JPH03232810A - Photopolymerizable dental composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable dental composition, composed of a specific organic composite filler, specified monomer mixture and specific photopolymerization initiator, readily polymerizable and curable by irradiation with visible light and excellent in mechanical strength and water resistance and good in abrasion resistance and aesthetic properties. CONSTITUTION:The aforementioned composition, composed of (A) an organic composite filler prepared by polymerizing a monomer expressed by formula I (R1 is H, halogen, etc.; R2 is formula II, etc.; (m) is an integer of 1-20; X is alkali metal, etc.) and a radically polymerizable vinyl monomer in a polymerization system containing an inorganic compound dispersed therein, (B) a mixture of 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane with a tri- or polyfunctional (meth)acrylic acid ester compound and a diluting ethylenic vinyl monomer and (C) a photopolymerization initiator containing a compound expressed by formula III (R6 and R7 are lower alkoxy, etc.; R8 is 2-18C alkyl, etc.), a reducing agent and a compound expressed by formula IV (R9 is H, halogen, etc.; R10 is phenylene; R11 is 1-10C alkyl, etc.) and useful as a dental crown reparative material, etc.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a dental filling composition such as a dental crown restoration material containing a high proportion of an organic composite filler as an inorganic substance. A photopolymerizable dental composition that can be easily polymerized and cured by irradiation with visible light using an agent system, and has high mechanical properties and excellent water resistance, as well as high wear resistance and good aesthetics. relating to things.

[Prior art] In dental filling compositions, mechanical strength, wear resistance,
It is important to have both physical properties such as water resistance and adhesiveness, and aesthetic properties such as transparency and abrasiveness to more closely resemble natural teeth, and the purpose of this material is to improve these properties as an amalgam alternative material. Many attempts have been made to develop so-called composite resins in which inorganic fillers are blended with resins.

In addition, for caries of more than one cavity, a composition material called a composite inlay is used, and higher mechanical strength and wear resistance are desired.

The main components of this composite resin and composite inlay are: (1) an inorganic filler, (2) an olefinic unsaturated compound, and (2) a polymerization initiator.

However, when an olefinically unsaturated compound is simply polymerized in the presence of an inorganic filler, the interfacial affinity such as compatibility and adhesiveness between the inorganic filler and the organic resin obtained by polymerization is poor, resulting in insufficient composite performance. I can't get it. Therefore, in order to improve this point, dental materials have been proposed in which the glass surface is blended with a filler treated with a silane coupling agent. It has the major drawback of being limited to glassy fillers having a surface of Therefore, when applied to dental compositions, quartz-based fillers, which are commonly used as fillers that provide high hardness and esthetics, are difficult to develop interfacial reinforcement properties, and furthermore, they are difficult to achieve in long-term clinical use in a moist oral cavity. On the other hand, due to poor water resistance, mechanical strength decreases over time.
It has clinical problems such as changes in color tone.

In addition, various studies have been conducted on the monomers constituting the organic resin, and for example, bisphenol A diglycidyl dimethacrylate (hereinafter abbreviated as Bis-GMA) is a representative example that provides a composite with a small polymerization shrinkage rate. The bisphenol A-based polyfunctional monomer is a hydrophobic monomer 2, which provides excellent water resistance.
Monomers such as 2-bis[4-(methacryloyloxyethoxy)phenyl]propane (hereinafter abbreviated as Bis-MEPP) have been found. However, Bis
-GMA has a hydroxyl group in its molecule, so the resulting cured product has a high water absorption rate and poor water resistance; on the other hand, Bis
- When using MEPP, there are problems in that the curability is low, sufficient crosslink density cannot be obtained, and mechanical strength is poor. Furthermore, in order to compensate for these drawbacks, for example, simply Bi
Even if s-GMA and Bis-MEPP are used together, a composite resin with excellent properties cannot be obtained.

Regarding photopolymerization initiators, various methods of polymerization and curing using visible light have been attempted; for example, a combination of an α-diketone compound and a reducing agent, particularly a combination of camphorquinone and an amine, is the most commonly used. However, the photosensitive area is 50
Since the light energy in the visible light region cannot be effectively utilized because it is limited to around 0 nm, polymerization is insufficient and wear resistance is reduced. In addition, α-
The diketone compound causes yellowing of the composition, impairing its aesthetics as a dental composition.

[Problems to be Solved by the Invention] An object of the present invention is to provide a photopolymerizable dental composition that has excellent mechanical strength and water resistance, as well as good wear resistance and aesthetics. .

[Means to solve the problem] The gist of the present invention is (A) - Formula (I) R.

