JP2005171213A - Multi-wavelength photopolymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photopolymerizable composition expressing a good property of adhering to dentin and/or physical characteristics and having good curability even when various photoirradiation apparatuses used in clinical dentistry, such as a halogen lamp, LED, and xenon lamp are used. <P>SOLUTION: The photopolymerizable composition contains a polymerization initiator containing (a) a coumarin compound, (b) an acylphosphine oxide and/or bisacylphosphine oxide, and (c) a polymerization promoter and further contains (d)α-diketones and/or thioxanthones. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a photopolymerizable composition comprising a radical polymerizable monomer and a photopolymerization initiator.
It is related with the photopolymerizable composition which can be hardened even if it is a light source of a different wavelength band between 350-500 micrometers.
The present invention relates to a photopolymerizable composition characterized by exhibiting sufficient photocurability in the visible light and near ultraviolet light regions.

In dental practice, D, L-camphorquinone is mainly used as a photopolymerization initiator for photopolymerization resin materials.
Recently, with the progress of photopolymerization technology, instead of halogen lamps, light emitted from a light-emitting diode (LED) irradiator that generates less heat and does not cause thermal stimulation to the dental pulp and has a long lamp life, and a xenon lamp that can shorten irradiation time with high output. The polymerization method has attracted attention in the dental clinic.
However, the current dental photopolymerization material has a high polymerization efficiency with a halogen lamp, but has a problem in dentistry such as a poor polymerization caused by a light irradiator such as an LED or a xenon lamp and a decrease in physical properties.
In other words, the development of a dental resin material that has excellent photocurability in the visible and near-ultraviolet regions and exhibits sufficient curability when irradiated with any light from halogen lamps, LEDs, and xenon lamps that are commonly used in general clinical practice. It is requested.

In Japanese Patent Publication No. 54-10986, α-diketone and N, N-dimethylaminoethyl methacrylate represented by D, L-camphorquinone, and in Japanese Patent Publication No. 60-26002, α-diketone and N, N-dimethylaminobenzoic acid. A photoinitiator effective for visible light polymerization passing through an exciplex is disclosed by an α-diketone excited by so-called light irradiation such as acid ethyl ester and a photoreductive agent as a hydrogen donor.
However, these photopolymerization initiators have a problem that photocurability is lowered when an adhesive monomer having an acid group coexists or when the initiator concentration is extremely low.

On the other hand, in JP-A-9-3109, a polymerizable composition comprising a visible light polymerization initiator comprising (A) a coumarin dye, (B) a photoacid generator, and (C) an aryl borate compound. Have been reported to develop high adhesive strength in dentin adhesion.
JP-A 2003-277424 discloses a visible light polymerization initiator comprising (A) a sensitizing dye (such as a coumarin compound), (B) a photoacid generator, and (C) an organic sulfinate. It is disclosed that when a polymerizable composition containing an adhesive is used as an adhesive with a tooth, it exhibits a high adhesive strength to the tooth without using a conventionally used tooth surface treatment agent. ing.
However, in these photopolymerization initiators, only the photopolymerization effect with a halogen lamp is presented, and the polymerization effect with an LED or a xenon lamp is not sufficient.

Japanese Patent No. 344276 and Japanese Patent Application Laid-Open No. 2000-212015 present a photopolymerizable composition comprising an acylphosphine oxide and an α-diketone.
These have also been proposed for applications in the dental field, such as acylphosphine oxide initiators and bisacylphosphine oxide initiators, which are said to be due to α-cleavage.
However, although these photopolymerization initiators are excellent only in the photopolymerization effect in the halogen lamp, the polymerization effect in the LED and the xenon lamp is not sufficient.

JP-A-1-26506 shows the effect of an acylphosphine oxide polymerization initiator in a photocurable crown material comprising a polyfunctional monomer and a filler. Acylphosphine oxide and amine compounds have been reported as polymerization initiators. JP-A-10-338610 discloses a dental polymerizable composition comprising a monomer having a polymerizable olefinic unsaturated group, an acyl phosphine oxide, an organic peroxide, and a tertiary amine, and JP-A-10 338611 discloses a dental polymerizable composition comprising a monomer having a polymerizable olefinically unsaturated group, an acyl phosphine oxide, an organic peroxide, an aromatic sulfinic acid or a salt thereof. Yes. However, in the case of these acylphosphine oxides alone or in the case of a photopolymerization initiator composed of a polymerization accelerator such as acylphosphine oxide and an amine compound, as a result of actual experiments, although the photopolymerization efficiency in a halogen lamp is high, LED and xenon The lamp has a problem that the photocurability is lowered when the photocurability is extremely low and the concentration of the polymerization initiator is extremely low.

