JP6441132B2 - Dental photopolymerizable composition - Google Patents

Description

  The present invention relates to a dental photopolymerizable composition used for dental treatment, and particularly to a dental photopolymerizable composition that can be suitably used for a large cavity.

  In restoration of dental material that has been damaged due to caries, etc., a restoration material mainly composed of a (meth) acrylate radical polymerizable monomer and an inorganic filler such as a metal oxide, called a composite resin for filling. The mainstream is a method of filling the defective portion with a paste and polymerizing and curing the tooth shape. In the defect portion, before filling the paste, in order to remove a lesion portion such as a caries, a treatment for cutting out the periphery of the defect portion and forming a cavity is performed.

  Polymerization methods in the dental field are roughly classified into photopolymerization and chemical polymerization. Since the photopolymerization type repair material using the radical polymerizable monomer and the photopolymerization initiator hardly undergoes the polymerization reaction if the light is blocked, all the components are in one paste state. It can be manufactured and stored, and there are advantages such as no need for mixing and kneading work at the time of use, which is necessary when using a chemical polymerization type restoration material, and a long pot life. Therefore, in recent years, photopolymerization type dental restoration materials have become mainstream. Hereinafter, such a photopolymerization type restorative material is referred to as a dental photopolymerizable composition.

In the field of dental treatment, it is difficult to use a photopolymerization initiator having activity in the ultraviolet region because of its harmfulness to the living body. Therefore, a photopolymerization initiator having activity in light (active light) in the visible light region is used. used. As such a photopolymerization initiator, α-diketone compounds that absorb light and decompose themselves to generate polymerization active species are widely used.
The dental photopolymerizable composition is polymerized and cured by filling with light in the patient's oral cavity. Therefore, if the irradiation time of the light for polymerization (active light) is made long, there is a problem that not only the operation takes time but also a heavy burden is imposed on the patient, and there is a demand for shortening the light irradiation time. Yes. Moreover, when the mechanical strength of the cured polymer of the dental photopolymerizable composition after light irradiation is low, there arises a problem that the shape at the time of treatment is impaired due to wear in addition to defects such as cracks and chips.

  For these reasons, the α-diketone compound is mechanically combined with a photoacid generator such as a triazine compound or an iodonium salt that shortens the polymerization time by combining an amine compound as a sensitizer. The thing which provides intensity | strength is proposed (for example, refer patent document 1, 2). Among these, when using a photopolymerization initiator composition of a high-speed polymerization system in which the amine compound and the triazine compound are combined with the α-diketone compound, the polymerization time of the radical polymerizable monomer is shortened. The polymer cured product can be provided with excellent mechanical strength (see Patent Document 1).

  However, since the radical polymerizable monomer contracts during polymerization, stress during contraction (contraction stress) may concentrate on the interface between the cavity and the polymerized cured body, and photopolymerization of the high-speed polymerization system starts. When an agent composition is used, a rapid contraction stress due to a polymerization reaction acts on the interface, so that a gap (gap) is easily generated between the cavity and the polymerized cured body. This problem is particularly obvious when polymerization is performed by filling the dental cavity with the dental photopolymerizable composition at one time. When the gap occurs, the polymerized cured product may fall off from the cavity, or may be secondary. Causes caries.

By the way, a polymerization inhibitor may be blended as a polymerization control component in order to prevent unintentional polymerization based on environmental light such as dental light for examining the oral cavity of a patient or indoor light in a treatment room.
However, if the blending amount of the polymerization inhibitor is increased in order to obtain stability against the ambient light, polymerization at a deep position in the cavity may be insufficient.
Therefore, for large cavities, a dental photopolymerizable composition containing an α-alkylstyrene compound such as α-methylstyrene dimer as a polymerization control component capable of obtaining relatively high curability in the deep cavity. Has been proposed (Patent Document 3).

However, in the dental photopolymerizable composition containing the α-alkylstyrene compound, although a deep depth of cure is obtained, the effect on the gap when the photopolymerization initiator composition of the high-speed polymerization system is added, and The strength of the polymerized cured product is unknown. Rather, the α-alkylstyrene compound is an additive used to control the degree of polymerization (average molecular weight) of the polymer as a polymerization control component. When the polymerization initiator composition is used, there is a concern that the merit is simply lost and the strength of the cured product is insufficient.
Therefore, as a cavity compatibility, a dental light capable of obtaining a polymerized cured body having an excellent mechanical strength, with a gap between the cavity and the polymerized cured body hardly generated even for a large cavity. The present condition is that there is no polymerizable composition.

Japanese Patent No. 4093974 Japanese Patent No. 4596786 Japanese Patent No. 3536879

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a dental photopolymerizable composition capable of obtaining a polymerized cured body having excellent cavity compatibility and mechanical strength even for a large cavity.

The present inventors have been proceeding with examinations through repeated trial and error from the current situation that there is no excellent cavity compatibility and mechanical strength even for a large cavity.
In such examination, even if the α-alkylstyrene compound was simply added to the dental photopolymerizable composition, the mechanical strength could not be obtained as previously feared. While proceeding with the study, in the system based on the combination of the α-diketone compound, the amine compound and the photoacid generator, the polymer cured product having excellent cavity compatibility and mechanical strength is obtained contrary to expectations. I got the knowledge.