... (I) R2 [; = [; R2SO3X [wherein, R1
is H, halogen atom, alkyl group having 1 to 20 carbon atoms, phenyl group, and their story 3 Conductor, R2 is -CONH-CONH-CRs-4 COO-(CH2) l1l- or -(CH2)n-
(In the formula, R3 and R4 are H or an alkyl group having 1 to 15 carbon atoms, R5 is an alkylene group having 1 to 15 carbon atoms, and m is 1 to
An integer of 20, n represents an integer of 0 to 2o. ), X represents H, NH4 or an alkali metal atom.

) An organic composite filler obtained by polymerizing at least one sulfonic acid monomer represented by the following formula and at least one radically polymerizable vinyl monomer in a polymerization system in which an inorganic compound is dispersed.

(B) A monomer consisting of 2.2-bis[4-(methacryloxyethoxy)phenyl]propane, at least one trifunctional or more functional (meth)acrylic acid ester compound, and an ethylenic vinyl monomer for dilution and a photopolymerizable dental composition comprising a photopolymerization initiator which is a mixture of an acylphosphine oxyto compound represented by fc + - formula [TI], a reducing agent, and a ketal compound represented by general formula [111]. be.

- Formula [11] % Formula % E In the formula, 16 is a lower alkyl group, a lower alkoxy group, or a phenyl group optionally substituted with a lower alkyl group, and R7 is a lower alkoxy group, or a phenyl group optionally substituted with a lower alkyl group. Good phenyl group, R8 is a linear or branched alkyl group having 2 to 18 carbon atoms, optionally substituted by an acetyl group, 3 to 12
a cycloalkyl group having 5 carbon atoms, or an aryl group optionally substituted by a lower alkyl group, a lower alkoxy group or a halogen atom, or a cycloalkyl group having the following formula % (R6 and R7 have the above meanings, means p-phenylene group)] Formula [III
]0R1゜[In the formula, R9 is ■, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, RIO is a phenylene group, and R11 is an alkyl group having 1 to 10 carbon atoms, a carbon number 7-9 aralkyl group or formula -((c++2)X
oL-R+2 (where x and y are integers from 1 to 5,
RI2 represents a group represented by (representing an alkyl group having 1 to 5 carbon atoms). [8] The organic composite filler (8) constituting the composition of the wood invention is a polymerization system in which an inorganic compound is dispersed, in which a sulfonic acid monomer and one or more other polymerizable vinyl monomers are added without a catalyst. It can be obtained by polymerization, and the manufacturing method is not particularly limited.

An example of a preferred production method is to suspend and disperse a vinyl monomer and an inorganic compound in an aqueous medium at a temperature that does not cause a thermal polymerization reaction, and then add sulfonic acid to the inorganic compound.
A method can be mentioned in which an aqueous heterogeneous polymerization reaction is caused by adding and stirring the mixture, and the polymerization is carried out for a predetermined period of time.

The specific sulfonic acid monomer represented by the above general formula (I) used for forming the organic composite filler (8) is a monomer that exhibits polymerization activity. As an active side, it is essential to have a double bond that has a sulfonic acid group and exhibits strong bonding between the produced polymer and the inorganic compound.
Any compound having a structural formula containing these functional groups can be applied, and specific examples include 2-acrylamido-2-methylpropanesulfonic acid, sodium 2-methacryloyloxyethanesulfonate, sodium 3-methacryloyloxypropanesulfonate, -Sodium methacryloyloxypropane sulfonate, sodium 2-methyl-2-methacryloyloxypropane sulfonate, etc., but especially 2-acrylamide-2-
Methylpropanesulfonic acid, sodium 2-methacryloyloxyethanesulfonate, and sodium 1.3-methacryloyloxypropanesulfonate are preferred because they have high polymerization activity.

In addition, the inorganic compounds used in the production of the organic composite filler (A) include those listed in Periodic Rule 1. TI, m, IV.

2) Group metals, transition metals, and their oxides, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates, and mixtures and complex salts of these metals, among which sulfuric acid Barium, barium fluoride, silicon dioxide, aluminum oxide, titanium oxide, quartz powder, glass powder, glass beads, glass fibers, glass fillers containing barium salts, lead salts or strontium salts, silica gel,
Zirconium oxide and tin oxide are preferred because they have a particularly remarkable effect of activating the vinyl monomer and strongly integrating it with the polymer. One of the major features of the present invention is that it can be applied to inorganic compounds for which ordinary coupling treatment is not effective, and the shape and size of the inorganic compound can also be selected as appropriate.

Furthermore, as the vinyl monomer used in the production of the organic composite filler (A), any ordinary radically polymerized vinyl monomer can be used, and specific examples include methyl methacrylate, acrylic acid, etc. (meth)acrylic acid alkyl esters such as butyl, aromatic 3-vinyl monomers such as styrene and α-methylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and as described below, Examples include monomers used as the ethylenic vinyl monomer mixture (B) in the present invention, and can be arbitrarily selected depending on the purpose.

