably 0.1 to 5 .mu.m. When the mean particle size
is less than 0.1 .mu.m, the filling rate of the spherical fillers
in the composition decreases and thereby the mechanical strength
may be reduced. On the other hand, when the mean particle size
exceeds 5 .mu.m, the surface areas of the spherical fillers are
reduced and a cured product with high mechanical strength may not
be obtained.
[0146] The inorganic fillers may be used after the surfaces thereof
are treated beforehand with a known surface-treating agent such as
a silane coupling agent in order to adjust fluidity of the
composition as required. Examples of such a surface-treating agent
include vinyltrimethoxysilane, vinyltriethoxysilane,
vinyltrichlorosilane, vinyltri(.beta.-methoxyethoxy)silane,
.gamma.-methacryloyloxypropyltrimethoxysilane,
11-methacryloyloxyundecyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane, and
.gamma.-aminopropyltriethoxysilane.
[0147] The organic-inorganic composite fillers used in the present
invention can be obtained as follows. That is, a monomer compound
is added to the aforementioned inorganic filler beforehand, this is
made into a paste and is then polymerized, and thereafter this is
crushed. The organic-inorganic composite filler that can be used
is, for example, a TMPT filler (obtained by mixing
trimethylolpropane methacrylate with a silica filler, polymerizing
it, and then crushing it). The shape of the organic-inorganic
composite filler is not particularly limited, and the particle size
of the filler to be used can be selected appropriately. From the
viewpoints of, for example, handling ability and mechanical
strength of the resultant composition, the mean particle size of
the organic-inorganic composite filler is preferably 0.001 to 50
.mu.m and more preferably 0.001 to 10 .mu.m.
[0148] The amount of the filler (H) to be added in the present
invention is not particularly limited, but it is preferable that 1
to 2000 parts by mass of filler (H) be contained with respect to
100 parts by mass of the whole amount of polymerizable monomer
components. The preferable amount of filler (H) to be added varies
considerably depending on the embodiment to be employed.
Accordingly, preferable amounts of the filler (H) to be added
according to the respective embodiments are indicated together with
description of specific embodiments of the composition of the
present invention described later.
[0149] In addition, for example, a pH adjuster, polymerization
inhibitor, ultraviolet absorbent, thickening agent, colorant,
antibacterial agent, and flavor may be added to the composition of
the present invention within a range that does not inhibit the
effect of the present invention.
[0150] The composition of the present invention is used suitably as
a dental composition. This dental composition can be used for
dental materials such as a primer, bonding material, cement (resin
cement, glass ionomer cement, and resin-reinforced glass ionomer
cement), composite resin, pit and fissure sealant, and denture base
resin, and particularly, it is used suitably as a primer, bonding
material, cement or composite resin. In this case, the composition
may be used as a two component type in which the components of the
composition are divided into two.
[0151] With respect to a dental material, generally, a dental
adhesive is used when a lost part of a tooth is filled or covered
with a restorative material. Typically, the dental adhesive is
allowed to act on dentin. In this case, when such a dental adhesive
is allowed to act on dentin, it is important for the dental
adhesive to have an decalcifying effect that allows a dentin
surface to be dissolved with an acidic component, a penetration
effect that allows a monomer component to penetrate into a collagen
layer of the dentin, and a curing effect that allows the monomer
component thus penetrated to solidify to form a hybrid layer
(hereinafter also referred to as a "resin-impregnated layer") with
collagen. Generally, a bonding system in which these three steps,
"decalcifying", "penetration", and "curing", are performed
separately is referred to as a "three-step bonding system".
Basically, a product used for the penetration step is a primer, and
a product used for the curing step is a bonding material.
[0152] Recently, in order to simplify the operation process, a
product that allows the decalcifying step and the penetration step
to be performed together in one step has been developed and has
been used practically. The product is referred to as a
"self-etching primer". Generally, the bonding system using a
self-etching primer and a bonding material is referred to as a
"two-step bonding system". The polymerizable monomer (A) used in
the present invention has high hydrophilicity (particularly when it
has at least three hydroxyl groups). Therefore, it easily
penetrates into a collagen layer of dentin. Accordingly, a
composition of the present invention containing a polymerizable
monomer (A) can be used as a dental primer and also can be used as
a dental self-etching primer.
[0153] Preferably, the primer using a composition of the present
invention is a composition containing a polymerizable monomer (A),
polymerizable monomer (C) having an acidic group, and solvent (E).
Furthermore, an embodiment containing a polymerization accelerator
(G) also is used preferably. The amounts of the above-mentioned (A)
and (C) to be added are preferably 10 to 99 parts by mass of (A)
and 1 to 90 parts by mass of (C), more preferably 10 to 95 parts by
mass of (A) and 5 to 90 parts by mass of (C), and further
preferably 20 to 90 parts by mass of (A) and 10 to 80 parts by mass
of (C), in 100 parts by mass of the whole amount of polymerizable
monomer components.
[0154] Furthermore, when penetrability of a primer composition into
a tooth structure (particularly dentin) is considered important, it
is preferable that further a polymerizable monomer (B) having one
polymerizable group and at least one hydroxyl group be contained.
When the primer composition contains (A), (B), and (C), the amounts
of respective components to be added are preferably 1 to 95 parts
by mass of (A), 1 to 90 parts by mass of (B), and 1 to 90 parts by
mass of (C), more preferably 10 to 85 parts by mass of (A), 5 to 80
parts by mass of (B), and 10 to 85 parts by mass of (C), and
further preferably 15 to 75 parts by mass of (A), 10 to 70 parts by
mass of (B), and 5 to 70 parts by mass of (C), in 100 parts by mass
of the whole amount of polymerizable monomer components.
[0155] When particularly the strength of the cured product of a
primer using a composition of the present invention is intended to
be improved, a crosslinkable polymerizable monomer (D) further may
be added. When consideration is given to penetrability into a tooth
structure (particularly dentin), the above-mentioned (D) is
preferably an aliphatic compound-based bifunctional polymerizable
monomer, more preferably ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate, triethylene glycol
di(meth)acrylate, or
1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and further
preferably triethylene glycol di(meth)acrylate, or
1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane. The amount of
the above-mentioned (D) to be added is preferably 0 to 30 parts by
mass, more preferably 1 to 25 parts by mass, and further preferably
3 to 20 parts by mass, in 100 parts by mass of the whole amount of
polymerizable monomer components.
[0156] Furthermore, the amount of polymerization initiator (F) to
be contained is preferably 0.001 to 30 parts by mass, more
preferably 0.05 to 20 parts by mass, and further preferably 0.1 to
10 parts by mass, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components. In the primer using a
composition of the present invention, the use of polymerization
initiator (F) and the polymerization accelerator (G) in combination
also is a preferable embodiment. As the polymerization accelerator
(G), amines are preferable. In this case, preferably, 0.001 to 20
parts by mass of (F) and 0.001 to 30 parts by mass of (G) are
contained, more preferably 0.05 to 15 parts by mass of (F) and 0.05
to 20 parts by mass of (G) are contained, and further preferably
0.1 to 10 parts by mass of (F) and 0.1 to 10 parts by mass of (G)
are contained, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components.
[0157] In the primer using a composition of the present invention,
the polymerizable monomer (A) has an appropriate hydrophilicity for
penetrating into a collagen layer of dentin. Furthermore, it is
preferable that the solvent (E) be used in the form of a mixed
solvent of water (I) and an organic solvent (J). The amount of
water (I) to be contained in the mixed solvent is not particularly
limited but is preferably at least 10 mass %, more preferably at
least 20 mass %, and further preferably at least 30 mass %.
Moreover, the organic solvent (J) may not need to be added
depending on the embodiment. The amount of the aforementioned
solvent (E) to be added is preferably 1 to 2000 parts by mass,
preferably 5 to 1000 parts by mass, and further preferably 10 to
500 parts by mass, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components. Furthermore, when the
solvent (E) is used in the form of a mixed solvent of water (I) and
the organic solvent (J), the amounts of the aforementioned (I) and
(J) to be added are preferably 6 to 2000 parts by mass of (I) and 0
to 2000 parts by mass of (J), more preferably 8 to 1000 parts by
mass of (I) and 2 to 1000 parts by mass of (J), and further
preferably 10 to 500 parts by mass of (I) and 5 to 500 parts by
mass of (J), with respect to 100 parts by mass of the whole amount
of polymerizable monomer components.
[0158] The composition of the present invention is used preferably
as a bonding material. Preferably, the bonding material in the
aforementioned "two-step bonding system" is a composition
containing the aforementioned polymerizable monomer (A),
polymerization initiator (F), and filler (H). More preferably, such
a composition further contains a polymerizable monomer (B) having
one polymerizable group and at least one hydroxyl group and/or
crosslinkable polymerizable monomer (D). Furthermore, an embodiment
containing a polymerization accelerator (G) also is used
preferably. The amounts of respective components to be added are
preferably 1 to 80 parts by mass of (A), 0 to 80 parts by mass of
(B), and 0 to 80 parts by mass of (D) and more preferably 3 to 80
parts by mass of (A), 3 to 80 parts by mass of (B), and 3 to 80
parts by mass of (D), in 100 parts by mass of the whole amount of
polymerizable monomer components. As in the case of the
above-mentioned (A) used in the present invention, the use of a
compound having at least two polymerizable groups allows a cured
product to have increased mechanical strength. From such a
viewpoint, the aforementioned (D) is more preferably a
polymerizable monomer having at least two polymerizable groups, and
from a viewpoint of obtaining a cured product with particularly
high strength, it is further preferable that the aforementioned (D)
contain an aromatic compound-based bifunctional polymerizable
monomer. The use of an aliphatic bifunctional polymerizable monomer
and aromatic compound-based bifunctional polymerizable monomer in
combination as the aforementioned (D) also is a preferable
embodiment.