In this way, development of a photopolymerization resin that can be applied to various light irradiators with different irradiation areas used in dentistry such as halogen lamps, LEDs, and xenon lamps is strongly desired. There is no provision of a photopolymerizable composition, particularly a photopolymerization initiator.

Japanese Patent Publication No.54-10986 JP-A-9-3109 JP 2003-277424 A Patent No. 3444276, JP 2000-212015 JP-A-1-26506 JP 2000-16910 A JP-A-10-338610 JP-A-10-338611

Conventionally, there has been no photopolymerization composition having excellent curing characteristics using an energy efficient LED or xenon lamp.
Conventionally, in the photopolymerization apparatus in the visible and near-ultraviolet region other than the halogen lamp that is widely used in the dental field, physical properties such as tooth adhesion, curability, polymerizability, abrasion resistance, and color developability None had excellent properties. Furthermore, the problem of coloring has not been improved.
In particular, as a result of testing with a plurality of light sources, there were many spots in the cured state due to the light sources, and it was necessary to take measures such as changing the curing method depending on the apparatus.
Photopolymerization composition that exhibits excellent dental adhesion and / or physical properties and excellent curability even when using various light irradiators used in dental practice such as halogen lamps, LEDs, and xenon lamps Nothing was provided.

The present invention is a photocurable composition comprising a radical polymerizable monomer and a photopolymerization initiator, wherein the photopolymerization initiator is (a) a coumarin compound,
(B) acylphosphine oxide and / or bisacylphosphine oxide,
(C) a polymerization accelerator,
It is a photopolymerizable composition characterized by including.

The present invention is a photopolymerizable composition capable of photocuring with a light emitting diode (LED) and a light irradiator of a xenon lamp.
The present invention relates to a photopolymerizable compound in which the coumarin compounds are 3,3′-carbonyl-7-dimethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin and 3,3′-carbonylbis (7-dibutylaminocoumarin). It is a composition.
In the present invention, the acyl phosphine oxide and / or bisacyl phosphine oxide may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4 , 6-trimethylbenzoyl) acylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

The present invention is a photopolymerizable composition in which the polymerization accelerator is a barbituric acid derivative, an amine, a tin compound and sulfinic acid and / or a metal salt thereof.
In the present invention, the barbituric acid derivatives of the polymerization accelerator are 1,3,5-trimethylbarbituric acid, 5-butylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, and 1-benzyl-5-phenylbarbituric acid. Tool acid, amines are 4-N, N-dimethylaminobenzoic acid ethyl ester, tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate, and sulfinic acid or its metal It is a photopolymerizable composition whose salt is sodium benzenesulfinate and sodium p-toluenesulfinate.
The present invention is a photopolymerizable composition to which (d) α-diketone and / or thioxanthone is added as a photopolymerization initiator.

The present invention is a photopolymerizable composition in which (d) D, L-camphorquinone and thioxanthone are added 2-chlorothioxanthen-9-one as a photopolymerization initiator.
The present inventors provide a photopolymerizable composition comprising a radical polymerizable monomer and a photopolymerization initiator, wherein the photopolymerization initiator is (a) a coumarin compound,
(B) acylphosphine oxide and / or bisacylphosphine oxide, and (c) a polymerization accelerator,
And (d) a photopolymerizable composition characterized by comprising an α-diketone and a thioxanthone, exhibiting excellent photocurability and adhesiveness. And the present inventors have found that the physical properties are improved.

    That is, the present invention is a photopolymerizable composition comprising a radical polymerizable monomer and a photopolymerization initiator, wherein (a) the coumarin compound of the photopolymerization initiator is 3,3′-carbonyl-7-dimethyl. Aminocoumarin-7′-bis (butoxyethyl) aminocoumarin and 3,3′-carbonylbis (7-dibutylaminocoumarin), (b) acylphosphine oxide is 2,4,6-trimethylbenzoyldiphenylacylphosphine oxide Bis (2,4,6-trimethylbenzoyl) acylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and (c) a polymerization accelerator are barbituric acid Consists of derivatives, amines, tin compounds and sulfinic acid or its metal salts The photopolymerizable composition characterized in that (d) α-diketones and thioxanthones may be added as desired differs in the irradiation light region used in dental clinics such as halogen lamps, LEDs, and xenon lamps. Even when using various light irradiators, it shows excellent photocurability in the photopolymerization composition, and it has been found that it gives excellent tooth adhesion and physical properties even in the aspect of bonding agent and composite resin, It came to make this invention.