The concentration of the sulfonic acid monomer when obtaining the organic composite filler (A) is about 0.05 to 100% by weight, preferably 0.1 to 5% by weight, based on the total weight of the inorganic compound and vinyl monomer.
It is used in amounts of 0% by weight, particularly preferably from 0.5 to 30% by weight. In most cases, it is preferred to increase the amount of sulfonic acid monomer as the vinyl monomer content increases. The weight ratio of vinyl monomers or mixtures thereof to inorganic compounds used can vary within a wide range and is from about 500:1 to 1:5, preferably from about 50:1 to 1:1. In addition, when polymerizing in an aqueous medium, the amount of water is approximately 1% based on the total weight of the inorganic compound and vinyl monomer.
It is from 100 times to several hundred times, preferably from about 10% to 10 times. The reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen 4 at a temperature of about 10 to 1
It is carried out at 00°C, preferably 20 to 80°C, but depending on the inorganic compound, it may be carried out in an oxygen-containing atmosphere. The specific reaction temperature here is selected as appropriate depending on the vinyl monomer used, but it is important to conduct the reaction at a temperature at which thermal polymerization is suppressed to a negligible degree. When carried out in this manner, the integrity and uniformity of the resulting composite filler is inhibited. Reaction time is 3
0 minutes to about 200 hours. Generated organic composite filler (
A) is about 10-300°C, preferably about 50-200°C
Can be dried in a temperature range of Note that the interaction between the surface of the inorganic compound particles and the polymer applied by the method of the present invention goes beyond simple adsorption or adhesion in the physical sense due to van der Waalska et al. This is clear from the fact that a large amount of unextracted polymer is observed even after extraction with a good solvent for vinyl polymer.

The above-mentioned organic composite filler (A) has high compatibility with the inorganic compounds and organic polymers in the composite resin because various mineralized compounds and organic polymers are strongly combined. Therefore, by arbitrarily selecting inorganic compounds necessary for the dental composition depending on the purpose, it is possible to obtain the dental composition targeted by the present invention.

The ethylenic vinyl monomer mixture (B
) contains Bis-MEPP and trifunctional or higher functional (meta)
It is necessary to contain at least one kind of acrylic ester compound.

By combining the above two types of monomers, surprisingly, when the composition of the present invention is cured, a composite resin with high crosslinking density, excellent mechanical strength, and good water resistance can be obtained. can.

The trifunctional or more functional (meth)acrylic acid ester compound may have any structure, for example, the following formulas (IV), (V), (Vl), [■], [■], ( IX
) is used.

6 (wherein, m is an integer of 1 to 10, n is an integer of 0 to 2, and R3 represents H or a methyl group), and may be the same or different. Well, R2 is ■
, represents an alkyl group having 1 to 3 carbon atoms or a hydroxymethyl group. ] 1 (In the formula, x and y are integers of 1 to 10, 2 is 0 or 1, and R3 represents H or a methyl group.) ] C1120-R,.

1 CH2 C-CH20-R,°“ (VI) CH20-Rloo.

R3 CH2 (In the formula, m is an integer of 1 to 10, n is an integer of 0 to 2, and R3 represents ■ or a methyl group.) Even if they are the same, different groups can be used. Good too. ] R, R4'' R3 (in the formula, R3 represents H or a methyl group) may be the same or different, and R5 is an alkylene group having 1 to 20 carbon atoms, a phenylene group, or Indicates a phenylene group optionally substituted with a lower alkyl group or a lower alkoxy group.] 8 R4R.

R4'-C-CH20CL-C-Rso
... [■] R4” R6” [In the formula, R4, R4°, R4”, R6+R6”, R
6” is -0H2-0-C-C=CH2 (in the formula, R3 is H
Or it represents a methyl group 1 R3. ) may be the same or different, but R6'' may be a hydroxyethyl group.] (In the formula, S is an integer from 1 to 10, and R3, 83゛ is 9 11 or a methyl group.] In the present invention, in consideration of curability and mechanical strength, the monomer represented by the formula (TV) is trimethylolmethanetri(meth). ) acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolbutane tri(
meth)acrylate, tri[(hydroxymethoxy)methylcomethanetri(meth)acrylate, tri[(hydroxyethoxy)methylcomethanetri(meth)acrylate, tri[(hydroxypropoxy)methylcomethanetri(meth)acrylate, tri ([(hydroxyethoxy)ethoxycomethyl)methanetri(meth)acrylate, tri([(hydroxypropoxy)propoxycomethyl)methanetri(meth)acrylate, pentaerythritoltri(meth)acrylate, among others, trimethylolmethanetri(meth)acrylate, etc. (meth)acrylate,
More preferred are trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