[0159] The amount of (F) to be contained is preferably 0.001 to 20
parts by mass, more preferably 0.05 to 15 parts by mass, and
further preferably 0.1 to 10 parts by mass, with respect to 100
parts by mass of the whole amount of polymerizable monomer
components. The use of polymerization initiator (F) and
polymerization accelerator (G) in combination also is a preferable
embodiment. As the polymerization accelerator (G), amines are
preferable. In this case, it is preferable that 0.001 to 20 parts
by mass of (F) and 0.001 to 30 parts by mass of (G) be contained,
more preferably 0.05 to 15 parts by mass of (F) and 0.05 to 20
parts by mass of (G) be contained, and further preferably 0.1 to 10
parts by mass of (F) and 0.1 to 10 parts by mass of (G) be
contained, with respect to 100 parts by mass of the whole amount of
polymerizable monomer components. Moreover, the amount of filler
(H) to be added is preferably 1 to 30 parts by mass, more
preferably 2 to 20 parts by mass, and further preferably 3 to 15
parts by mass, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components.
[0160] Recently, since there are demands for further simplification
in operations, products that allow three steps of "decalcifying",
"penetration", and "curing" to be performed together in one step
also have been developed and are referred to as "one-step bonding
systems". Two typical products of the bonding material used in such
a one-step bonding system are a bonding material in which two
separate liquids of liquid A and liquid B are mixed together
immediately before use and a bonding material that is provided in
the form of one liquid from the beginning and that is a so-called
one-component one-step bonding system. Among these, the
one-component type product further simplifies the process and
therefore has a greater advantage in use. When a composition of the
present invention is used as the bonding material of the
aforementioned one-component one-step bonding system, the
composition is preferably a composition containing a polymerizable
monomer (A), polymerizable monomer (C) having an acidic group,
polymerization initiator (F), filler (H), and solvent (E), and
further preferably, such a composition further contains a
crosslinkable polymerizable monomer (D). The amounts of respective
components to be added are preferably 1 to 80 parts by mass of (A),
1 to 80 parts by mass (C), and 0 to 80 parts by mass of (D), more
preferably 3 to 70 parts by mass of (A), 2 to 60 parts by mass of
(C), and 3 to 70 parts by mass of (D), and further preferably 5 to
70 parts by mass of (A), 3 to 40 parts by mass of (C), and 5 to 70
parts by mass of (D), in 100 parts by mass of the whole amount of
polymerizable monomer components. In the one-component one-step
bonding system, since the "penetration" and "curing" are performed
at one time, the use of a polymerizable monomer, like the
aforementioned (A), having an appropriate hydrophilicity for
penetrating into a collagen layer of dentin as well as at least two
polymerizable groups is of great significance.
[0161] In the one-component one-step bonding system, when
penetrability into a tooth structure (particularly dentin) is
considered important, it is preferable that a polymerizable monomer
(B) having one polymerizable group and at least one hydroxyl group
further be contained. When the one-component one-step bonding
system contains (A), (B), (C), and (D), the amounts of respective
components to be added are preferably 1 to 80 parts by mass of (A),
1 to 90 parts by mass of (B), 1 to 90 parts by mass of (C), and 5
to 90 parts by mass of (D), more preferably 5 to 70 parts by mass
of (A), 5 to 75 parts by mass of (B), 3 to 75 parts by mass of (C),
and 10 to 80 parts by mass of (D), and further preferably 10 to 60
parts by mass of (A), 10 to 60 parts by mass of (B), 5 to 60 parts
by mass of (C), and 15 to 75 parts by mass of (D), in 100 parts by
mass of the whole amount of polymerizable monomer components.
[0162] The amount of (F) to be contained is preferably 0.001 to 20
parts by mass, more preferably 0.05 to 15 parts by mass, and
further preferably 0.1 to 10 parts by mass, with respect to 100
parts by mass of the whole amount of polymerizable monomer
components. The use of polymerization initiator (F) and
polymerization accelerator (G) in combination also is a preferable
embodiment. As the polymerization accelerator (G), amines are
preferable. In this case, it is preferable that 0.001 to 20 parts
by mass of (F) and 0.001 to 30 parts by mass of (G) be contained,
more preferably 0.05 to 15 parts by mass of (F) and 0.05 to 20
parts by mass of (G) be contained, and further preferably 0.1 to 10
parts by mass of (F) and 0.1 to 10 parts by mass of (G) be
contained, with respect to 100 parts by mass of the whole amount of
polymerizable monomer components. Moreover, the amount of filler
(H) to be added is preferably 1 to 30 parts by mass, more
preferably 2 to 20 parts by mass, and further preferably 3 to 20
parts by mass, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components.
[0163] The amount of solvent (E) to be added is preferably 1 to
1000 parts by mass, more preferably 5 to 1000 parts by mass, and
further preferably 7 to 500 parts by mass, with respect to 100
parts by mass of the whole amount of polymerizable monomer
components. The one-component one-step bonding system needs to
perform all the processes of decalcifying, penetration, and curing
with one liquid in one step. Therefore, from the viewpoint that
penetrability is considered important, it is preferable that water
(I) be contained as the solvent (E). On the other hand, from the
viewpoint that curability is considered important, it is preferable
that the bonding system contain a suitable amount of crosslinkable
polymerizable monomer (D). From the viewpoints of increasing the
solubility of the aforementioned (D) and obtaining a uniform
solution, it is preferable that an organic solvent (J) be contained
as the aforementioned solvent (E). A more preferable embodiment is
the use of the solvent (E) in the form of a mixed solvent of water
(I) and an organic solvent (J). In such an embodiment, the amounts
of the aforementioned (I) and (J) to be added are preferably 1 to
1000 parts by mass of (I) and 2 to 1000 parts by mass of (J), more
preferably 2 to 1000 parts by mass of (I) and 4 to 1000 parts by
mass of (J), and further preferably 5 to 500 parts by mass of (I)
and 6 to 500 parts by mass of (J), with respect to 100 parts by
mass of the whole amount of polymerizable monomer components.
[0164] The composition of the present invention is used preferably
as composite resin. When the composition of the present invention
is used as composite resin, the composition is preferably one
containing a polymerizable monomer (A), crosslinkable polymerizable
monomer (D), polymerization initiator (F), and filler (H).
Generally, the composite resin is used in the form of filling a
cavity after the cavity is formed by cutting a site of caries
incidence. Thereafter, generally, the composite resin filling the
cavity is cured through photopolymerization. Therefore, it is
preferable that a photopolymerization initiator be used as the
aforementioned (F). Furthermore, since the composite resin that has
filled the cavity and that has been cured as described above is
subjected to occlusal pressure inside an oral cavity, high
mechanical strength is required. Accordingly, the content of the
filler (H) in the composition is preferably 50 to 2000 parts by
mass and more preferably 100 to 1500 parts by mass, with respect to
100 parts by mass of the whole amount of polymerizable monomer
components. When the content of the filler (H) is less than 50
parts by mass, mechanical strength of the cured product may be
insufficient. On the other hand, when the content of the filler (H)
exceeds 1500 parts by mass, it may become difficult to disperse the
filler (H) uniformly throughout the whole amount of polymerizable
monomer components, which may result in a composition that is
insufficient in mechanical strength and handling ability.
[0165] The amounts of respective components to be added are
preferably 10 to 80 parts by mass of (A) and 20 to 90 parts by mass
of (D), more preferably 10 to 70 parts by mass of (A) and 30 to 90
parts by mass of (D), and further preferably 10 to 60 parts by mass
of (A) and 40 to 90 parts by mass of (D), in 100 parts by mass of
the whole amount of polymerizable monomer components. The amount of
(F) to be contained is preferably 0.001 to 20 parts by mass, more
preferably 0.05 to 10 parts by mass, and further preferably 0.05 to
5 parts by mass, with respect to 100 parts by mass of the whole
amount of polymerizable monomer components. The use of
polymerization initiator (F) and polymerization accelerator (G) in
combination also is a preferable embodiment. As the polymerization
accelerator (G), amines are preferable. In this case, it is
preferable that 0.001 to 20 parts by mass of (F) and 0.001 to 30
parts by mass of (G) be contained, more preferably 0.05 to 10 parts
by mass of (F) and 0.05 to 20 parts by mass of (G) be contained,
and further preferably 0.05 to 5 parts by mass of (F) and 0.1 to 10
parts by mass of (G) be contained, with respect to 100 parts by
mass of the whole amount of polymerizable monomer components.
[0166] Since the polymerizable monomer (A) of the present invention
has both excellent curability and penetrability into a tooth
structure, it is preferable that it be used particularly as a
self-adhesive composite resin among composite resins. When the
composition of the present invention is used as a self-adhesive
composite resin, it is preferable that the composition contain a
polymerizable monomer (A), polymerizable monomer (C) having an
acidic group, crosslinkable polymerizable monomer (D),
polymerization initiator (F), and filler (H). The amounts of
respective components to be added are preferably 1 to 80 parts by
mass of (A), 1 to 80 parts by mass (C), and 1 to 97 parts by mass
of (D), more preferably 3 to 70 parts by mass of (A), 2 to 60 parts
by mass of (C), and 5 to 93 parts by mass of (D), and further
preferably 5 to 70 parts by mass of (A), 2 to 40 parts by mass of
(C), and 10 to 90 parts by mass of (D), in 100 parts by mass of the
whole amount of polymerizable monomer components. Furthermore, when
the penetrability into a tooth structure (particularly dentin) is
considered important, it is preferable that the composition further
contain a polymerizable monomer (B) having one polymerizable group
and at least one hydroxyl group. When the self-adhesive composite
resin contains (A), (B), (C), and (D), the amounts of respective
components to be added are preferably 1 to 80 parts by mass of (A),
1 to 80 parts by mass of (B), 1 to 80 parts by mass of (C), and 1
to 97 parts by mass (D), more preferably 3 to 70 parts by mass of
(A), 2 to 70 parts by mass of (B), 2 to 60 parts by mass of (C),
and 5 to 93 parts by mass of (D), and further preferably 5 to 70
parts by mass of (A), 3 to 50 parts by mass of (B), 2 to 40 parts
by mass of (C), and 10 to 90 parts by mass of (D), in 100 parts by
mass of the whole amount of polymerizable monomer components. With
respect to the amounts of polymerization initiator (F) and filler
(H) to be added, the same amounts as those used in the
aforementioned general composite resin can be employed.