The photopolymerization composition comprising the novel photopolymerization initiator and radically polymerizable monomer of the present invention is excellent in photocurability even in various light irradiations with different irradiation regions such as halogen light, LED, xenon lamp, etc. Have In the embodiment as the photopolymerizable bonding agent of the photopolymerizable composition of the present invention, it is clear that even if various light irradiators are used, the adhesive strength to the tooth is high, and in the embodiment as the photopolymerizable composite resin, It was revealed that physical properties such as photocuring depth, hardness, and compressive strength are high.

Specific examples of light rays for curing the photopolymerizable composition of the present invention are halogen lamps, LEDs, and xenon lamps. Among these, even when various irradiators having different irradiation light regions used in dentistry clinics are used, sufficient photocurability is exhibited.

The photopolymerizable composition of the present invention includes a dental bonding agent, a composite resin, a fisher sealant, an orthodontic adhesive, a teeth coating agent, a dual-curing resin cement, a crown and bridge composite resin, and an opaque material. It can be used for agents.
In addition, because of its high photopolymerization performance, it can be used not only in the dental field, but also in fields such as plastic surgery materials for general plastic surgery and general industrial fields, printing plate making materials, hologram materials, paints, lacquers, adhesives, and semiconductor substrate materials. .

    The radically polymerizable monomer of the photopolymerizable composition of the present invention is selected from monomers, oligomers, prepolymers and the like having radically polymerizable unsaturated double bonds used in the dental field and general industry. Can be used. As an abbreviation in the present invention, for example, methyl (meth) acrylate means methyl methacrylate and methyl acrylate.

Examples of the radical polymerizable monomer of the present invention include (meth) acrylic acid ester derivatives, alkylene glycol di (meth) acrylates, alkyl di (meth) acrylates, epoxy di (meth) acrylates, and bisphenol A-alkyldi (meth). Examples include acrylates, urethane di (meth) acrylates, urethane tri (meth) acrylates, urethane tetra (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylates having a Si group, and styrene derivatives. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanedi (meth) ) Acrylate, 2,2-bis {4- (meth) acryloxypropoxyphenyl} propane = bisphenol A-diglycidyl (meth) acrylate, di (meth) acryloxyethyl-2,2,4-trimethylhexamethylenediurethane, Di (meth) acryloxyisophorone diurethane, 2-hydroxyethyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, 6- Roxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 2- (meth) acryloxyethyl phosphate, bis [2- (meth) acryloxyethyl] phosphate, 2- (meth) acryloxyethylphenyl Examples include hydrogen phosphate, 10- (meth) acryloxydecyl hydrogen phosphate, vinyl phosphonic acid, p-vinylbenzyl phosphonic acid, γ-methacryloxypropyltrimethoxysilane, styrene, and the like. Particularly suitable monomers are ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, 1,6-hexanedi (meth) acrylate, di (meth) acryloxyethyl- 2,2,4-trimethylhexamethylene diurethane, di (meth) acryloxyisophorone diurethane, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, γ- And methacryloxypropyltrimethoxysilane.

Moreover, all the monomers conventionally used as dental monomers can be used, and in particular, carboxyl group, phosphate ester group, phosphonic acid group, sulfonic acid group, -SH group, polysulfide group, and cyclic disulfide group are included in the molecule. Adhesive functional monomers having one or more can also be used. For example, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 6- (meth) Acryloxyhexyl-3-phosphonoacetate, phosphonoacetate, 10- (meth) acryloxydecyl-3-phosphonopropionate, 6- (meth) acryloxyhexylphosphonoacetate, 10- (meth) acryloxy Decylphosphonopropionate 2- (meth) acryloxyethyl phosphate, bis [2- (meth) acryloxyethyl] phosphate, 2- (meth) acryloxyethylphenyl hydrogen phosphate, 10- (meth) Acryloxydecyl hydrogen phosphate, thioctic acid and hydro Esterification reaction product of sialkyl (meth) acrylate, 2- (meth) acryloxyethyl phosphate, bis [2- (meth) acryloxyethyl] phosphate, 2- (meth) acryloxyethylphenyl hydrogen phosphate, 10- (meth) acryloxydecyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 6,8-dithiooctanoate, 6- (meth) acryloyloxyhexyl as an esterification reaction product of thioctic acid and hydroxyalkyl (meth) acrylate Examples include 6,8-dithioctanoate, 10- (meth) acryloyloxydecyl 6,8-dithioctanoate, and the like.
These radically polymerizable compounds are used alone or in appropriate combination. Among them, polymerizable prepolymers such as 2,2-bis {4- (meth) acryloxypropoxyphenyl} propane, urethane (meth) acrylate and the like A combination with a polymerizable monomer such as triethylene glycol di (meth) acrylate is preferred. Furthermore, in embodiments such as a bonding agent, in addition to these polymerizable monomers, 4- (meth) acryloxyethyl trimellitic acid, 6- (meth) acryloxyhexylphosphonoacetate, 10- (meth) acryloxy It is preferable to blend a radical polymerizable monomer having an acidic group such as decyl hydrogen phosphate.