For the same reason, the monomer represented by formula (V) includes ethyl isocyanurate tri(meth)acrylate,
Examples include propyl isocyanurate tri(meth)acrylate, butyl isocyanurate tri(meth)acrylate, pentyl incyanurate tri(meth)acrylate, hexyl isocyanurate tri(meth)acrylate, (hexylketo)ethyl isocyanurate tri(meth)acrylate, etc. Ethyl incyanurate tri(meth)acrylate and the like are more preferred, and as the monomer represented by formula (Vl), pentaerythritol tetra(meth)acrylate and the like are more preferred.

For the same reason, in the monomer represented by formula [■], R5 is a methylene group, an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a 1,4-tolylene group. , 1 CH2C(C113)2CH2CH(CH3) C11
Examples include tetrafunctional urethane (meth)acrylates, which are groups represented by z-CH2-, -φ-C■2-φ- (in the formula, φ represents a phenylene group), and among others, R5 is a hexamethylene group or -CL-C(CH
3) 2c82cH(CL) Tetrafunctional urethane (meth)acrylate, which is a group represented by CH2CH2-, is more preferable, and the monomer represented by the formula [■] is,
dipentaerythritol penta(meth)acrylate,
Pentaerythritol hexa(meth)acrylate and the like are more preferred, and as the monomer represented by formula (IX), hexafunctional urethane (meth)acrylate in which S is 6 is more preferred.

In the present invention, as the diluting ethylenic vinyl monomer used in the vinyl monomer mixture (B), conventionally known monomers used in dental composite resins can be used, and specific examples include: , alkanediol di(meth)acrylates such as propylene glycol dimethacrylate, 1,6-hexamethylene glycol dimethacrylate, triethylene glycol dimethacrylate (
(hereinafter abbreviated as 3G), polyalkylene glycol di(meth)acrylate such as tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate
Examples include (meth)acrylic acid alkyl esters such as acrylate, glycidyl (meth)acrylate, methyl methacrylate, and butyl acrylate, aromatic hydrocarbons such as styrene and α-methylstyrene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. It will be done. In addition, in the present invention, organic composite filler (A)
The radically polymerizable vinyl monomer and monomer mixture (B) used may be the same.

In the present invention, Bis in the monomer mixture (B)
-MEPP, the trifunctional or higher functional (meth)acrylic acid ester compound, and the diluent ethylenic monomer are not particularly limited. The composition of the invention has a viscosity of 1000 to 50
It is preferable to mix it to 30,000 poise (25°C). Usually, the amount of Bis-MEPP and trifunctional or higher functional (meth)acrylic acid ester compound in the monomer mixture (B) varies greatly depending on the type of trifunctional or higher functional (meth)acrylic acid ester compound. Although it cannot be generalized, 20 to 90% by weight of each
, about 5 to 70% by weight. In addition, from the point of view of water resistance and mechanical strength, Bis-MEPP and trifunctional or higher functional (
Blending ratio (weight ratio) with meth)acrylic acid ester compound
Generally, the ratio is preferably about 1:0.1 to 1:1.

The amount of the organic composite filler (A) and monomer mixture (B) can be arbitrarily selected depending on the type of inorganic compound and monomer mixture (B) used in the filler (A), the purpose of use, etc. However, usually an organic composite filler (^) 20~
90 parts by weight, and the monomer mixture (B) is used in a range of 10 to 80 parts by weight.

Since the photopolymerization initiator (C) used in the present invention is for dental use, one that polymerizes with visible light with a wavelength of 400 to 800 nm is used, excluding the near ultraviolet region, in consideration of its toxicity in the oral cavity. , also clinically, 30
It is desired that it harden in about seconds. Furthermore, in recent years, the aesthetics of dental compositions has become more important, and α-diketone compounds such as camphorquinone, which are commonly used as photopolymerization initiators, are undesirable because they cause yellowing. From the above points, the preferred photopolymerization initiator (C) is an acylphosphine oxyto compound represented by the general formula (II), dimethylaminoethyl methacrylate, 4-(
N,N-dimethylamino)benzoic acid alkyl ester,
Using a reducing agent such as p-methoxybenzaldehyde, and further utilizing light energy of 500 nm or less, polymerization and curing are promoted, and in order to particularly develop wear resistance, a ketal compound represented by the above general formula (m) is used in combination. It is characterized by

The acylphosphine oxyto compound used in the present invention is represented by the following general formula (n).