Furthermore, in the same manner as in the case of the
aforementioned general composite resin, the combined use of the
polymerization initiator (F) and the polymerization accelerator (G)
also is a preferable embodiment. The amounts of the aforementioned
(F) and (G) to be added are as described above. Moreover, when
particularly the penetrability into a tooth structure is considered
important, it also is possible to add a solvent (E), and it is
further preferable that the solvent (E) contain water (I). The
amount of solvent (E) to be added is preferably 0 to 15 parts by
mass and more preferably 1 to 10 parts by mass, with respect to 100
parts by mass of the whole amount of polymerizable monomer
components.
[0167] Furthermore, the use of a composition of the present
invention as a dental cement also is one of preferable embodiments.
Examples of preferable cements include a resin cement, glass
ionomer cement, and resin-reinforced glass ionomer cement. When the
composition of the present invention is used as a resin cement, the
composition is preferably one containing a polymerizable monomer
(A), crosslinkable polymerizable monomer (D), polymerization
initiator (F), polymerization accelerator (G), filler (H), and
water (I) to serve as a solvent (E). Such a composition further can
contain a polymerizable monomer (C) having an acidic group. The
dental cement is used suitably as, for example, a luting material
that is used in fixing a metal or ceramics dental crown restorative
material, which is referred to as an "inlay" or "crown", to a
tooth. As in the case of the aforementioned (A) used in the present
invention, when at least two polymerizable groups are included, the
resultant cured product has increased mechanical strength and can
withstand, for example, occlusal pressure. From such a viewpoint,
it is more preferable that the aforementioned (D) be a
polymerizable monomer having at least two polymerizable groups.
Furthermore, in the case of the form of usage as described above,
since many of the dental crown restorative materials have optical
opacity, it is not easy to cure the cement by only
photopolymerization. Therefore, it is preferable that a chemical
polymerization initiator be used as the aforementioned (F).
Furthermore, when polymerization is performed by using a chemical
polymerization initiator, in order to improve the reactivity
thereof, the use of amines and/or sulfinic acid and salt thereof as
the aforementioned (G) is preferable and the simultaneous use of
amines and sulfinic acid and salt thereof is more preferable. The
filler (H) used is not particularly limited.
[0168] When the cement is intended to be provided with a property
of sustained-release of fluoride, it is preferable that at least
one selected from the group consisting of fluoroaluminosilicate
glass, calcium fluoroaluminosilicate glass, strontium
fluoroaluminosilicate glass, barium fluoroaluminosilicate glass,
and strontium calcium fluoroaluminosilicate glass be used as the
filler (H), and it is more preferable that fluoroaluminosilicate
glass and/or barium fluoroaluminosilicate glass be used as the
filler (H). On the other hand, when the cement is intended to be
provided with radiopacity, it is preferable that at least one
selected from the group consisting of barium glass, strontium
glass, barium boroaluminosilicate glass, strontium
boroaluminosilicate glass, strontium fluoroaluminosilicate glass,
and barium fluoroaluminosilicate glass be used as the filler (H),
and it is more preferable that barium glass and/or barium
fluoroaluminosilicate glass be used as the filler (H).
[0169] When a chemical polymerization initiator is used, from the
viewpoint of storage stability, it is preferable that the
aforementioned (F) and (G) be stored in separate containers,
respectively. That is, in a preferred embodiment, the resin cement
is used in the form of a two component type. In a more preferred
embodiment, the resin cement is used in the form of two paste type.
Preferably, the respective pastes are stored while being separated
from each other, the two pastes are mixed together immediately
before use, and thereby chemical polymerization is allowed to
proceed to cure the mixture. The aforementioned pastes each are
prepared by mixing a liquid component of, for example,
polymerizable monomer with a filler (H) (powder) together.
Furthermore, when sulfinic acid and salt thereof are used as the
aforementioned (G), from the viewpoint of storage stability, it is
preferable that the aforementioned (C) and (G) be stored in
separate containers, respectively. Suppose that the aforementioned
two pastes are referred to as a paste A and a paste B,
respectively, an embodiment in which the paste A contains (A), (C),
(F), and (H) and the paste B contains (A), (G), and (H) is used
particularly appropriately.
[0170] When the composition of the present invention is used as a
dental cement, the amounts of respective components to be added are
not particularly limited. However, in 100 parts by mass of the
whole amount of polymerizable monomer components, the composition
contains preferably 1 to 90 parts by mass of (A), 1 to 90 parts by
mass of (B), 1 to 90 parts by mass of (C), and 1 to 90 parts by
mass of (D), and more preferably 2 to 90 parts by mass of (A), 2 to
80 parts by mass of (B), 2 to 80 parts by mass of (C), and 2 to 80
parts by mass of (N. When consideration is given to obtaining a
suitable setting time, the amounts of the aforementioned (F) and
(G) to be added are preferably 0.001 to 20 parts by mass of (F) and
0.001 to 30 parts by mass of (G) and more preferably 0.05 to 15
parts by mass of (F) and 0.05 to 20 parts by mass of (G), with
respect to 100 parts by mass of the whole amount of polymerizable
monomer components.
[0171] Moreover, the content of (H) is preferably 30 to 2000 parts
by mass and more preferably 50 to 1500 parts by mass, with respect
to 100 parts by mass of the whole amount of polymerizable monomer
components. When the content of (H) is less than 30 parts by mass,
mechanical strength of the cured product may be insufficient. On
the other hand, in the case where the content of (H) exceeds 2000
parts by mass, when the resin cement is used as a two-paste-type
cement, which is a preferred embodiment, the pastes lack fluidity,
which makes it difficult to carry out sufficient mixing, and
therefore the cured product may have reduced strength.
[0172] The composition of the present invention is used preferably
as a glass ionomer cement and more preferably as a resin-reinforced
glass ionomer cement. The glass ionomer cement is typically one in
which an inorganic filler such as fluoroaluminosilicate glass and
polyalkenoic acid such as polyacrylic acid are reacted with each
other through an acid-base reaction to be cured. Conceivably, the
polyacrylic acid interacts with calcium contained in hydroxyapatite
composing a tooth structure and thereby a bonding function is
exhibited. When a composition of the present invention is used as a
glass ionomer cement, particularly preferably as a resin-reinforced
glass ionomer cement, the composition is preferably one containing
(A), (E), (F), (G), (H), and polyalkenoic acid, and more preferably
one containing (A), (D), (E), (F), (G), (H), and polyalkenoic acid,
one containing (A), (B), (E), (F), (G), (H), and polyalkenoic acid,
or one containing (A), (B), (D), (E), (F), (G), (H), and
polyalkenoic acid. Such compositions further can contain (C).
[0173] The polymerizable monomer (B) having one polymerizable group
and at least one hydroxyl group to be used is not particularly
limited. As described later, from the viewpoint that an acid-base
reaction is allowed to proceed smoothly, it is preferable that the
solvent (E) contain water (I). Therefore, from the viewpoints of
maintaining the uniformity of the composition and obtaining
consistent performance, it is more preferable that a monomer with
high affinity for water (I) be used as the aforementioned (B). Such
a monomer with high affinity for water (I) is preferably
2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate,
glycerol mono(meth)acrylate, or erythritol mono(meth)acrylate and
particularly preferably 2-hydroxyethylmethacrylate.
[0174] The crosslinkable polymerizable monomer (D) to be used is
not particularly limited, but as described above, the use of a
monomer with high affinity for water (I) as the aforementioned (D)
is more preferable from the viewpoints of maintaining the
uniformity of the composition and obtaining consistent performance.
In terms of a balance between such affinity for water (I) and the
mechanical strength of the cured product, the aforementioned (D) is
preferably an aliphatic compound-based bifunctional polymerizable
monomer and more preferably triethylene glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate, neopentyl glycol
di(meth)acrylate,
1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, or
2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate
(commonly known as "UDMA").
[0175] The aforementioned polyalkenoic acid is a polymer of
unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
Specific examples of the polyalkenoic acid include homopolymers of,
for example, acrylic acid, methacrylic acid, 2-chloroacrylic acid,
2-cyanoacrylic acid, aconitic acid, mesaconic acid, maleic acid,
itaconic acid, fumaric acid, glutaconic acid, citraconic acid, and
utraconic acid, or copolymers of these unsaturated carboxylic acids
and monomers copolymerizable therewith. In the case of the
copolymers, the ratio of the unsaturated carboxylic acid unit is
preferably at least 50 mol % with respect to the total structure
unit. An ethylenically unsaturated polymerizable monomer is
preferable as the copolymerizable monomer, and examples thereof
include styrene, acrylamide, acrylonitrile, methyl methacrylate,
acrylic acid salts, vinyl chloride, allyl chloride, vinyl acetate,
and 1,1,6-trimethylhexamethylene dimethacrylate ester. Among those
polyalkenoic acids, a homopolymer or copolymer of acrylic acid or
maleic acid is preferable. When these polyalkenoic acids have a
weight-average molecular weight of less than 5,000, the cured
product of the dental cement composition may have reduced strength
and poor durability. On the other hand, when it has a
weight-average molecular weight exceeding 40,000, it may have high
consistency during mixing of the dental cement composition and
therefore may have lower operability. Accordingly, a preferable
weight-average molecular weight of the polyalkenoic acid is 5,000
to 40,000.