The present invention is based on the above knowledge, and means for solving the above problems are as follows. That is,
<1> (A) a radically polymerizable monomer, (B) an α-diketone compound, (C) an amine compound, (D) a photoacid generator, and (E) an α-alkylstyrene compound. a dental photopolymerizable composition comprising Nde containing, (a) the amount of the relative radical-polymerizable monomer 100 parts by (E) alpha-alkylstyrene compound 0.1 part by mass to 0.5 After filling the dental photopolymerizable composition into a simulated cavity having a diameter of 6 mm and a depth of 2 mm, the dental photopolymerizable composition is polymerized by irradiating light from above the simulated cavity. When cured, the dental photopolymerizable composition has a maximum stress arrival time which is a time until the polymerization shrinkage stress generated by the polymerization and curing reaches a maximum value of 48 seconds or more . Photopolymerizable composition.
<2> The dental photopolymerizable composition according to <1>, wherein the (E) α-alkylstyrene compound is an α-methylstyrene dimer .
< 3 > (D) The dental agent according to any one of <1> to < 2 >, wherein the photoacid generator is at least one of an s-triazine compound substituted with a trihalomethyl group and a diaryliodonium salt compound. Photopolymerizable composition.
< 4 > (C) The dental photopolymerizable composition according to any one of <1> to < 3 >, wherein the amine compound contains an aliphatic tertiary amine compound and an aromatic tertiary amine compound. .
< 5 > The dental photopolymerizable composition according to any one of <1> to < 4 >, further comprising (F) a filler.
< 6 > The dental photopolymerizable composition according to any one of <1> to < 5 >, which is used as a dental composite resin for filling and repairing a cavity having a depth of 3 mm to 6 mm.

  ADVANTAGE OF THE INVENTION According to this invention, the dental photopolymerization which can solve the said various problems in a prior art, and can obtain the polymeric hardening body which has the outstanding cavity compatibility and mechanical strength also with respect to a large cavity. Sex compositions can be provided.

(Dental photopolymerizable composition)
The dental photopolymerizable composition of the present invention comprises at least (A) a radical polymerizable monomer, (B) an α-diketone compound, (C) an amine compound, (D) a photoacid generator, E) an α-alkylstyrene compound, and optionally other components.

<(A) Radical polymerizable monomer>
The (A) radical polymerizable monomer is a component that is polymerized and cured by light irradiation using (B) an α-diketone compound, (C) an amine compound, and (D) a photoacid generator as a polymerization initiation component.
The (A) radical polymerizable monomer is not particularly limited and may be appropriately selected depending on the intended purpose, but does not have an acidic group (such as a sulfonic acid group, a carboxyl group, or a phosphoric acid residue) (meta ) An acrylate-based polymerizable monomer is preferably used from the viewpoints of curing speed, mechanical properties of the cured product, water resistance, color resistance, and the like. In particular, a polyfunctional monomer having a plurality of polymerizable functional groups. A (meth) acrylate polymerizable monomer is preferred.
There is no restriction | limiting in particular as said polyfunctional (meth) acrylate type | system | group polymerizable monomer, Although it selects suitably according to the objective, The water-insoluble compound whose solubility with respect to water is 5 mass% or less is preferable.
Examples of the water-insoluble compound include the following (I) bifunctional polymerizable monomer, (II) trifunctional polymerizable monomer, and (III) tetrafunctional polymerizable monomer described in detail below. Can be mentioned.

(I) Bifunctional polymerizable monomer Examples of the (I) bifunctional polymerizable monomer include (i) aromatic compound-based monomers and (ii) aliphatic compound-based monomers.

(I) Aromatic compound type As the above (i) aromatic compound type, for example, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane ("bis-GMA"), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane ("D-2 .6E "), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) ) Propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) pro Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having a hydroxyl group such as acrylate corresponding to these methacrylates, and diisocyanate methylbenzene Emissions, etc. diadduct obtained from adducts of a diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate.

(Ii) Aliphatic compound-based (ii) Aliphatic compound-based compounds include, for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (“3G”), tetraethylene glycol dimethacrylate, Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxy Vinylates having hydroxyl groups such as methacrylates such as propyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates 1,2-bis (3-methacryloyloxy), a diadduct obtained from an adduct of a monomer and a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 2-hydroxypropoxy) ethyl and the like.

(II) Trifunctional polymerizable monomer Examples of the (II) trifunctional polymerizable monomer include trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate. Examples thereof include methacrylates and acrylates corresponding to these methacrylates.

(III) Tetrafunctional polymerizable monomer Examples of the (III) tetrafunctional polymerizable monomer include pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate; diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene. Examples thereof include a diadduct obtained from an adduct of a diisocyanate compound such as diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4,4-diphenylmethane diisocyanate, tolylene-2,4-diisocyanate and glycidol dimethacrylate.

As the polyfunctional (meth) acrylate polymerizable monomer, one kind may be used alone, or two or more kinds may be used in combination.
Furthermore, if necessary, for example, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. You may use together with a mer.
In the dental photopolymerizable composition, from the viewpoint of obtaining good cured product properties (mechanical strength, non-eluting property, etc.), the amount of monomers other than the polyfunctional (meth) acrylate monomer However, the total amount of the (A) radical polymerizable monomer is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

<(B) α-diketone compound>
The α-diketone compound is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said alpha-diketone compound, According to the objective, it can select suitably, For example, camphor quinones, such as camphor quinone, camphor quinone carboxylic acid, camphor quinone sulfonic acid; diacetyl, acetyl benzoyl, 2 , 3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, acenaphthenequinone, and the like. Among these, the camphorquinones having a maximum absorption wavelength in the visible light region are preferable, and the camphorquinone is particularly preferable.
In addition, these may be used individually by 1 type and may use 2 or more types together.