General formula (II) 5 [In the formula, R6 is a lower alkyl group, a lower alkoxy group, or a phenyl group which may be substituted with a lower alkyl group, and R7 is a lower alkoxy group, or a phenyl group which may be substituted with a lower alkyl group. Phenyl group, R8 is a linear or branched alkyl group having 2 to 18 carbon atoms, which may be substituted with an acetyloxy group, 3 to 1
A cycloalkyl group having 2 carbon atoms, or an aryl group optionally substituted by a lower alkyl group, a lower alkoxy group or a halogen atom, or a cycloalkyl group having the following formula % (R8 and R7 have the above meanings, [X means a p-phenylene group]] 6 The object of the present invention is particularly a phenyl group in which R8 in the formula - above is at least di-substituted, and at least adjacent to the bonding position with the carbonyl group. have substituents A and B, which may be the same or different, on two carbon atoms, and A and B
is a lower alkyl group, a lower alkoxy group or a halogen atom, preferably a chlorine atom or a bromine atom, or an α-naphthyl group in which R1□ is substituted by A and B in at least the 2.8-position, or at least one
．． It is an acylphosphine oxyto compound which is a β-naphthyl group substituted by A and B at the 3-position.

Formula (II) of the acylphosphine oxyto compound of the present invention
) will be explained in detail below.

R6 is a linear or branched lower alkoxy group such as a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an n-butyl group, a lower alkoxy group such as a methoxy group, an ethoxy group, an inpropoxy group, a butoxy group, or Ethyloxyethoxy group, aryl group such as phenyl group, naphthyl group, halogen-substituted aryl group such as chino- or dichlorophenyl group, alkyl-substituted phenyl group such as methylphenyl group, ethylphenyl group, isopropylphenyl group, tertiary butylphenyl group , dimethylphenyl group.

R7 may be the same as R6 except for the lower alkyl group.

Examples of R8 are as follows. Ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, tertiary butyl group, isoamyl group, n-hexyl group, heptyl group, n-octyl group, 2-ethylhexyl group, isononyl group, dimethyl group Butyl group, lauryl group, stearyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclobentyl group, cyclohexyl group,
■-Methylcyclohexyl group, norbornagenyl group,
adamantyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, tertiary butylphenyl group, isobutyryl phenyl group, methoxyphenyl group, dimethoxyphenyl group,
Impropoxyphenyl group, α- and β-naphthyl group, β-acetoxyethyl group, particularly preferably 2,6-dimethylphenyl group, 2,6-dimethoxyphenyl group, 2
．． 6-dichlorophenyl group, 2.6-dibromphenyl group, 2-chloro-6-methoxyphenyl group, 2.4.6
-trimethylphenyl group, 2.4.6-)-dimethoxyphenyl group, 2.3.4.6-titramethylphenyl group, 2.6-dimethyl-4-tertiary methylphenyl group, 1.
2 groups of 3-dimethylnaphthalene, 1 group of 2,8-dimethylnaphthalene, 2 groups of 1,3-dimethoxy-naphthalene, 2 groups of 1,3-dichloronaphthalene, and 1 group of 2,8-dimethoxynaphthalene.

R6 and R7 can additionally contain a C--C double bond which makes it possible to polymerize the photoinitiator into the binder.

Examples of acylphosphine oxyto compounds of the present invention are as follows. Isobutyryl-phenylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-)-rui phenylphosphinic acid methyl ester, 0-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphinic acid methyl ester, p-tertiary butylbenzoyl-phenylphosphinic acid isopropyl ester, pivaloyl-(4-methylphenyl )-phosphinic acid methyl ester, pivaloyl-phenylphosphinic acid vinyl ester, acryloyl-phenylphosphinic acid methyl ester, isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-1-cyclohexanoyl-diphenylphosphine oxide, 2-Ethylhexanoyl-diphenylphosphine oxide, p-tolyl-diphenylphosphine oxide, o-toluyl-diphenylphosphine oxide, p-tertiary butylbenzoyl-diphenylphosphine oxide, acryloyldiphenylphosphine oxide, benzoyl-diphenylphosphine oxide Oxide, 2.2
-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, and especially 2,6-dimethylbenzoylphenylphosphine acid methyl ester, 2,6-cymethoxybenzo Iluphenylphosphinic acid methyl ester, 2.
6-dimethylbenzoyl diphenylphosphine oxide, 2.6-simethoxybenzoyl diphenylphosphine oxide, 2.4.6-trimethylbenzoyl diphenylphosphine methyl ester, 2.4.6-1-
Limethylbenzoyl-diphenylphosphine oxide,
2.3.6- Trimethylbenzoyl-diphenylphosphine oxide, 2.4.6- Trimethylbenzoyl-tolylphosphinic acid methyl ester, 2,4.6-
trimethoxybenzoyl-diphenylphosphine oxide, 2.6-1 dichlorobenzoyl-phenylphosphine acid ethyl ester, 2.6-dichlorobenzoyl-diphenylphosphine oxide, 2.3.4.6-titramethylbenzoyl-dif enylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 1.3-
Dimethylnaphthalene-2-carbonyl-diphenylphosphine oxyto, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxyto, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxyto, 1,3-dichlor Naphthalene-2carbonyl-diphenylphosphine oxyto.