[0176] From the viewpoints of curability in the acid-base reaction
and the property of sustained-release of fluoride of the
composition, the filler (H) to be used is preferably at least one
selected from the group consisting of fluoroaluminosilicate glass,
calcium fluoroaluminosilicate glass, strontium
fluoroaluminosilicate glass, barium fluoroaluminosilicate glass,
and strontium calcium fluoroaluminosilicate glass, and more
preferably fluoroaluminosilicate glass and/or barium
fluoroaluminosilicate glass.
[0177] Furthermore, the solvent (E) to be used is not particularly
limited. However, from the viewpoint that an acid-base reaction is
allowed to proceed smoothly, it is preferable that the solvent (E)
contain water (I). When a mixed solvent of water (I) and an organic
solvent (J) is used as the solvent (E), the content of water (I) in
the mixed solvent is preferably at least 50 mass %, more preferably
at least 70 mass %, and further preferably at least 90 mass %. In
an embodiment in which particularly progress of the acid-base
reaction is considered important, it is particularly preferable
that the solvent (E) consist substantially of water (I) alone.
[0178] When a composition of the present invention is used as a
glass ionomer cement, particularly preferably as a resin-reinforced
glass ionomer cement, the amounts of respective components to be
added are not particularly limited. When the composition contains
(A) and (B), it contains preferably 1 to 90 parts by mass of (A), 1
to 90 parts by mass of (B), and 0 to 50 parts by mass of (C) and
more preferably 2 to 90 parts by mass of (A), 5 to 90 parts by mass
of (B), and 0 to 30 parts by mass of (C), in 100 parts by mass of
the whole amount of polymerizable monomer components. When the
composition contains (A) and (D), it contains preferably 1 to 90
parts by mass of (A), 1 to 90 parts by mass of (D), and 0 to 50
parts by mass of (C) and more preferably 2 to 90 parts by mass of
(A), 5 to 90 parts by mass of (D), and 0 to 30 parts by mass of
(C), in 100 parts by mass of the whole amount of polymerizable
monomer components. Furthermore, when the composition contains (A),
(B), and (D), it contains preferably 1 to 90 parts by mass of (A),
1 to 90 parts by mass of (B), 1 to 90 parts by mass of (D), and 0
to 50 parts by mass of (C) and more preferably 2 to 90 parts by
mass of (A), 5 to 90 parts by mass of (B), 5 to 90 parts by mass of
(D), and 0 to 30 parts by mass of (C), in 100 parts by mass of the
whole amount of polymerizable monomer components.
[0179] When consideration is given to obtaining a suitable setting
time, the amounts of the aforementioned (F) and (G) to be added are
preferably 0.001 to 30 parts by mass of (F) and 0.001 to 30 parts
by mass of (G), more preferably 0.05 to 20 parts by mass of (F) and
0.05 to 20 parts by mass of (G), with respect to 100 parts by mass
of the whole amount of polymerizable monomer components. Moreover,
the content of (H) is preferably 30 to 2000 parts by mass and more
preferably 50 to 1500 parts by mass, with respect to 100 parts by
mass of the whole amount of polymerizable monomer components. When
the content of (H) is less than 30 parts by mass, mechanical
strength of the cured product may be insufficient. On the other
hand, when the content of (H) exceeds 2000 parts by mass, the
composition paste has lower fluidity, which makes sufficient mixing
difficult, and therefore the acid-base reaction may not proceed
smoothly. As a result, the cured product may have reduced
strength.
[0180] With respect to 100 parts by mass of the whole amount of
polymerizable monomer components, the content of solvent (E) is
preferably 7 to 500 parts by mass, more preferably 10 to 300 parts
by mass, and further preferably 10 to 100 parts by mass. When the
solvent (E) is contained in such ranges, the acid-base reaction can
proceed smoothly, and the resultant cured product has excellent
mechanical strength and excellent adhesive properties to a tooth
structure.
[0181] With respect to 100 parts by mass of the whole amount of
polymerizable monomer components, the content of the aforementioned
polyalkenoic acid is preferably 1 to 200 parts by mass, more
preferably 5 to 100 parts by mass, and further preferably 10 to 50
parts by mass. When the polyalkenoic acid is contained in such
ranges, curing through the acid-base reaction proceeds smoothly and
decay of the resultant cured product inside an oral cavity by, for
example, hydrolysis can be diminished.
[0182] As described above, since curing of a glass ionomer cement
occurs through progress of an acid-base reaction, from the
viewpoint of storage stability, it is preferable that a basic
filler (H) and polyalkenoic acid be packed in separate containers
and be used after being mixed immediately before use. The
preferable types of products to be employed include a so-called
powder-liquid type, but from the viewpoint of improving handling
ability, the form of so-called two paste-type glass ionomer cement
containing two types of pastes is more preferable. In the case
where the type of product is the two paste type, when the
aforementioned two pastes are referred to as a paste A and a paste
B, respectively, an embodiment is preferable in which the paste A
contains (A), (E), (F), (H), and polyalkenoic acid and the paste B
contains (B) and (H). Furthermore, an embodiment in which the paste
A contains (A), (E), (F), (H), and polyalkenoic acid and the paste
B contains (D) and (H) also is used preferably. In addition, an
embodiment in which the paste A contains (D), (F), (H), and
polyalkenoic acid and the paste B contains (A), (E), (G), and (H)
also is used preferably. In this case, when particularly adhesive
properties are considered important, it is preferable that the
paste A further contain (C), and from the similar viewpoint, it
also is preferable that the paste B further contain (B). In all of
the embodiments, since the paste A contains polyalkenoic acid, it
is preferable that at least one selected from the group consisting
of fluoroaluminosilicate glass, calcium fluoroaluminosilicate
glass, strontium fluoroaluminosilicate glass, barium
fluoroaluminosilicate glass, and strontium calcium
fluoroaluminosilicate glass be used as the filler (H) contained in
the paste B, and it is more preferable that fluoroaluminosilicate
glass and/or barium fluoroaluminosilicate glass be used as the
filler (H). On the other hand, the filler (H) contained in the
paste A to be used is preferably one that exhibits no reactivity
with polyalkenoic acid, and particularly preferably quartz.
[0183] These dental materials can be prepared and used according to
a conventional method, and bonded to a tooth structure with high
bond strength.
[0184] Hereinafter, the present invention is described in detail
using examples but is not limited thereto.
[0185] [HPLC Measurement on Polymerizable Monomer]
(1) Method for Preparing Sample
[0186] A monomer was weighed to be about 20 mg in a sample tube
bottle, and diluted with 1 g of methanol (for high-performance
liquid chromatography, manufactured by Wako Pure Chemical
Industries, Ltd.). The sample tube bottle was shaken to dissolve
the monomer component. After that, dilution was filtered using a
disposable syringe (manufactured by Terumo Corp., "Terumo Syringe"
(trade name) for tuberculin, 1 mL) and a disposable filter unit for
HPLC (manufactured by Nihon Pall Ltd., "Ekicrodisk" (trade name),
13CR, 0.45 .mu.m, PTFE). Thus a measurement sample for HPLC was
prepared.
(2) HPLC Measurement
[0187] The HPLC measurements on the polymerizable monomers used in
the Examples and the Comparative Examples were performed using, in
the HPLC, CBM-20A, manufactured by Shimadzu Corp., as the system
controller, SIL-20A, manufactured by Shimadzu Corp., as the
autosampler, SPD-M20A, manufactured by Shimadzu Corp., as the
detector, CTO-20A, manufactured by Shimadzu Corp., as the column
oven, LC-20AT as the liquid-sending unit, and .mu.Bondapak
(registered trademark) C.sub.18 analytical column (C18 packing
material (crushed type) with an average particle size of 10
micrometers and a pore size of 125 angstroms, and the column size
is 3.9 mm.times.300 mm), manufactured by Waters Corp., as the
column. When using these, the dead volume from the sample inlet to
the detection point excluding the column was 87 .mu.L. A mixed
solvent of methanol and water contained at a ratio of 3:7 was used
as the eluent. The flow rate was 1.0 mL/minute, the measurement
temperature was 50.degree. C., and the sample injection volume was
10 .mu.L. The pressure during the measurement was 5 MPa to 10 MPa
(50 kgf/cm.sup.2 to 100 kgf/cm.sup.2). Table 1 shows the
measurement results.
TABLE-US-00001 TABLE 1 HPLC measurement results Retention time
(min) HEMA 6.02 SDMA *13.64 MDMA *12.68 EDMA *18.23 XDMA *21.27
ErMA 34.12 GDMA 41.52 #801 >45 *denotes retention times falling
in claimed range.
Example 1
Application of Polymerizable Composition Containing Polymerizable
Monomer (A) to a One-Step Bonding System (One-Component Bonding
Material)
[0188] (1) Production of One-Component Bonding Materials
[0189] One-component bonding materials using the polymerizable
composition containing the polymerizable monomer (A) were prepared.
Table 2 shows the compositions thereof.