The blending amount of the α-diketone compound is not particularly limited and may be appropriately selected depending on the intended purpose. It is 0.01 parts by mass with respect to 100 parts by mass of the (A) radical polymerizable monomer. 10 mass parts is preferable, and 0.03 mass parts to 5 mass parts is more preferable.
When the blending amount is less than 0.01 parts by mass, the polymerization of the radically polymerizable monomer (A) becomes insufficient, and when it exceeds 10 parts by mass, the ambient light stability may be lowered.

<(C) Amine compound>
The (C) amine compound is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said (C) amine compound, Although it can select suitably according to the objective, Any of a primary amine compound, a secondary amine compound, and a tertiary amine compound can be used. Among these, the tertiary amine compound is preferable from the viewpoint of odor and the like.
The amine compound (C) is not particularly limited, and is an amine compound in which one or more aromatic groups are directly bonded to the nitrogen atom (hereinafter also referred to as “aromatic amine compound”), or bonded to the nitrogen atom. Any compound (hereinafter also referred to as “aliphatic amine compound”) in which all organic groups are aliphatic groups (however, they may have a substituent) can be used.

  There is no restriction | limiting in particular as said aromatic amine compound, According to the objective, it can select suitably, For example, aromatic primary amine compounds, such as aniline and toluidine; N-methylaniline, N-methyl-p- Aromatic secondary amine compounds such as toluidine; N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N- There may be mentioned tertiary amine compounds such as di (β-hydroxyethyl) -p-toluidine, p-dimethylaminobenzoic acid, ethyl p-dimethylaminobenzoate and amyl p-dimethylaminobenzoate. Among these, the tertiary aromatic amine compound is preferable from the viewpoint of odor, etc. in consideration of use as a dental product, and further exhibits high polymerization activity, stability to ambient light, and a short time due to irradiation light. The aromatic tertiary amine compound represented by the following general formula (1) is particularly preferable in that it can maintain the polymerization curability of the polymer and can exhibit high cured product properties.

However, in said general formula (1), R < ¹ > and R < ² > shows an alkyl group mutually independently, R < ³ > is any of an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and an alkyloxycarbonyl group. Indicate. Moreover, n shows the integer of 0-5. When n is 2 or more, the plurality of R ³ may be the same as or different from each other. Further, R ³ may be bonded to each other to form a ring.

In the general formula (1), the alkyl group represented by R ^{1 to} R ³ is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -A butyl group, n-hexyl group, etc. can be mentioned. These alkyl groups may be substituted alkyl groups having a substituent. Examples of such substituted alkyl groups include halogen-substituted alkyl groups such as a fluoromethyl group and a 2-fluoroethyl group; 2-hydroxy Examples thereof include a hydroxyl group-substituted alkyl group such as an ethyl group.

In the general formula (1), the aryl group, alkenyl group, alkoxy group and alkyloxycarbonyl group represented by R ³ may have a substituent.
As said aryl group, C6-C12 things, such as a phenyl group, p-methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, can be mentioned. Examples of the alkenyl group include those having 2 to 12 carbon atoms such as vinyl group, allyl group, and 2-phenylethenyl group. As said alkoxy group, C1-C10 things, such as a methoxy group, an ethoxy group, a butoxy group, can be mentioned. Examples of the alkyloxycarbonyl group include those having 1 to 10 carbon atoms in the alkyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, amyloxycarbonyl group, and isoamyloxycarbonyl group. it can.

In the general formula (1), R ¹ and R ² are particularly preferably an unsubstituted alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group) or a 2-hydroxyethyl group. .
In addition, when n = 1, the bonding position of R ³ is preferably the para position, and it is particularly preferable that R ³ is an alkyloxycarbonyl group. On the other hand, when n is 2 to 3, the bonding position is preferably at least one of the ortho position and the para position. In particular, the solar stability of the cured product can be improved by bonding a plurality of R ³ to the ortho and para positions.

Specifically, the tertiary aromatic amine compound represented by the general formula (1) is specifically exemplified as a compound in which R ³ is an alkyloxycarbonyl group bonded to the para-position, methyl p-dimethylaminobenzoate, p- Examples include ethyl dimethylaminobenzoate, propyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, propyl p-diethylaminobenzoate, and the like.
Specific examples of the other aromatic amine compounds include N, N-dimethylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine. N, N-di (β-hydroxyethyl) -p-toluidine, N, N, 2,4,6-pentamethylaniline, N, N, 2,4-tetramethylaniline, N, N-diethyl-2 , 4,6-trimethylaniline and the like.
In addition, as said aromatic amine compound, it may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said aliphatic amine compound, According to the objective, it can select suitably, Aliphatic primary amines, such as 2-ethylhexylamine, n-butylamine, n-hexylamine, n-octylamine, etc. Compound: Aliphatic secondary amine compound such as diethylamine, dibutylamine, diallylamine, diisopropylamine, di-2-ethylhexylamine, di-n-octylamine; triethylamine, triethanolamine, tributylamine, triallylamine, N, N -Aliphatic tertiary amine compounds such as dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate, and among these, two of the three saturated aliphatic groups bonded to the nitrogen atom The above has an electron-withdrawing group as a substituent. The aliphatic tertiary amine compound can achieve a higher polymerization activity, it is possible to obtain a more excellent storage stability. Examples of such aliphatic tertiary amines include those having two electron-withdrawing group-substituted saturated aliphatic groups such as N-methyldiethanolamine and N-ethyldiethanolamine, and triethanolamine and tri (isopropanol) amine. In which the number of electron-withdrawing group-substituted saturated aliphatic groups is 3.
In addition, as said aliphatic amine compound, it may be used individually by 1 type and may use 2 or more types together.