Particularly good are aroyl-phenylphosphinic acid esters or aroyldiphenylphosphine oxytos whose aroyl group is substituted in each ○-position by an alkyl group, an alkoxy group, a halogen atom, or a combination thereof. The example is 2.6-
Dimethylbenzoyldiphenylphosphine oxide, 2
．． 4.6-trimethylbenzoyldiphenylphosphine oxy2-cyto, 2.4.6-1-limethylbenzoyl-phenyl-phosphinic acid methyl ester, 2.6-dichlorobenzoyl or 2,6-simethoxybenzoylcyphenyl It is phosphine oxide.

Among them, 2.4.6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as TMDPO) is most preferred.

In the composition of the present invention, 4-(
Using an alkyl ester of N,N-dimethylamino)benzoic acid having 5 to 1O carbon atoms, such as isoamyl 4-(N,N-dimethylamino)benzoate (hereinafter abbreviated as DABA), - represented by the formula [■1] Examples of ketal compounds include benzyl dimethyl ketal, benzyl diethyl ketal,
Benzyl di(2-methoxyethyl) ketal, 4.4°
A photopolymerization initiator in which any of -dimethylbenzyl dimethyl ketals is combined with an acylphosphine oxyto compound represented by the above-mentioned general formula [11] is preferred from the viewpoint of high curability.

The amount of the photopolymerization initiator to be added may be arbitrarily selected in consideration of the curability and storage stability of the composition, but usually, the amount of the acylphosphine oxyto compound relative to the monomer mixture (B) is 0. .1-15% by weight, preferably 0.05-15% by weight
5% by weight, more preferably 0.1 to 2% by weight, 0.05 to 10% by weight of the reducing agent, and 0.0% of the ketal compound.
It is used in a range of 2 to 15% by weight.

In the composition of the present invention, a filler may be added to the above-mentioned components as necessary to control viscosity adjustment, transparency, masking properties, etc. The filler components include periodic rule Z, n, m, group (3), transition metals and their oxides, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates, and Mixtures of these, composite salts, etc. may be mentioned, among which glass fillers containing silicon dioxide, quartz powder, aluminum oxide, barium sulfate, titanium oxide, talc, glass powder, glass peas, glass fibers, barium salts, lead salts, Silica gel, colloidal silica, carbon fiber, zirconium oxide,
Tin oxide 4 and other ceramic powders are preferred. The above-mentioned filler may be any of untreated filler, filler surface-treated with a silane coupling agent, etc., and filler coated with a polymer.

The amount of the filler blended can be changed as appropriate depending on the purpose of use of the photopolymerizable dental composition, but is usually 0.1 to 103% by weight, preferably 0. It is blended in a range of .5 to 102% by weight, particularly preferably 1 to 102% by weight, and used as a paste composition.

Furthermore, the composition of the present invention may optionally contain colorants, polymerization inhibitors (e.g., hydroquinone, methoxybenzophenone, methylphenol, hydroquine monomethyl ether, etc.), oxidation stabilizers, ultraviolet absorbers (e.g., benzophenone, etc.). ), pigments (for example, iron oxide, titanium oxide, etc.), dyes, etc. can also be blended.

[Example] Next, the present invention will be explained in detail using Examples 5. However, the present invention is not limited to the following examples.

In addition, in the examples, parts indicate parts by weight.

Moreover, physical property evaluation in this example was performed according to the following method.

・Various photopolymerizable dental compositions prepared using the Tagusu Tougai composition were filled into a stainless steel mold with an inner diameter of 4 mm and a height of 6 mm, and cover glasses with a thickness of approximately 0.1 mm were adhered to both the top and bottom surfaces. After that, a visible light irradiator (manufactured by 3M, “0ptilux”)
), the distance between the cover glass and the irradiator was set to 1 mm, and irradiation was performed from both the top and bottom for 30 seconds each, and then evaluated. Strength measurement was performed using Tensilon (Shimadzu IS-500
) at a crosshead speed of 1.0 mm/min.

・The compressive strength after storing the same cured product in water at 37° C. for one month was evaluated as the water resistance strength by comparing it with the previous compressive strength.

6. After storing a cured product obtained in the same manner in water at 37°C for one week using a stainless steel mold with an inner diameter of 20 mm and a height of 1 mm, the increase in weight per unit surface area of the cured product was determined. was measured and the water absorption rate was evaluated.