TABLE-US-00002 TABLE 2 One-Component Bonding Material Compositions
and Bonding Evaluation Results C. C. C. C. Exam- Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple ple ple
ple ple Components 1-1 1-2 1-3 1-4 1-5 1-6 1-1 1-2 1-3 1-4
Polymerizable monomer (A) EDMA 15 15 30 XDMA 15 SDMA 15 MDMA 15
Polymerizable monomer for #801 15 comparison with (A) GDMA 15 ErMA
15 Polymerizable monomer (B) HEMA 15 15 15 15 15 15 15 15 30 having
one polymerizable group and at least one hydroxyl group
Polymerizable monomer (C) MDP 10 10 10 10 10 10 10 10 10 10 having
acidic group Crosslinkable polymerizable Bis-GMA 30 30 30 30 30 30
30 30 30 30 monomer (D) Solvent (E) Distilled water 15 15 15 15 15
15 15 15 15 15 Ethanol 15 15 15 15 15 15 15 15 15 15 Polymerization
initiator (F) TMDPO 5 5 5 5 5 5 5 5 5 CQ 2 Polymerization
accelerator (G) DBB 1 Filler (H) Inorganic filler 1 5 5 5 5 5 5 5 5
5 5 Bond strength with respect to After 24 hours 18.7 16.5 17.5
19.9 18.5 12.9 10.2 12.8 12.8 12.9 dentin (MPa) After thermal 19.0
18.2 18.4 19.5 18.6 15.1 9.5 9.8 11.2 8.6 cycles load Retention
time of (A) used (min) 18.2 21.3 13.6 12.7 10.1 13.6 >45 41.5
34.1 6.0 (The amounts of respective components added each are
indicated in the unit of parts by mass.) EDMA: erythritol
dimethacrylate [1,4-bis(methacryloyloxy)-2,3-butanediol] XDMA:
xylitol dimethacrylate
[1,5-bis(methacryloyloxy)-2,3,4-pentanetriol] SDMA: sorbitol
dimethacrylate [1,6-bis(methacryloyloxy)-2,3,4,5-hexanetetraol]
MDMA: mannitol dimethacrylate (3,4-di-O-methacryloyl-D-mannitol)
#801: 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane GDMA:
glycerol dimethacrylate [polymerizable monomer for comparative
examples that does not correspond to polymerizable monomer (A)]
ErMA: pentaerythritol dimethacrylate HEMA:
2-hydroxyethylmethacrylate MDP:
10-methacryloyloxydecyldihydrogenphosphate Bis-GMA: bisphenol A
diglycidyl methacrylate TMDPO:
2,4,6-trimethylbenzoyldiphenylphosphine oxide CQ: camphorquinone
DBB: N,N-dimethylaminobenzoic acid n-butoxyethyl ester Inorganic
filler1: "R972" manufactured by Japan Aerosil Inc. MDMA is a new
compound and it was synthesized by the following method.
Reference Example
Synthesis of MDMA
(i) Synthesis of
1,2:5,6-Di-O-isopropylidene-3,4-di-O-methacryloyl-D-mannitol
[0190] After 700 mL of anhydrous pyridine was added to a 2 L
separable flask equipped with a condenser tube, 65 g of
1,2:5,6-Di-O-isopropylidene-D-mannitol (manufactured by Wako Pure
Chemical Industries, Ltd.) was added into the flask gradually and
was dissolved completely. An ice bath was set for the reaction
system and the reaction system was cooled to 0.degree. C.
Subsequently, while the temperature of the reaction system was
maintained around 0.degree. C. and the reaction system was stirred,
60 g of methacryloyl chloride (manufactured by Wako Pure Chemical
Industries, Ltd.) was dropped into the reaction system in a
nitrogen atmosphere using a dropping funnel over approximately one
hour. The dropping funnel was replaced by a glass stopper, and the
reaction system was heated to 70.degree. C. using an oil bath. This
heating was continued for eight hours. After completion of heating,
the oil bath was removed and the reaction system was then cooled to
room temperature. Subsequently, the reaction system was poured into
a beaker containing 1 L of ice water and thereby the reaction was
stopped. After the reaction was stopped, extraction was performed
five times using 1500 mL of diethyl ether. Thereafter, the
resultant organic layer was subjected to vacuum concentration using
an evaporator and thus an oily material was obtained. The oily
material was purified using silica gel column chromatography
(diluents: hexane:diethyl ether=7:3). After concentration, hexane
was added and thereby recrystallization was carried out. Thus, a
target compound was obtained. The yield amount was 36.3 g, and the
yield rate was 37%.
[0191] .sup.1H-NMR (400 MHz, CDCl.sub.3, .delta.) 1.31 (s, 6H),
1.36 (s, 6H), 1.96 (s, 6H), 3.85-3.96 (m,4H), 4.21-4.27 (m, 2H),
5.43 (dd, 2H), 5.64 (s, 2H), 6.15 (s, 2H) (ppm)
[0192] .sup.13C-NMR (100 MHz, CDCl.sub.3, .delta.) 18.2, 25.1,
26.3, 65.5, 71.6, 74.7, 109.3, 126.6, 135.6, 166.0 (ppm)
(ii) Synthesis of MDMA (3,4-di-O-methacryloyl-D-mannitol)
[0193] 540 mL of acetic acid and 180 mL of water were added to a 2
L round-bottom flask. While the resultant acetic acid aqueous
solution was stirred, 18 g of
1,2:5,6-Di-O-isopropylidene-3,4-di-O-methacryloyl-D-mannitol
synthesized above was added gradually thereto and was dissolved
completely. The solution thus prepared was stirred for 18 hours,
with the temperature thereof being maintained at 25.degree. C.
After completion of stirring, the solution was subjected to vacuum
concentration using an evaporator and thus an oily material was
obtained. The oily material was purified using silica gel column
chromatography (diluent:ethyl acetate 100%) and was concentrated.
As a result, white crystals were precipitated. It was confirmed by
NMR that these crystals were a target compound. The yield amount
was 8.7 g and the yield rate was 60%.
[0194] .sup.1H-NMR (400 MHz, CD.sub.3OD, .delta.) 1.84 (s, 6H),
3.39 (dd, 2H), 3.51 (dd,2H), 3.59-3.66 (m,2H), 5.28 (d, 2H), 5.56
(s, 2H), 6.03 (s, 2H (ppm)
[0195] .sup.13C-NMR (100 MHz, CD.sub.3OD, .delta.) 18.4, 64.2,
71.6, 73.1, 126.8, 137.4, 167.9 (ppm)
[0196] (2) Method for Evaluating Bonding to Bovine Dentin
[0197] The labial surface of a bovine mandibular incisor was ground
with #80 silicon carbide paper (manufactured by Nihon Kenshi Co.,
Ltd.) under running water, and thereby a sample with an exposed
flat surface of dentin was obtained. The sample thus obtained
further was ground with #1000 silicon carbide paper (manufactured
by Nihon Kenshi Co., Ltd.) under running water. After completion of
grinding, water on the surface was air-blown to be dried. An
adhesive tape with a thickness of about 150 .mu.m having a circular
hole whose diameter was 3 mm was attached to the smooth surface
that had been dried and thereby the adhesive area was defined.
[0198] Each one-component bonding material produced above was
applied into the above-mentioned circular hole using a brush and
was then allowed to stand for 20 seconds. Thereafter, the surface
thereof was air-blown and thereby the one-component bonding
material thus applied was dried until it lost fluidity.
Subsequently, it was irradiated with light using a dental visible
light unit "JET LITE 3000" (manufactured by J. Morita USA) for 10
seconds. Thus, the one-component bonding material that had been
applied was cured.
[0199] A dental filling composite resin (manufactured by Kuraray
Medical Inc., "CLEARFIL AP-X" (trade name, registered trademark))
was filled on the surface of the resultant cured product of the
one-component bonding material, and it was then covered with a mold
release film (polyester). Next, slide glass was placed on the mold
release film to press it, and thereby the surface of the applied
composite resin was smoothed. Subsequently, the composite resin was
irradiated with light for 20 seconds using the aforementioned unit
"JET LITE 3000" through the mold release film. Thus, the composite
resin was cured.
[0200] One end face (circular section) of a stainless-steel
cylindrical rod (with a diameter of 7 mm and a length of 2.5 cm)
was bonded to the surface of the resultant cured product of the
dental filling composite resin using a commercially available
dental resin cement (manufactured by Kuraray Medical Inc.,
"PANAVIA21" (trade name)). After bonding, this sample was allowed
to stand still at room temperature for 30 minutes and was then
immersed in distilled water. Ten bonding test samples were produced
in total, and all the samples that had been immersed in distilled
water were allowed to stand still for 24 hours inside a thermostat
whose temperature was maintained at 37.degree. C. With respect to
five samples out of the ten samples, in order to evaluate the bond
strength in the early bonding stage, the bond strength was measured
immediately after they were allowed to stand still for 24 hours.
With respect to the other five samples, in order to evaluate bond
durability, bond strength was measured after 4000 thermal cycles
had been performed, with one cycle being a process for further
immersing each sample in 4.degree. C. cold water and 60.degree. C.
warm water alternately for one minute.
[0201] (3) Bonding Evaluation Test (Evaluations of Bond Strength
and Bond Durability)
[0202] The tensile bond strengths of the above-mentioned bonding
test samples were measured with a universal testing machine
(manufactured by Shimadzu Corporation), with the crosshead speed
being set at 2 mm/min, and the average value thereof was taken as
tensile bond strength.
Example 1-1
[0203] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, EDMA that corresponds to the
polymerizable monomer (A).
Example 1-2
[0204] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, XDMA that corresponds to the
polymerizable monomer (A).
Example 1-3
[0205] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, SDMA that corresponds to the
polymerizable monomer (A).
Example 1-4
[0206] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, MDMA that corresponds to the
polymerizable monomer (A).
Example 1-5
[0207] The evaluation test was performed in the same way as in
Example 1-1, except that the polymerization initiator used in
Example 1-1 was changed as shown in Table 2, and that a
polymerization accelerator was used.