Any of these (C) amine compounds may be used, but it is preferable to contain the aromatic amine compound and the aliphatic amine compound. When these are used in combination, it is possible to suppress discoloration when the polymerized cured product is exposed to ultraviolet light such as sunlight, compared to the case where only the aromatic amine compound is blended, and only the aliphatic amine compound. The curing rate can be improved as compared with the case of blending.
Among these, the combined use of the aromatic tertiary amine compound represented by the general formula (1) and the aliphatic tertiary amine compound having the radical polymerizable functional group is particularly preferable.

There is no restriction | limiting in particular as a compounding quantity of the said (C) amine compound, Although it can select suitably according to the objective, 0.01 mass with respect to 100 mass parts of said (A) radically polymerizable monomers. Part-10 mass parts is preferable, and 0.02 mass part-5 mass parts is more preferable.
Moreover, when using together the said aromatic amine compound and the said aliphatic amine compound, as these compounding ratios, the said aromatic amine compound: the said aliphatic amine compound = 1: 99-99: 1 is a mass ratio. Preferably, 3:97 to 97: 3 is more preferable.

Furthermore, other known polymerization initiators can be used as necessary. Examples of the other polymerization initiator components include organic peroxides such as benzoyl peroxide and cumene hydroperoxide; + IV value or + V such as vanadium (IV) acetylacetonate, bis (maltolate) oxovanadium (IV), etc. Valent vanadium compounds; tetraphenyl boron sodium, tetraphenyl boron triethanolamine salt, tetraphenyl boron dimethyl-p-toluidine salt, tetrakis (p-fluorophenyl) boron sodium, butyltri (p-fluorophenyl) boron sodium, etc. Aryl borate compounds; coumarin-based dyes such as 3,3′-carbonylbis (7-diethylamino) coumarin, 7-hydroxy-4-methyl-coumarin; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxa B , Acylphosphine oxides such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether; Examples include thioxanthone derivatives such as 4-diethoxythioxanthone, 2-chlorothioxanthone, and methylthioxanthone; benzophenone derivatives such as benzophenone, p, p′-dimethylaminobenzophenone, and p, p′-methoxybenzophenone. .
In addition, as said other polymerization initiator, 1 type may be used individually and 2 or more types may be used together.

<(D) Photoacid generator>
The (D) photoacid generator is blended as a polymerization initiating component of the (A) radical polymerizable monomer.
There is no restriction | limiting in particular as said (D) photo-acid generator, According to the objective, it can select suitably, For example, a triazine compound, an aryl iodonium salt, etc. are mentioned.

There is no restriction | limiting in particular as said triazine compound, According to the objective, it can select suitably, For example, the s-triazine compound which has at least one trihalomethyl group, such as a trichloromethyl group and a tribromomethyl group, is mentioned.
Examples of the s-triazine compound substituted with the trihalomethyl group include compounds represented by the following general formula (2).

However, in said general formula (2), R < ⁴ > and R < ⁵ > shows either the organic group which has an unsaturated bond which can be conjugated with a triazine ring, an alkyl group, and an alkoxy group mutually independently, X is Represents a halogen atom.

The halogen atom represented by X in the general formula (2) may be any of chlorine, bromine and iodine, but chlorine is generally used. Therefore, as the substituent (CX ₃ ) bonded to the triazine ring, A trichloromethyl group is common.

In the general formula (2), when at least one of R ⁴ and R ⁵ is an organic group having an unsaturated bond that can be conjugated to the triazine ring, the storage stability of the dental photopolymerizable composition is improved. It can be made particularly excellent. On the other hand, it is easier to obtain better polymerization activity when at least one of R ⁴ and R ⁵ is a halogen-substituted alkyl group, and when both are halogen-substituted alkyl groups, the polymerization activity is particularly good.

In the general formula (2), the organic group bonded by an unsaturated bond that can be conjugated with the triazine ring represented by R ⁴ and R ⁵ is not particularly limited and may be appropriately selected depending on the purpose. An organic group having 2 to 30 carbon atoms is preferable, and an organic group having 2 to 14 carbon atoms is particularly preferable.
Specific examples of such an organic group include carbon number such as phenyl group, methoxyphenyl group, p-methylthiophenyl group, p-chlorophenyl group, 4-biphenylyl group, naphthyl group, 4-methoxy-1-naphthyl group, etc. C6-C14 alkenyl groups, such as a 6-14 aryl group; a vinyl group, 2-phenylethenyl group, 2- (substituted phenyl) ethenyl group, etc. are mentioned. In addition, as a substituent which the said substituted phenyl group has, C1-C6 alkyl groups, such as a methyl group, an ethyl group, and a propyl group; C1-C6 alkoxy groups, such as a methoxy group, an ethoxy group, and a propoxy group An alkylthio group having 1 to 6 carbon atoms such as a methylthio group, an ethylthio group and a propylthio group; a phenyl group; a halogen atom and the like.

In the general formula (2), the alkyl group and alkoxy group represented by R ⁴ and R ⁵ may have a substituent.
As said alkyl group, a C1-C10 thing is preferable, For example, unsubstituted alkyl groups, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, n-hexyl group A halogen-substituted alkyl group such as a trichloromethyl group, a tribromomethyl group, and an α, α, β-trichloroethyl group;
The alkoxy group is preferably one having 1 to 10 carbon atoms, for example, an unsubstituted alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group; 2- {N, N-bis (2-hydroxyethyl) amino} Amino such as ethoxy group, 2- {N-hydroxyethyl-N-ethylamino} ethoxy group, 2- {N-hydroxyethyl-N-methylamino} ethoxy group, 2- {N, N-diallylamino} ethoxy group And an alkoxy group substituted by a group.