11 Weight loss per unit surface area of the cured product when a cured product obtained in the same manner was rubbed with a toothbrush 5,000 times using a stainless steel mold with a wear surface of 10 mm x 30 mm and a thickness of 3 mm. The amount of wear was evaluated by measuring the amount of wear.

Example 1 90 g of a mixed organic composite filler obtained by the manufacturing method shown below was mixed with 10 g of hydrophobized amorphous silica (Aerosil R-972, manufactured by Degussa). Mixture (B) is 18 parts of 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane (hereinafter abbreviated as Bis-MEPP), and 7s=6, R3, R3° of the structural formula (IX) is 6 parts of isocyanuric acid skeleton hexafunctional urethane acrylate (manufactured by Shin Nakamura Chemical ■, hereinafter abbreviated as U-6HA), 6 parts of triethylene glycol dimethacrylate (hereinafter abbreviated as 3G) and further photopolymerization initiation. As the agent (C), 2,4.6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as TMDPO), isoamyl 4-(N,N-dimethylamino)benzoate (hereinafter abbreviated as DABA), and benzyldimethyl Ketal (hereinafter abbreviated as BDK) was added to the monomer mixture (B) at 0.4% by weight, 2.0% by weight, and 0.0% by weight, respectively.
After preparing a photopolymerizable composition containing 5% by weight, it was cured, and the obtained cured product was evaluated, and the results shown in Table 1 were obtained.

[Method for manufacturing organic composite filler]

Into four 500nl rosetable flasks equipped with a cooling tube, a nitrogen introduction tube, a stirring rod, and a thermocouple for internal temperature detection, add quartz fine powder (Tatsumori-2) as an inorganic compound with an average particle size of 1 to 2JLI+. 50 g of barium glass (7724, manufactured by Corning, pulverized to an average particle size of 1 to 2 scales) were suspended and dispersed in 300 nl of deionized water, and the mixture was purged with nitrogen for 30 minutes. Next, 3.0 g of methyl methacrylate as a vinyl monomer was added under nitrogen atmosphere with vigorous stirring. Next, the temperature of the suspension was raised to 70°C in a hot water bath, and after confirming that the added monomer was uniformly dispersed, 0.5 g of sodium 2-methacryloyloxyethanesulfonate was removed as a sulfonic acid monomer. A solution dissolved in 10 ml of ionized water was gradually added, and a polymerization reaction was carried out at the same temperature for 8 hours.

After the reaction was completed, the product was filtered under reduced pressure, thoroughly washed with deionized water, and then dried with hot air at 100'C to remove moisture, yielding about 100 g of an organic composite filler. This organic composite filler had a polymer content of 2.0% as measured by a calcination method, and a 50-hour Soxhlet extraction test using hot benzene as an extraction solvent revealed that the polymer content after the extraction process was 1.0%. 8%, it was found that the surface of the quartz fine powder and barium glass and most of the polymer composited by this method were extremely strongly integrated. In addition, even if 100 g of quartz fine powder and barium 9 glass were separately polymerized using the same recipe, each showed almost the same polymer content as the mixed system, so the two types of inorganic fillers in the above mixed system were It is thought that both are uniformly composited with polymers.

Comparative Examples 1 to 2 For comparison, instead of the organic composite filler according to the present invention, a mixed filler of 50 g of quartz fine powder and 50 g of barium glass was used as a silane coupling agent (KBM manufactured by Shin-Etsu Silicone).
-#503: Silanized filler 9 treated with 3% of 3-methacryloyloxypropyltrimethoxysilane
When using a silane-treated filler obtained by mixing and preparing 10 g of Aerosil R-972 with 0 g (Comparative Example 1)
, untreated quartz fine powder and barium glass, respectively.
In the case of using an untreated filler prepared by mixing 5 g of Aerosil R-972 LOg (Comparative Example 2), a photopolymerizable composition was prepared with the same composition as in Example 1, A similar evaluation was conducted.

0 As is clear from Table 1, the organic composite filler f of the present invention
The dental materials using A) (Example 1) were superior to those containing conventionally used silane-treated fillers (Comparative Example 1) or untreated fillers (Comparative Example 2). It can be seen that a cured product having good mechanical strength and water resistance can be obtained.

Furthermore, the organic composite filler fA) used in the present invention is
Since the wetting with the monomer mixture fBl was extremely good, compounding was easy, and the appearance of the prepared cured product was significantly better than that of the comparative example.