Example 1-6
[0208] The evaluation test was performed in the same way as in
Example 1-1, except that 30 parts by mass of EDMA corresponding to
the polymerizable monomer (A) was used as the hydrophilic monomer
to be added to the one-component bonding material, and that HEMA
corresponding to the polymerizable monomer (B) was not added.
Comparative Example 1-1
[0209] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, #801 (with a long retention time)
that does not correspond to the polymerizable monomer (A).
Comparative Example 1-2
[0210] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, GDMA (with a long retention time)
that does not correspond to the polymerizable monomer (A).
Comparative Example 1-3
[0211] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, using, as the hydrophilic monomer to be added to the
one-component bonding material, ErMA (with a long retention time)
that does not correspond to the polymerizable monomer (A).
Comparative Example 1-4
[0212] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the one-component bonding material to
bovine dentin, not adding, as the hydrophilic monomer to be added
to the one-component bonding material, EDMA corresponding to the
polymerizable monomer (A) but adding 30 parts by mass of HEMA (with
a short retention time) corresponding to the polymerizable monomer
(B).
[0213] Table 2 shows the results. Table 2 reveals that the
one-component bonding materials using the polymerizable composition
containing the polymerizable monomer (A) of the present invention
have excellent initial bond strength and bond durability with
respect to dentin.
Example 2
Application of Polymerizable Composition Containing Polymerizable
Monomer (A) to a Two-Step Bonding System (Two-Component Bonding
Material)
[0214] (1) Production of Primers Using a Polymerizable Composition
Containing the Polymerizable Monomer (A)
[0215] Primers using a polymerizable composition containing the
polymerizable monomer (A) were produced. Table 3 shows the
compositions of the primers.
TABLE-US-00003 TABLE 3 Primer Compositions and Bonding Evaluation
Results C. C. C. C. Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam-
Example Example ple ple ple ple ple ple ple ple Components 2-1 2-2
2-3 2-4 2-5 2-6 2-1 2-2 2-3 2-4 Polymerizable monomer (A) EDMA 35
35 70 XDMA 35 SDMA 35 MDMA 35 Polymerizable monomer for GDMA 35
comparison with (A) ErMA 35 Polymerizable monomer (B) HEMA 35 35 35
35 35 35 35 35 70 having one polymerizable group and at least one
hydroxyl group Polymerizable monomer (C) MDP 20 20 20 20 20 20 20
20 20 20 having acidic group Crosslinkable polymerizable #801 10 10
10 10 10 10 45 10 10 10 monomer (D) Solvent (E) Distilled water 50
50 50 50 50 50 50 50 50 50 Ethanol 50 50 50 50 50 50 50 50 50 50
Polymerization initiator (F) TMDPO 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
0.8 CQ 0.8 Polymerization accelerator (G) DBB 1 Bond strength with
respect to After 24 hours 23.6 21.2 20.3 22.7 23.9 21.8 13.2 13.8
14.9 14.4 dentin (MPa) After thermal 23.9 21.8 20.4 21.5 22.4 20.2
10.8 9.3 12.4 8.7 cycles load (The amounts of respective components
added each are indicated in the unit of parts by mass, and the
respective abbreviations have the same meanings as described
above.)
[0216] (2) Method for Evaluating Bonding to Bovine Dentin
[0217] The labial surface of a bovine mandibular incisor was ground
with #80 silicon carbide paper (manufactured by Nihon Kenshi Co.,
Ltd.) under running water, and thereby a sample with an exposed
flat surface of dentin was obtained. The sample thus obtained
further was ground with #1000 silicon carbide paper (manufactured
by Nihon Kenshi Co., Ltd.) under running water. After completion of
grinding, water on the surface was air-blown to be dried. An
adhesive tape with a thickness of about 150 .mu.m having a circular
hole whose diameter was 3 mm was attached to the smooth surface
that had been dried and thereby the adhesive area was defined.
[0218] Each primer produced above was applied into the
above-mentioned circular hole using a brush and was then allowed to
stand for 20 seconds. Thereafter, the surface thereof was air-blown
and thereby the primer thus applied was dried until it lost
fluidity. Next, the bonding material having a composition indicated
in Table 4 was applied over the tooth surface where the primer had
been applied and dried. Subsequently, it was irradiated with light
using a dental visible light unit "JET LITE 3000" (manufactured by
J. Morita USA) for 10 seconds. Thus, the primer and bonding
material that had been applied were cured.
[0219] A dental filling composite resin (manufactured by Kuraray
Medical Inc., "CLEARFIL AP-X" (trade name, registered trademark))
was applied to the surface of the resultant cured product of the
bonding material, and it was then covered with a mold release film
(polyester). Next, slide glass was placed on the mold release film
to press it, and thereby the surface of the applied composite resin
was smoothed. Subsequently, the composite resin was irradiated with
light for 20 seconds using the aforementioned unit "JET LITE 3000"
through the mold release film. Thus, the composite resin was
cured.
[0220] One end face (circular section) of a stainless-steel
cylindrical rod (with a diameter of 7 mm and a length of 2.5 cm)
was bonded to the surface of the resultant cured product of the
dental filling composite resin using a commercially available
dental resin cement (manufactured by Kuraray Medical Inc.,
"PANAVIA21" (trade name)). After bonding, this sample was allowed
to stand still at room temperature for 30 minutes and was then
immersed in distilled water. Ten bonding test samples were produced
in total, and all the samples that had been immersed in distilled
water were allowed to stand still for 24 hours inside a thermostat
whose temperature was maintained at 37.degree. C. With respect to
five samples out of the ten samples, in order to evaluate the bond
strength in the early bonding stage, the bond strength was measured
immediately after they were allowed to stand still for 24 hours.
With respect to the other five samples, in order to evaluate bond
durability, bond strength was measured after 4000 thermal cycles
had been performed, with one cycle being a process for further
immersing each sample in 4.degree. C. cold water and 60.degree. C.
warm water alternately for one minute.
TABLE-US-00004 TABLE 4 Composition of Bonding Material Amount added
Components (parts by mass) HEMA 40 Bis-GMA 40 NPG 20 Photoinitiator
(TMDPO) 3 Inorganic Filler 1 5.5 Inorganic Filler 2 1.5 NPG:
neopentyl glycol dimethacrylate Inorganic filler 2: "Ar380",
manufactured by Japan Aerosil Inc. (The other abbreviations have
the same meanings as described above.)
[0221] (3) Bonding Evaluation Test (Evaluations of Bond Strength
and Bond Durability)
[0222] The tensile bond strengths of the above-mentioned bonding
test samples were measured with a universal testing machine
(manufactured by Shimadzu Corporation), with the crosshead speed
being set at 2 mm/min, and the average value thereof was taken as
tensile bond strength.
Example 2-1
[0223] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, EDMA that
corresponds to the polymerizable monomer (A).
Example 2-2
[0224] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, XDMA that
corresponds to the polymerizable monomer (A).
Example 2-3
[0225] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, SDMA that
corresponds to the polymerizable monomer (A).
Example 2-4
[0226] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, MDMA that
corresponds to the polymerizable monomer (A).
Example 2-5
[0227] The evaluation test was performed in the same way as in
Example 2-1, except that the polymerization initiator used in
Example 2-1 was changed as shown in Table 3 and that a
polymerization accelerator was used.
Example 2-6
[0228] The evaluation test was performed in the same way as in
Example 2-1, except that 70 parts by mass of EDMA corresponding to
the polymerizable monomer (A) was added as the hydrophilic monomer
to be added to the primer, and that HEMA corresponding to the
polymerizable monomer (B) was not added.
Comparative Example 2-1
[0229] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, #801 (with a long
retention time) that does not correspond to the polymerizable
monomer (A).
Comparative Example 2-2
[0230] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, GDMA (with a long
retention time) that does not correspond to the polymerizable
monomer (A).
Comparative Example 2-3
[0231] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, using, as the
hydrophilic monomer to be added to the primer, ErMA (with a long
retention time) that does not correspond to the polymerizable
monomer (A).
Comparative Example 2-4
[0232] The above-mentioned bonding evaluation test was conducted to
evaluate the bonding of the primer to bovine dentin, not adding, as
the hydrophilic monomer to be added to the primer, EDMA
corresponding to the polymerizable monomer (A) but adding 70 parts
by mass of HEMA (with a short retention time) corresponding to the
polymerizable monomer (B).
[0233] Table 3 shows the results. Table 3 reveals that the primers
using the polymerizable composition containing the polymerizable
monomer (A) of the present invention have excellent initial bond
strength and bond durability with respect to dentin.
Example 3
Application of Polymerizable Composition Containing Polymerizable
Monomer (A) to Dental Composite Resin
[0234] (1) Production of Dental Composite Resins Using a
Polymerizable Composition Containing the Polymerizable Monomer
(A)
[0235] Pasty dental composite resins using a polymerizable
composition containing the polymerizable monomer (A) were produced.
Two types of the dental composite resins were produced, which are
filling composite resins and self-adhesive composite resins. Table
5 shows the compositions of the filling composite resins, and Table
6 shows those of the self-adhesive composite resins.