  Specific examples of the s-triazine compound having the trihalomethyl group represented by the general formula (2) include 2,4,6-tris (trichloromethyl) -s-triazine (“TCT”), 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-methylthio) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4- Chlorophenyl) -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- (α, α, β-trichloroethyl) -4,6-bis (Trichloromethyl) -s-triazine, 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) eth L] -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-triazine, 2- [2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N -Hide Roxyethyl-N-methylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl)- Examples include s-triazine.

Among the above examples, a particularly preferred triazine compound is 2,4,6-tris (trichloromethyl) -s-triazine in terms of polymerization activity, and 2-phenyl-4,6 in terms of storage stability. -Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis (trichloromethyl) ) -S-triazine.
In addition, these triazine compounds may be used individually by 1 type, and may use 2 or more types together.

  The aryliodonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) Iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p-octyl Cations such as oxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, bis (p-dodecylphenyl) iodonium, chloride, bromide, p-toluenesulfonate, tri Le Oro methanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, tetrakis pentafluorophenyl gallate, hexafluorophosphate, hexafluoroarsenate, diaryliodonium salt compounds composed of anions such as hexafluoroantimonate are preferred.

Among these, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluoro from the viewpoint of solubility in the (A) radical polymerizable monomer. Compounds having phosphate, hexafluoroarsenate and hexafluoroantimonate as anions are preferred, and hexafluoroantimonate, tetrakispentafluorophenylborate, tetrakispenta are from the viewpoint of low anion nucleophilicity and high polymerization rate. A compound having fluorophenyl gallate as an anion is more preferable, and tetrakispentafluorophenyl borate is particularly preferable because toxicity derived from the anion is lower. Arbitrariness.
In addition, as these aryl iodonium salts, you may use individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a compounding quantity of the said (D) photo-acid generator, Although it can select suitably according to the objective, It is 0.00 with respect to 100 mass parts of said (A) radically polymerizable monomers. 001 mass part-10 mass parts are preferable, and 0.05 mass part-5 mass parts are more preferable.

<(E) α-alkylstyrene compound>
The (E) α-alkylstyrene compound is blended for the purpose of obtaining a polymerized cured product having excellent cavity compatibility and mechanical strength even for a large cavity.
The (E) α-alkylstyrene compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 2-phenyl-1-propene (α-methylstyrene), 2,4-diphenyl- 4-methyl-1-pentene (α-methylstyrene dimer), 3,5-diphenyl-5-methyl-2-heptene, 1,3-diphenyl-1-butene, 2,4-diphenyl-4-methyl- 2-pentene, 3,5-diphenyl-5-methyl-3-heptene, 1,1-diphenylethylene and the like can be mentioned. Among these, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene dimer) is preferable because the effects of the present invention are particularly easily obtained and it is easily available.

There is no restriction | limiting in particular as a compounding quantity of the said (E) alpha-alkyl styrene compound, Although it can select suitably according to the objective, It is 0 with respect to 100 mass parts of said (A) radically polymerizable monomers. 0.01 parts by mass to 1 part by mass is preferable, and 0.1 parts by mass to 0.5 parts by mass is more preferable.
When the blending amount is less than 0.01 parts by mass, the polymerization rate of the radically polymerizable monomer (A) may be limited and the shrinkage stress may not be sufficiently relaxed. In some cases, the mechanical strength of the polymerized cured product may decrease.

<Other ingredients>
The other components are not particularly limited as long as the effects of the present invention are not hindered, and can be appropriately selected depending on the purpose. For example, the filler (F) known as a compounding component of a dental restoration material ( Filler), (G) polymerization inhibitor, and the like.

-(F) Filler-
The filler (F) is blended for the purpose of imparting mechanical strength to the polymerized cured product of the dental photopolymerizable composition and reducing polymerization shrinkage and thermal expansion.
There is no restriction | limiting in particular as said (F) filler, According to the objective, it can select suitably, A well-known inorganic filler and an organic filler can be used, Above all, the said inorganic filler is preferable.

  The material for the inorganic filler is not particularly limited, and examples thereof include metal oxides such as quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Moreover, you may mix | blend a well-known cation elution inorganic filler as dental inorganic fillers, such as silicate glass and fluoroaluminosilicate glass, as needed.

  Alternatively, the above-mentioned inorganic filler (A) may be added with the radical polymerizable monomer (A) to form a paste, and then polymerized and cured, and then pulverized to obtain a granular organic-inorganic composite filler. Good.

The particle size of these (F) fillers is not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm (preferably 0.01 μm to 5 μm) that are generally used as dental materials are used. Can be used. Among these, when the spherical inorganic filler is used, the surface smoothness of the obtained cured product can be improved.
Moreover, there is no restriction | limiting in particular also as the refractive index of the said (F) filler, The refractive index of the range of 1.4-1.7 which is the refractive index of the inorganic filler used as a general dental material. A filler having can be used.

The inorganic filler is a surface treatment agent typified by a silane coupling agent from the viewpoint of improving familiarity with the (A) radical polymerizable monomer and improving mechanical strength and water resistance. A surface treatment is preferred.
Examples of the surface treatment method include known methods, and examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, Vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane, etc. Can be mentioned.
In addition, as said (F) filler, it may be used individually by 1 type and may use 2 or more types together.

  The blending amount of the filler (F) is not particularly limited and may be appropriately selected depending on the intended purpose. Viscosity (operability) when mixed with the (A) radical polymerizable monomer. In consideration of the mechanical properties of the cured product and the cured product, 50 parts by weight to 1,500 parts by weight is preferable with respect to 100 parts by weight of the radically polymerizable monomer (A). More preferred.