Specific examples of the (a) component coumarin compound contained in the photopolymerizable composition of the present invention include 3-cenoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, 3- ( 4-cyanobenzoyl) coumarin, 3-thienoyl-7-methoxycoumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-cyanobenzoyl) -7- Methoxycoumarin, 5,7-dimethoxy-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,7-dimethoxycoumarin, 3-acetyl- 7-dimethylaminocoumarin, 7-diethylamino-3-thienoylcoumarin, 7-diethylamino-3- (4- Toxibenzoyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylamino Coumarin, 3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-carboxy-7-diethylaminocoumarin, 3- (4-carboxybenzoyl) -7-diethylaminocoumarin, 3 -Benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3,5-carbonylbis (7- Methoxy bear 3-benzoyl-6-bromocoumarin, 3-benzoyl-7-dimethylaminomarin, 3-benzoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl- 6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminomarine, 7-dimethylamino-3- ( 4-iobenzoyl) coumarin, 7-diethylamino-3- (4-iobenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-Ethoxycinnamoyl) -7-methoxycoumarin, 3- ( 4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3-[(3-dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2 -D] thiazol-2-ylidene) acetyl] coumarin, 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-Benzimidazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) coumarin, 3-cabetoxy-7- (dimethylamino) coumarin, 10- [3- [4- (Dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl) -2,3,6,7-tetrahydro-1,1, 7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1H , 5H, 11H,-[1] benzopyrano [6,7,8-ij] quinolidine, 3,3′-carbonylbis (7-diethylaminocoumarin), 3,3′-carbonylbis (6-methoxycoumarin), 3 , 3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3,3′-carbonylbis (7-dibutylaminocoumarin), 3 3 ′ monocarbonyl-7-dimethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin, 3,3′-carbonyl-7-diethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin, 3,3′- Carbonylbiscoumarin, 3,3′-carbonylbis (7-diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,3,3′-carbonylbis (5,7-) dimethoxy-3,3 '-Biscoumarin, 3- (2'-benzimidazoloyl) -7-diethylaminocoumarin, 3- (2'-benzoxazoyl) -7-diethylaminocoumarin, 3- (5'-phenylthiadiazoyl-2') ) -7-diethylaminocoumarin, 3- (2′-benzthiazoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis ( And compounds such as 4-cyano-7-diethylamino) coumarin.

Of these coumarin compounds, 3,3′-carbonyl-7-dimethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferred.
The compounding amount of these coumarin compounds is 0.0001% by weight to 10% by weight, preferably 0.001% by weight to 3% by weight, based on the total amount of the photopolymerizable composition of the present invention. Preferably it is 0.005 weight%-1 weight%.
If it is less than 0.0001% by weight, the photocurability and physical properties or adhesiveness of the photopolymerizable composition tend to be lowered, and if it exceeds 10% by weight, the cured product is colored yellow.

In the photopolymerizable composition of the present invention, an acyl phosphine oxide compound and / or a bisacyl phosphine oxide compound are added and used as the component (b).
For example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4 , 6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

Of these acylphosphine oxides and / or bisacylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) acylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are particularly preferred.

The compounding amount of these acyl phosphine oxide compounds and / or bisacyl phosphine oxide compounds is 0.01 wt% to 10 wt% with respect to the total amount of the photopolymerizable composition of the present invention, preferably It is 0.1 to 5% by weight, particularly preferably 0.5 to 2% by weight.
When it is less than 0.01% by weight and more than 10% by weight, the photocurability of the photopolymerizable composition becomes insufficient, and physical properties or adhesiveness tends to be lowered.
As the polymerization accelerator which is the component (c) contained in the photopolymerizable composition of the present invention, a compound conventionally used as a photopolymerization accelerator or a room temperature polymerization accelerator can be used, and in particular, a barbituric acid derivative, Amines, tin compounds and sulfinic acids or their salts are preferred.
The barbituric acid derivative has the following general formula [1]

（Ｒ１、Ｒ２およびＲ３は同一もしくは異なっていてもよく、それぞれハロゲン原子、アルキル基、アルコキシ基、アリル基またはシクロヘキシル基等の置換基を有してもよい脂肪族、芳香族、脂環式または複素環式残基もしくは水素元素を表す。）で表される。

(R1, R2 and R3 may be the same or different and each may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, an allyl group or a cyclohexyl group, an aliphatic, aromatic, alicyclic or Represents a heterocyclic residue or a hydrogen element).