TABLE-US-00005 TABLE 5 Filling Composite Resin Compositions and
Bonding Evaluation Results C. C. C. C. C. C. Exam- Exam- Exam-
Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple ple ple ple ple ple
ple ple ple ple 3-1 3-2 3-3 3-4 3-1 3-2 3-3 3-4 3-5 3-6
Polymerizable monomer (A) EDMA 20 MDMA 20 XDMA 20 SDMA 20
Polymerizable monomer for GDMA 20 comparison with (A) ErMA 20 #801
20 Polymerizable monomer (B) HEMA 20 having one polymerizable group
and at least one hydroxyl group Crosslinkable polymerizable 3G 30
30 30 30 30 30 30 50 30 30 monomer (D) D-2.6E 50 50 50 50 70 50 50
50 50 50 Polymerization initiator (F) CQ 1 1 1 1 1 1 1 1 1 1
Polymerization accelerator (G) PDE 1 1 1 1 1 1 1 1 1 1 Filler (H)
Inorganic filler 3 280 280 280 280 280 280 280 280 280 280
Inorganic filler 4 20 20 20 20 20 20 20 20 20 20 Bond strength with
respect to dentin (MPa) 18.5 16.4 16.0 15.9 9.5 15.0 12.5 11.2 12.2
12.5 (when used with adhesive) Bending strength (MPa) 122 113 110
111 135 91 125 123 117 119 PDE: ethyl p-(N,N-dimethylamino)benzoate
Inorganic filler 3: Silane-treated barium glass powder Barium glass
(manufactured by STEC, Product Code: "Raysorb E-3000") was crushed
with a ball mill and thus barium glass powder was obtained. The
mean particle size of the barium glass powder thus obtained was
measured with a laser diffraction particle size distribution
analyzer (manufactured by Shimadzu Corporation, Type "SALD-2100")
and it was 2.4 .mu.m. The surface treatment was performed by a
conventional method using 3 parts by weight
of3-methacryloyloxypropyltrimethoxysilane with respect to 100 parts
by weight of this barium glass powder. Thus, silane-treated barium
glass powder was obtained. Inorganic filler 4: Silane-treated
colloidal silica powder 0.3 part by weight of acetic acid and 3
parts by weight of 3-methacryloyloxypropyltrimethoxysilane were
added to 100 parts by weight of distilled water, which was then
stirred. Further 50 parts by weight of colloidal silica powder
(manufactured by Japan Aerosil Inc., Product Code: "Aerosil OX50")
was added thereto, which was then stirred for one hour. After water
was removed by lyophilization, this was heat-treated at 80.degree.
C. for five hours and thussilane-treated colloidal silica powder
was obtained. (The amounts of respective components added each are
indicated in the unit of parts by mass, and the other abbreviations
have the same meanings as described above.)
TABLE-US-00006 TABLE 6 Self-Adhesive Composite Resin Compositions
and Bonding Evaluation Results C. C. C. C. Example Example Example
Example Example Example Example Example 3-5 3-6 3-7 3-8 3-7 3-8 3-9
3-10 Polymerizable monomer (A) EDMA 25 MDMA 25 XDMA 25 SDMA 25
Polymerizable monomer for GDMA 25 comparison with (A) ErMA 25 #801
25 Polymerizable monomer (B) HEMA 25 25 25 25 50 25 25 25 having
one polymerizable group and at least one hydroxyl group
Polymerizable monomer (C) MDP 10 10 10 10 10 10 10 10 having acidic
group Crosslinkable polymerizable Bis-GMA 40 40 40 40 40 40 40 40
monomer (D) Polymerization initiator (F) CQ 1 1 1 1 1 1 1 1
Polymerization accelerator (G) PDE 1 1 1 1 1 1 1 1 Filler (H)
Inorganic filler 3 230 230 230 230 230 230 230 230 Inorganic filler
4 20 20 20 20 20 20 20 20 Bond strength with respect to dentin
(MPa) 12.3 11.5 10.8 10.9 9.3 8.5 9.2 9.0 (when used without
adhesive) Bending strength (MPa) 100 98 96 95 92 103 97 102 (The
amounts of respective components added each are indicated in the
unit of parts by mass, and the respective abbreviations have the
same meanings as described above.)
[0236] (2) Method for Evaluating Bonding to Bovine Dentin
Filling Composite Resin (Examples 3-1 to 3-4, and Comparative
Examples 3-1 to 3-6)
[0237] A bovine incisor was wet-ground with #1000 silicon carbide
paper (manufactured by Nihon Kenshi Co., Ltd.) to be smooth and
thereby an enamel surface or dentin surface was exposed.
Thereafter, water on the surface was blown away using a dental air
syringe. An adhesive tape with a thickness of about 150 .mu.m
having a circular hole whose diameter was 3 mm was attached to the
exposed enamel surface or dentin surface. A dental adhesive
(manufactured by Kuraray Medical Inc., "CLEARFIL TRI-S BOND" (trade
name)) was applied into the circular hole using a brush and was
then allowed to stand for 20 seconds. Thereafter, the dental
adhesive composition was dried using a dental air syringe until it
lost fluidity. Then, it was irradiated with light for 10 seconds
using the dental light unit (manufactured by MORITA Corp., "JET
LITE 3000" (trade name)). Subsequently, the filling composite resin
composition produced above was placed on the dental adhesive, and
covered with a mold release film (polyester). Thereafter, slide
glass was placed on the mold release film to press it, and this was
irradiated with light for 20 seconds using the dental light unit
"JET LITE 3000". Thus, the composite resin composition was cured.
Next, one end face (circular section) of a stainless-steel
cylindrical rod with a diameter of 7 mm and a length of 2.5 cm was
bonded to the cured surface using the dental resin cement
(manufactured by Kuraray Medical Inc., "PANAVIA21" (trade name)).
This was allowed to stand still for 30 minutes and thus a test
piece was obtained. Five bonding test samples were produced in
total.
Self-Adhesive Composite Resin (Examples 3-5 to 3-8, Comparative
Examples 3-7 to 3-10)
[0238] A bovine incisor was wet-ground with #1000 silicon carbide
paper (manufactured by Nihon Kenshi Co., Ltd.) to be smooth and
thereby an enamel surface or dentin surface was exposed.
Thereafter, water on the surface was blown away using a dental air
syringe. An adhesive tape with a thickness of about 150 .mu.m
having a circular hole whose diameter was 3 mm was attached to the
exposed enamel surface or dentin surface. Each self-adhesive
composite resin composition produced above was placed in the
circular hole and this was covered with a mold release film
(manufactured by Kuraray Co., Ltd., "EVAL" (trade name)).
Thereafter, slide glass was placed on the mold release film to
press it, and this was irradiated with light for 20 seconds using
the dental light unit (manufactured by MORITA Corp., "JET LITE
3000" (trade name)). Thus, the composite resin was cured. Next, one
end face (circular section) of a stainless-steel cylindrical rod
with a diameter of 5 mm and a length of 1.5 cm was bonded to the
cured surface using the dental resin cement (manufactured by
Kuraray Medical Inc., "PANAVIA21" (trade name)). This was allowed
to stand still for 30 minutes and thus a test piece was obtained.
Five bonding test samples were produced in total.
[0239] (3) Bonding Evaluation Test
[0240] The tensile bond strengths of the above-mentioned bonding
test samples were measured with a universal testing machine
(manufactured by Shimadzu Corporation), with the crosshead speed
being set at 2 mm/min, and the average value thereof was taken as
tensile bond strength.
[0241] (4) Measurement of Bending Strength
[0242] Each composite resin compositions was charged into a
stainless steel mold (2 mm.times.2 mm.times.25 mm in size), pressed
from an upper side and a lower side via slide glass placed on each
of the sides, and irradiated with light from both of the sides by
using a dental technique light unit (manufactured by MORITA Corp.,
"ALPHA LIGHT II") for 2 minutes to be cured. Five cured products
were produced in each of the Examples and the Comparative Examples.
The cured products were taken out from the molds and kept in
37.degree. C. distilled water for 24 hours. Then, bending strengths
of the cured products were measured, using an Instron universal
testing machine, with the span being set at 20 mm and the crosshead
speed being set at 1 mm/min. The average of the measured values on
these specimens was calculated and taken as bending strength.
[0243] Tables 5 and 6 show the evaluation results. These tables
reveal that the dental composite resins using the polymerizable
composition containing the polymerizable monomer (A) of the present
invention have excellent adhesive properties to dentin and
excellent bending strength.
Example 4
Application of Polymerizable Composition Containing Polymerizable
Monomer (A) to Dental Self-Adhesive Cement
[0244] (1) Production of Dental Self-Adhesive Cements Using a
Polymerizable Composition Containing the Polymerizable Monomer
(A)
[0245] The components shown in Table 7 were mixed together at
ordinary temperature and thereby a paste A and a paste B were
prepared. Subsequently, these were mixed to prepare cement
compositions that are dental compositions. The bond strengths of
the cement compositions with respect to bovine dentin were
measured.
TABLE-US-00007 TABLE 7 Dental Self-Adhesive Cement Compositions and
Bonding Evaluation Results C. C. Example Example Example Example
Example Example Example Example Components 4-1 4-2 4-3 4-4 4-5 4-6
4-1 4-2 A Polymerizable monomer (A) EDMA 20 -- -- -- 20 20 -- --
MDMA -- 20 -- -- -- -- -- -- XDMA -- -- 20 -- -- -- -- -- SDMA --
-- -- 20 -- -- -- -- Polymerizable monomer for GDMA -- -- -- -- --
-- 20 -- comparison with (A) Polymerizable monomer (B) HEMA 50 50
50 50 50 50 50 70 having one polymerizable group and at least one
hydroxyl group Polymerizable monomer (C) MDP 30 30 30 30 30 30 30
30 having acidic group Polymerization initiator (F) THP 5 5 5 5 --
-- 5 5 CHP -- -- -- -- 5 -- -- -- BPO -- -- -- -- -- 2 -- -- Filler
(H) Inorganic filler 3 140 140 140 140 140 140 140 140 Inorganic
filler 4 45 45 45 45 45 45 45 45 Stabilizer BHT 0.2 0.2 0.2 0.2 0.2
0.2 0.2 0.2 B Polymerizable monomer (B) HEMA 50 50 50 50 50 50 50
50 having one polymerizable group and at least one hydroxyl group
Crosslinkable polymerizable D-2.6E 50 50 50 50 50 50 50 50 monomer
(D) Polymerization accelerator PTU 1 1 1 1 1 -- 1 1 (G) DEPT -- --
-- -- -- 0.4 -- -- TPBSS -- -- -- -- -- 1 -- -- Filler (H)
Inorganic filler 3 140 140 140 140 140 140 140 140 Inorganic filler
4 45 45 45 45 45 45 45 45 Stabilizer BHT 0.05 0.05 0.05 0.05 0.05
0.05 0.05 0.05 Bond strength with respect After 24 hours 5.4 7.5
4.9 4.6 5 6.5 1.4 4 to dentin (MPa) After thermal 5.3 7.1 4.5 4.4
4.5 6 1.2 1.5 cycles load THP: 1,1,3,3-tetramethylbutyl
hydroperoxide CHP: cumene hydroperoxide BPO: benzoyl peroxide BHT:
dibutylhydroxytoluene (4-methyl-2,6-di-tert-butylphenol) D-2.6E:
2,2-bis(4-methacryloyloxypolyethoxyphenyl)propane PTU:
1-(2-pyridyl)-2-thiourea DEPT: N,N-diethanol-p-toluidine TPBSS:
sodium 2,4,6-triisopropylbenzenesulfinate (The amounts of
respective components added each are indicated in the unit of parts
by mass, and the other abbreviations have the same meanings as
described above.)