-(G) Polymerization inhibitor-
The (G) polymerization inhibitor is blended for the purpose of obtaining storage stability.
There is no restriction | limiting in particular as said (G) polymerization inhibitor, For example, hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene etc. can be mentioned.

  In addition, as the other components, pigments, fluorescent pigments, dyes for the purpose of matching the color tone of the teeth, ultraviolet absorbers for the purpose of preventing discoloration against ultraviolet rays may be blended, and additives known for use in dental composite resins. You may mix | blend.

<Application>
The dental photopolymerizable composition provides a polymerized cured product having excellent cavity compatibility with a large cavity and mechanical strength. Therefore, the dental photopolymerizable composition is suitable as a dental restoration resin for filling and repairing cavities having a depth of 3 mm to 6 mm as a filling and restoration material for large cavities. Further, when used in such applications, the dental photopolymerizable composition can be filled into the cavity at a time and irradiated with light to complete the polymerization and curing operation.

  Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the technical idea of the present invention is not limited by these.

(Each component and its abbreviations and abbreviations)
<(A) Radical polymerizable monomer>
bis-GMA: 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane 3G: triethylene glycol dimethacrylate <(B) α-diketone compound>
CQ: camphorquinone <(C) amine compound>
DMBE: N, N-dimethylamino-p-ethylbenzoate MDEOA: N-methyldiethanolamine <(D) Photoacid generator>
IPDPI: p-isopropylphenyl-p-methylphenyliodonium tetrakispentafluorophenylborate TCT: 2,4,6-tris (trichloromethyl) -s-triazine <(E) α-alkylstyrene compound>
MSD: α-methylstyrene dimer MS: α-methylstyrene <(F) filler>
F-1: Spherical silica-zirconia surface-treated product of γ-methacryloyloxypropyltrimethoxysilane having an average particle size of 0.2 μm F-2: Bis- of the spherical silica-zirconia (F-1) GMA / 3G = 60/40 dispersed in a polymerizable monomer, polymerized and cured, and then pulverized, and average particle size is 30 μm F-3: γ-methacryloyloxy of spherical silica-zirconia F-4: Spherical silica-zirconia γ-methacryloyloxypropyltrimethoxysilane surface-treated product with an average particle size of 0.08 μm <(G) Polymerization inhibitor>
HQME: Hydroquinone monomethyl ether

Example 1
As the (A) radical polymerizable monomer, bis-GMA (60 parts by mass) and 3G (40 parts by mass) were mixed to prepare a mixture of the (A) radical polymerizable monomer.
Next, 0.3 parts by mass of CQ as the (B) α-diketone compound, 0.45 parts by mass of DMBE as the (C) amine compound, and (D) the photoacid generator with respect to 100 parts by mass of the mixture. As a result, 0.75 parts by mass of IPDPI, 0.3 parts by mass of MSD as the (E) α-alkylstyrene compound, and 0.15 parts by mass of HQME as the (G) polymerization inhibitor were added, and these became uniform. Until mixed.
Next, in a mortar, 450 parts by mass of F-1 and F-2 as the filler (F) with a mass ratio of 60:40 (= F-1: F-2) are weighed, and the homogeneous mixture is 100 masses. The portion was gradually added under red light and sufficiently kneaded in a dark place to obtain a uniform curable paste.
Subsequently, defoaming was performed under reduced pressure to remove bubbles from the paste, and a dental photopolymerizable composition according to Example 1 was produced.

(Examples 2 , 4, 6-12 and Reference Examples 1, 2 )
Example 1 except that the types and blending amounts of the (C) amine compound, the (D) photoacid generator, and the (E) α-alkylstyrene compound were changed to the types and blending amounts shown in Table 1 below. Similarly, each dental photopolymerizable composition according to Examples 2 , 4, 6 to 12 and Reference Examples 1 and 2 was produced.

(Comparative Examples 1-4)
Other than not blending at least one of the (C) amine compound, the (D) photoacid generator, and the (E) α-alkylstyrene compound, and blending them in the types and amounts shown in Table 1 below. Each dental photopolymerizable composition according to Comparative Examples 1 to 4 was produced in the same manner as in Example 1.

(Characteristic evaluation)
<Evaluation test for polymerization shrinkage stress>
The polymerization shrinkage stress test was performed with reference to a test method described in a reference (Nemoto et al., Dental Materials and Instruments, Vol. 11 No. 4 697-702 (1992)). A universal testing machine (manufactured by Shimadzu Corp., Autograph AG5000D) was used as the main body and control unit of the shrinkage stress measuring device. The open cavity sample portion was used, and the size of the simulated cavity was 6 mm in diameter and 2 mm in depth. A dental adhesive (One Nap Bond F Plus, manufactured by Tokuyama Dental Co., Ltd.) was applied to the inside of the cavity and left for 10 seconds, and then irradiated with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for 10 seconds. For each test, the simulated cavity was filled with each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4, and a visible light irradiator (TOXOH). Power light, manufactured by Tokuyama Co., Ltd.) was used for light irradiation for 10 seconds from above the simulated cavity and polymerized and cured.
After the start of the light irradiation, the shrinkage stress caused by polymerization and curing was measured for 3 minutes, and the maximum value was defined as the “maximum stress” of the polymerization shrinkage stress. Further, the time until the polymerization shrinkage stress reaches the maximum stress after the start of the light irradiation was measured as “maximum stress arrival time”.
Table 1 shows “maximum stress” and “maximum stress arrival time” of each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4. Show.