Table 1 ■ Example 2 Aluminum oxide powder (reagent special grade) as an inorganic compound
An aqueous heterogeneous polymerization reaction was carried out in the same manner as in Example 1, except that ong was used, and an organic composite filler was obtained. The polymer content of this organic composite filler was 1.6%, and the polymer content after extraction treatment was 1.5%. Organic composite filler 30 of aluminum oxide powder obtained by
Bis-MEPP as monomer mixture fB)
42 parts, IJ-fiHA 14 parts, 3 parts 14 parts, and further photopolymerization initiators (TMDPO, DABA, and BD as C1).
0.4% by weight of K in each case based on the monomer mixture fIl)
, 2.0% by weight, 0 parts by 5% by weight, a photopolymerizable composition was prepared and cured, and the physical properties of the obtained cured product were evaluated, and the results shown in Table 2 were obtained.

Comparative Examples 3 to 4 When a silane-treated filler in which aluminum oxide powder was treated with 3% of a silane coupling agent was used instead of the organic composite filler in Example 2 (Comparative Example 3), untreated aluminum oxide powder was In the case where 2 was used (Comparative Example 4), a photopolymerizable composition was prepared with the same formulation as in Example, and the same evaluations were conducted.

As is clear from Table 2, similar to the results in Table 1, the use of the dental composition of the present invention is superior to the use of conventional silane-treated filler a and untreated filler. It can be seen that it has certain characteristics.

Table 2 Examples 3 to 9, Comparative Examples 5 to 11 A dental composition was prepared using the monomer mixture (Bl composition) shown in Table 3 in the same manner as in Example 1 except for 6. The tumor properties of the obtained cured products were evaluated in the same manner as in 1.The obtained results are shown in Table 3.As is clear from Table 3, specific monomers were used as the monomer mixture CB+. It has been found that by using this method, a cured product for dental materials having excellent mechanical strength, abrasion resistance, and water resistance can be obtained.

4 45 Examples 1O to 19, Comparative Examples 12 to 18 The composition of the photopolymerization initiator (C) shown in Table 4 was used, and the monomer mixture fB) was mixed with 18 parts of Bis-MEPP and U-611A.
6 parts, 3G A dental composition was prepared in the same manner as in Example 1 or Comparative Example 1 except that the amount was changed to 6 parts, and the physical properties of the cured product were evaluated. The results obtained are shown in Table 4.

It can be seen that the addition of BDK dramatically improves the wear resistance compared to the conventional initiator system containing only camphorquinone and amine.

Further, by using the acylphosphine oxytate compound of the present invention in place of camphorquinone, a dental composition with excellent aesthetics and no yellowing of the cured product can be obtained.

[Effects of the Invention] As detailed above, the composition of the present invention not only has excellent mechanical strength and water resistance, but also has unprecedented performance in terms of abrasion resistance and aesthetics. Therefore, it can exhibit excellent effects when used not only as a dental crown restoration material such as a composite resin, but also as a dental composition such as a composite resin inlay or a resin for a hard tooth crown.

Claims (1)

[Claims] (1) (A) General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼…[I] [In the formula, R_1 is H, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, and Derivative, R_2 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, or ▲ There are mathematical formulas, chemical formulas, tables, etc. 1~
15 alkylene groups, m is an integer of 1 to 20, n is 0 to 2
Indicates an integer of 0. ), X is H, NH_4
Or indicates an alkali metal atom. ] An organic composite filler obtained by polymerizing at least one sulfonic acid monomer represented by the following and at least one radically polymerizable vinyl monomer in a polymerization system in which an inorganic compound is dispersed; (B) A monomer consisting of 2,2-bis[4-(methacryloyloxyethoxy)phenyl]propane, at least one trifunctional or more functional (meth)acrylic acid ester compound, and an ethylenic vinyl monomer for dilution and (C) a photopolymerizable dental composition comprising a photopolymerization initiator that is a mixture of an acylphosphine oxide compound represented by general formula [II], a reducing agent, and a ketal compound represented by general formula [III]. . General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼... [II] [In the formula, R_6 is a lower alkyl group, a lower alkoxy group, or a phenyl group that may be substituted with a lower alkyl group, and R_7 is a lower alkoxy group. , or a phenyl group optionally substituted with a lower alkyl group, R_8 is a linear or branched alkyl group having 2 to 18 carbon atoms optionally substituted with an acetyloxy group, 3
A cycloalkyl group having ~12 carbon atoms, or a lower alkyl group, a lower alkoxy group, or an aryl group optionally substituted with a halogen atom, or the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_6 and R_7 has the above-mentioned meaning, and X means a p-phenylene group)] General formula [III
] (In the formula, R_9 is H, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, R_1_
0 is a phenylene group, R_1_1 is an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 9 carbon atoms, or the formula -((C
H_2)_xO)_y-R_1_2 (where x and y are 1
R_1_2 represents an alkyl group having 1 to 5 carbon atoms. ]