[0246] (2) Method for Evaluating Bonding to Bovine Dentin
[0247] The labial surface of a bovine mandibular incisor was ground
with #80 silicon carbide paper (manufactured by Nihon Kenshi Co.,
Ltd.) under running water, and thereby a sample with an exposed
flat surface of dentin was obtained. The sample thus obtained
further was ground with #1000 silicon carbide paper (manufactured
by Nihon Kenshi Co., Ltd.) under running water. After completion of
grinding, water on the surface was air-blown to be dried. An
adhesive tape with a thickness of about 150 .mu.m having a circular
hole whose diameter was 3 mm was attached to the smooth surface
that had been dried and thereby the adhesive area was defined.
[0248] A cement composition obtained by mixing the paste A and the
paste B that had been produced as described above at a mass ratio
of 1:1 was applied in a mound form onto one end face (circular
section) of a stainless-steel cylindrical rod (with a diameter of 7
mm and a length of 2.5 cm). The end face on which the mound of
cement composition was made was placed on the circular hole to
press it so that the center of the stainless-steel cylindrical rod
coincided with the center of the circular hole. Thus, the
stainless-steel cylindrical rod was set vertically to the tooth
surface.
[0249] After setting the stainless-steel cylindrical rod, excess
cement composition flowing out around the rod was removed with an
instrument, and this sample was allowed to stand still at room
temperature for 30 minutes and was then immersed in distilled
water. Ten bonding test samples were produced in total, and all the
samples that had been immersed in distilled water were allowed to
stand still for 24 hours inside a thermostat whose temperature was
maintained at 37.degree. C. With respect to five samples out of the
ten samples, in order to evaluate the bond strength in the early
bonding stage, the bond strength was measured immediately after
they were allowed to stand still for 24 hours. With respect to the
other five samples, in order to evaluate bond durability, bond
strength was measured after 4000 thermal cycles had been performed,
with one cycle being a process for further immersing each sample in
4.degree. C. cold water and 60.degree. C. warm water alternately
for one minute.
[0250] (3) Bonding Evaluation Test (Evaluation of Bond Strength and
Bond Durability)
[0251] The tensile bond strengths of the above-mentioned five
bonding test samples were measured by using a universal testing
machine (manufactured by Shimadzu Corporation), with the crosshead
speed being set at 2 mm/min, and the average value thereof was
taken as tensile bond strength.
[0252] Table 7 shows the results. Table 7 reveals that the dental
self-adhesive cements using the polymerizable composition
containing the polymerizable monomer (A) of the present invention
have excellent initial bond strength and bond durability with
respect to dentin.
Example 5
Application of Polymerizable Composition Containing Polymerizable
Monomer (A) to Dental Resin-Reinforced Glass Ionomer Cement
[0253] (1) Production of Dental Resin-Reinforced Glass Ionomer
Cements Using a Polymerizable Composition Containing the
Polymerizable Monomer (A)
Example 5-1, Comparative Examples 5-1 to 5-2
[0254] The respective components indicated in Table 8 were mixed
together at ordinary temperature and thereby a liquid material was
prepared. 2.5 parts by mass of DEPT and 1.5 parts by mass of BSS
were added to a mixed solvent containing 80 parts by mass of
toluene and 20 parts by mass of methanol, and the resultant mixture
was stirred for 10 minutes. Then, 500 parts by mass of
fluoroaluminosilicate powder (manufactured by SCHOTT, Product Code
"G018-117") (hereinafter also referred to as FAS glass) was added
thereto, and the resultant mixture was stirred for 10 minutes.
After the solvent was distilled off under reduced pressure, the
resultant mixture was dried. Thereafter, it was subjected to
sieving with a mesh (#150) and thereby a powder material was
prepared. Next, a dental resin-reinforced glass ionomer cement was
prepared by mixing these liquid material and powder material at a
weight ratio of 1:3. The bond strengths of the cements with respect
to bovine dentin were measured as in Example 4. Table 8 shows the
results.
TABLE-US-00008 TABLE 8 Powder-Liquid-Type Resin-Reinforced Glass
Ionomer Cement Compositions and Bonding Evaluation Results C.
Example C. Example Example Components 5-1 5-1 5-2 Polymerizable
monomer (A) EDMA 30 -- -- Polymerizable monomer for GDMA -- -- 30
comparison with (A) Polymerizable monomer (B) HEMA 35 65 35 having
one polymerizable group and at least one hydroxyl group Solvent (E)
Water 20 20 20 Polymerization initiator (F) BPO 3 3 3 Polyalkenoic
acid Polyacrylic acid 35 35 35 Stabilizer BHT 0.05 0.05 0.05 Bond
strength with respect to After 24 hours 4.6 3.9 1.4 dentin (MPa)
After thermal 4.0 0.5 0.9 cycles load (The amounts of respective
components added each are indicated in the unit of parts by mass,
and the respective abbreviations have the same meanings as
described above.)
Examples 5-2 to 5-6, Comparative Examples 5-3
[0255] The respective components indicated in Table 9 were mixed
together at ordinary temperature and thereby a paste A and a paste
B were prepared. Subsequently, these were mixed to prepare dental
resin-reinforced glass ionomer cements. The bond strengths of the
cements with respect to bovine dentin were measured as in Example
4. Table 9 shows the results.
TABLE-US-00009 TABLE 9 Two-Paste-Type Resin-Reinforced Glass
Ionomer Cement Compositions and Bonding Evaluation Results C.
Example Example Example Example Example Example Example Example
Components 5-2 5-3 5-4 5-5 5-6 5-7 5-8 5-3 A Polymerizable monomer
(B) HEMA 35 50 50 50 50 50 50 50 having one polymerizable group and
at least one hydroxyl group Polymerizable monomer (C) MDP 25 -- --
-- -- -- -- -- having acidic group Polymerization initiator (F) BPO
2 2 2 2 2 2 -- 2 THP -- -- -- -- -- -- 5 Filler (H) Inorganic
filler 3 220 220 220 220 220 220 220 220 Inorganic filler 1 15 15
15 15 15 15 15 15 Stabilizer BHT 0.05 0.05 0.05 0.05 0.05 0.05 0.05
0.05 Polyalkenoic acid polyacrylic acid 40 50 50 50 50 50 50 50 B
Polymerizable monomer (A) EDMA 40 40 -- -- -- 40 40 -- XDMA -- --
40 -- -- -- -- -- SDMA -- -- -- 40 -- -- -- -- MDMA -- -- -- -- 40
-- -- -- Polymerizable monomer for GDMA -- -- -- -- -- -- -- 40
comparison with (A) Polymerizable monomer (B) HEMA 40 40 40 40 40
40 40 40 having one polymerizable group and at least one hydroxyl
group Crosslinkable polymerizable Bis-GMA 20 20 20 20 20 20 20 20
monomer (D) Solvent (E) Water 20 -- -- -- -- 20 -- --
Polymerization accelerator DEPT 0.5 0.5 0.5 0.5 0.5 0.5 -- 0.5 (G)
TPBSS 0.5 0.5 0.5 0.5 0.5 0.5 -- 0.5 PTU -- -- -- -- -- -- 1 --
Filler (H) FAS glass 220 220 220 220 220 220 220 220 Inorganic
filler 1 15 15 15 15 15 15 15 15 Stabilizer BHT 0.05 0.05 0.05 0.05
0.05 0.05 0.05 0.05 Bond strength with respect to dentin (MPa) 5.5
4.4 4.1 3.9 4.2 4.6 4.5 1.7 (The amounts of respective components
added each are indicated in the unit of parts by mass, and the
respective abbreviations have the same meanings as described
above.)
[0256] Tables 8 and 9 reveal that the dental resin-reinforced glass
ionomer cements using the polymerizable composition containing the
polymerizable monomer (A) of the present invention have excellent
initial bond strength and bond durability with respect to
dentin.
INDUSTRIAL APPLICABILITY
[0257] The polymerizable monomer (A) of the present invention has a
plurality of polymerizable groups and is hydrophilic. Thus, the
polymerizable monomer (A) of the present invention is useful for
applications that require the polymerizable monomer (A) to be
curable and applications that require a polymer of the
polymerizable monomer (A) to be hydrophilic. Polymerizable
compositions containing the polymerizable monomer can be used for
various applications including dental applications. Particularly,
the compositions are suitable for dental materials, such as
primers, bonding materials, cements, and composite resins.
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