<Cavity compatibility test>
The cows were slaughtered, and the lip side surface of the cow's front teeth removed within 24 hours after slaughtering was polished with # 600 water-resistant abrasive paper.
Next, a dental adhesive (Bond Force II, manufactured by Tokuyama Dental Co., Ltd.) was applied to the polished surface, left standing for 10 seconds, dried with compressed air, and a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). For 10 seconds.
Next, a wax sheet with a 2 mm-thick φ8 mm hole formed is attached to the surface treated with the dental adhesive, and the hole is filled with a dental composite resin (Palfique Estelite, manufactured by Tokuyama Dental Co., Ltd.). And irradiated with light for 30 seconds using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.) for polymerization and curing.
Next, under water injection, using a diamond bar, excavation is performed from the upper surface side of the composite resin cured body exposed from the hole of the wax sheet to the teeth positioned under the composite resin cured body, and the composite A simulated cavity having a diameter of 4 mm and a depth of 4 mm was formed in the cured resin body. In the formation of the simulated cavity, the excavation is performed up to a depth (depth 2 mm) where the dentin of the teeth is exposed after a through hole is formed in the cured composite resin (thickness 2 mm), The simulated cavity has a depth of 4 mm.
Next, after the inside of the simulated cavity was treated with the dental adhesive in the same manner as the treatment on the polished surface , Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 were placed in the simulated cavity for each test. And each dental photopolymerizable composition according to Comparative Examples 1 to 4 was filled, irradiated with light for 10 seconds using the visible light irradiator, polymerized and cured, and each test piece of the cavity compatibility evaluation test was produced. .
Next, after immersing the test piece in water at 37 ° C. for 24 hours, a diamond cutter was used to cut the central portion of the simulated cavity perpendicular to the bottom of the cavity, and the cut surface was # 1500 water-resistant abrasive paper And polished with # 3000 water-resistant abrasive paper.
The polished surface of the test piece was observed with a laser microscope, and it was observed whether a gap (gap) was present at the interface between the teeth (depth 2 mm) constituting the simulated cavity and the polymer cured body. With respect to the observation result, all the simulated cavities at the positions where gaps are observed with respect to the “boundary length” between the teeth constituting the simulated cavities and the polymerized cured body, which show the interface at the cut surface. Take the ratio of the “gap length” (the ratio of “gap length” / “boundary length”), which is the sum of the lengths of the (parts composed of the teeth), and the ratio is 0.1 or more An evaluation of “◯” was given for those less than 0.3, “Δ” was given for those of 0.3 or more and less than 0.5, and “x” was given for those of 0.5 or more.

<Bending strength test>
Each of the dental photopolymerizable compositions according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4 was filled into a stainless steel mold using a filling device, and polypropylene. Test samples of the respective dental photopolymerizable compositions were prepared by pressure welding.
Next, with respect to each test sample, using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Co., Ltd.), light is applied to the entire test sample for 30 seconds × 3 times on one surface. While changing the place, the light source was brought into close contact with the polypropylene to perform light irradiation.
Next, the opposite surface was similarly irradiated with light to cure each of the test samples, and then this was shaped into a 2 × 2 × 25 mm prismatic shape using # 800 water-resistant abrasive paper. Each specimen of the dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 , Reference Examples 1 and 2, and Comparative Examples 1 to 4 was obtained.
Each test piece was mounted on a testing machine (manufactured by Shimadzu Corporation, Autograph AG5000D), and the three-point bending fracture strength was measured under the conditions of a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min.
The breaking strength was calculated as the bending strength σ _B by the following formula.
In addition, the said test piece produced 5 pieces for every dental photopolymerizable composition which concerns on Example 1 , 2, 4 , 6-12, Reference Examples 1 and 2, and Comparative Examples 1-4 , and calculated bending strength. The average value of the five pieces of thickness σ _{B was taken} as the bending strength (MPa) of each dental photopolymerizable composition. The bending strength of these dental photopolymerizable compositions is shown in Table 1 below.

However, in said formula, P shows the load (N) at the time of the said test piece fracture, S shows the distance (m) between fulcrums, W shows the width | variety (m) of the said test piece, B Indicates the thickness (m) of the test piece.

As shown in Table 1 above, each of the dental photopolymerizable compositions according to Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 has a cavity compatibility evaluation of Δ or more and bending strength. Is 75 MPa or more, and both good cavity compatibility and mechanical strength can be achieved.
On the other hand, each dental photopolymerizable composition according to Comparative Examples 1 to 4 has a cavity compatibility evaluation of Δ or more and a bending strength of 75 MPa or more, and has cavity compatibility and mechanical strength. It is not possible to achieve both.

  That is, with respect to the dental photopolymerizable composition according to Example 1, the dental photopolymerizable composition according to Comparative Example 1 in which the (D) photoacid generator and the (E) alkylstyrene are not blended is the maximum. The stress arrival time is short, and it is considered that a large amount of gap was generated due to a rapid polymerization shrinkage stress acting at the interface between the polymerized cured body and the simulated cavity. In addition, by not blending the (D) photoacid generator, the amount of radicals generated by the (B) α-diketone compound and the (C) amine compound can be suppressed, and the (A) radical polymerizable monomer can be reduced. It is considered that sufficient mechanical strength could not be imparted to the polymerized cured product.

  Further, in the dental photopolymerizable composition according to Comparative Example 2 in which the (D) photoacid generator was not blended and only the (E) α-alkylstyrene compound was blended, Comparative Example 1 in which both of these were not blended. Although the cavity compatibility is slightly improved as compared with the dental photopolymerizable composition according to the present invention, the mechanical strength is further reduced. This is because, by not blending the (D) photoacid generator, the amount of radicals generated by the (B) α-diketone compound and the (C) amine compound is suppressed, and the (E) It means that even if only the α-alkylstyrene compound is blended, it functions to lower the degree of polymerization of the (A) radical polymerizable monomer.

Further, in the dental photopolymerizable composition according to Comparative Example 3 in which the (E) α-alkylstyrene compound is not added to the dental photopolymerizable composition according to Example 6, the maximum stress arrival time is extremely short. It is time, the (D) photoacid generator continues to generate a large amount of radicals immediately after the start of light irradiation, and the polymerization reaction of the (A) radical polymerizable monomer proceeds rapidly and sufficiently. However, on the other hand, it is considered that the polymerization shrinkage stress acted more rapidly at the interface between the polymerized cured body and the simulated cavity and many gaps were generated.
This tendency is similar, and through comparison between the dental photopolymerizable composition according to Example 12 and the dental photopolymerizable composition according to Comparative Example 4, the type of the (D) photoacid generator It is confirmed that even if it is changed, it does not change.

Therefore, from comparison between each dental photopolymerizable composition according to Examples 1 , 2, 4, 6 to 12 and Reference Examples 1 and 2 and each dental photopolymerizable composition according to Comparative Examples 1 to 4, (D) The photoacid generator and the (E) alkyl styrene polymerize the (A) radical polymerizable monomer at a moderate rate, and as a result, a gap is generated due to a rapid polymerization shrinkage stress. It is thought that it can be suppressed. In addition, it is considered that the polymerization reaction itself of the (A) radical polymerizable monomer proceeds sufficiently by continuing the light irradiation, and can impart excellent mechanical strength to the polymerized cured product. This means that some of the radical species generated from the (B) α-diketone compound and the (C) amine compound by the (D) photoacid generator migrate to the (E) α-alkylstyrene compound. As a result, the radical species that has become a rate-determining factor for the polymerization reaction of the (A) radical polymerizable monomer, and has moved to the (E) α-alkylstyrene compound, the radical polymerizable monomer (A) This is considered to be used for the polymerization reaction of the monomer.

Particularly, (E) / (A), which is a blending ratio of the (E) α-alkylstyrene compound to the (A) radical polymerizable monomer (100 parts by mass), is 0.1 to 0.00 by mass ratio. The dental photopolymerizable compositions according to Examples 1, 2, and 4 within the range of 5 are superior to the dental photopolymerizable compositions according to Reference Examples 1 and 2 that are outside the range. Compatibility and mechanical strength are obtained.

Moreover, in each dental photopolymerizable composition which concerns on Examples 6-8 which uses together an aromatic tertiary amine compound and an aliphatic tertiary amine compound as said (C) amine compound, in said aromatic amine Compared to each of the dental photopolymerizable compositions according to Examples 1 and 2 and Reference Example 1 where the compound alone is used, the maximum stress arrival time is long and excellent cavity compatibility is obtained, and more excellent mechanical strength is obtained. Yes.
In addition, with respect to the dental photopolymerizable composition according to Example 6, in the dental photopolymerizable composition according to Example 9 in which the blending amount of the filler (F) was reduced, a decrease in mechanical strength was confirmed. However, the mechanical strength can be improved by changing the type of the filler (F) to the spherical one used in the dental photopolymerizable composition according to Example 10.

  Further, in the dental photopolymerizable composition according to Example 6 in which an α-alkylstyrene dimer is blended as the (E) α-alkylstyrene compound, the dental light according to Example 11 in which α-alkylstyrene is blended. The maximum stress arrival time is longer than that of the polymerizable composition, and excellent cavity compatibility is exhibited, and superior mechanical strength is obtained.

  Moreover, in the dental photopolymerizable composition according to Example 6 in which a diaryliodonium salt compound is blended as the photoacid generator (D), the dental photopolymerizability according to Example 12 in which an s-triazine compound is blended. The maximum stress arrival time is longer than that of the composition, and excellent cavity compatibility is exhibited, and superior mechanical strength is obtained.

Claims (6)

(A) a radical polymerizable monomer, comprising Nde containing and (B) alpha-diketone compound, and (C) an amine compound, and (D) photoacid generator, and a (E) alpha-alkylstyrene compounds A dental photopolymerizable composition comprising:
The blending amount of the (E) α-alkylstyrene compound with respect to 100 parts by mass of the (A) radical polymerizable monomer is 0.1 parts by mass to 0.5 parts by mass,
When the dental photopolymerizable composition is filled into the inside of a simulated cavity having a diameter of 6 mm and a depth of 2 mm, and then the dental photopolymerizable composition is polymerized and cured by irradiation with light from above the simulated cavity, The dental photopolymerizable composition having a maximum stress arrival time of 48 seconds or more, which is a time until the polymerization shrinkage stress generated by the polymerization and curing of the dental photopolymerizable composition reaches a maximum value . .   (E) The dental photopolymerizable composition according to claim 1, wherein the α-alkylstyrene compound is an α-methylstyrene dimer. The dental photopolymerizable composition according to any one of claims 1 to 2, wherein (D) the photoacid generator is at least one of an s-triazine compound substituted with a trihalomethyl group and a diaryliodonium salt compound. The dental photopolymerizable composition according to any one of claims 1 to 3, wherein the amine compound (C) comprises an aliphatic tertiary amine compound and an aromatic tertiary amine compound. The dental photopolymerizable composition according to any one of claims 1 to 4, further comprising (F) a filler. The dental photopolymerizable composition according to any one of claims 1 to 5, which is used as a dental composite resin for filling and repairing a cavity having a depth of 3 mm to 6 mm.