Specifically, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-ethylbarbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n-butylbarbituric acid 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3-dimethyl-5-cyclohexylbarbituric acid, , 3-Dimethyl-5-phenylbarbituric acid, l-cyclohexyl-1-ethylbarbituric acid, 1-benzyl-5-phen Rubarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1, 3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5 Hexyl barbituric acid, 5-butyl-1-cyclohexyl barbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (especially preferred are alkali metals or alkaline earth metals), For example, sodium 5-butyl barbiturate, 1,3,5-trimethyl Sodium Rubitsuru acid and 1-cyclohexyl-5-ethyl barbituric sodium tools acids and the like.
Particularly preferred barbituric acid derivatives are 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid and 1-benzyl-5-phenylbarbituric acid. .
Examples of the aromatic amine include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, and N, N-dimethyl. -3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4 -T-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2- Hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N- (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di- Isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, methyl 4-N, N-dimethylaminobenzoate Examples include esters, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, and the like.

Examples of the aliphatic amine include trimethylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, triethanolamine, 2- (dimethylamino) ethyl methacrylate, and N-methyl. Examples include diethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate, triethanolamine dimethacrylate, and triethanolamine trimethacrylate.
A particularly suitable amine is 4-N, N-dimethylaminobenzoic acid ethyl ester.

The tin compound is di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, di-n-butyltin dilaurate or mixtures thereof. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.
Examples of sulfinic acid or a salt thereof include benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, lithium benzenesulfinate, such as p-position toluenesulfinate, toluenesulfinate sodium, toluenesulfinate Potassium, calcium toluenesulfinate, lithium toluenesulfinate, 2,4,6-trimethylbenzenesulfinic acid, sodium 2,4,6-trimethylbenzenesulfinate, potassium 2,4,6-trimethylbenzenesulfinate, 2,4 , 6-trimethylbenzenesulfinate calcium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-triethylbenzenesulfinate, 2,4,6-triethyl Sodium sulfenate, potassium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-isopropylbenzenesulfine Acid, sodium 2,4,6-isopropylbenzenesulfinate, calcium 2,4,6-isopropylbenzenesulfinate, potassium 2,4,6-isopropylbenzenesulfinate, lithium 2,4,6-isopropylbenzenesulfinate, etc. Among them, sodium benzenesulfinate and sodium p-toluenesulfinate are particularly preferable.

You may add the compound which has aldehydes and a thiol group as a polymerization accelerator of (c) component of the photopolymerizable composition of this invention. Examples of aldehydes include dimethylaminobenzaldehyde and terephthalaldehyde. Examples of the compound having a thiol group include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid.

These polymerization accelerators for component (c) may be used alone or in combination of two or more compounds. The amount of component (c) used is usually 0.01% to 10% by weight, preferably 0.1% to 5% by weight, based on the total amount of the photopolymerizable composition of the present invention. Particularly preferably 0.5 to 2% by weight. When it is less than 0.01% by weight and more than 10% by weight, the photocuring property of the photopolymerizable composition becomes insufficient, and physical properties and adhesiveness tend to be lowered or colored.

In addition to the components (a) to (c) of the photopolymerizable composition of the present invention, an α-diketone, in particular, a photosensitizer other than a coumarin compound having a maximum absorption wavelength at 300 to 500 nm as component (d). Thioxanthones may be added. For example, diacetyl, dibenzyl, D, L-camphorquinone, thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N , N, N-trimethyl-1-propanaminium chloride, etc. can be used, and D, L-camphorquinone and 2-chlorothioxanthen-9-one are particularly preferred.

These (d) component α-diketones and thioxanthones may be used alone or in combination of two or more compounds. The amount of component (d) used is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total amount of the photopolymerizable composition of the present invention. Particularly preferably 0.5 to 2% by weight. When it is less than 0.01% by weight and more than 10% by weight, the photocurability and physical properties of the photopolymerizable composition tend to be lowered or colored.

These photopolymerizable compositions may be used as a dual cure adhesive, resin cement, or composite resin in combination with a conventional chemical polymerization initiator such as a combination of an oxide and an amine. Examples of the peroxide include diacyl peroxides, peroxyesters, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides and the like. Specific examples of diacyl peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide. Examples of peroxyesters include t-butyl peroxybenzoate, bis-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy- Examples include 2-ethylhexanoate, t-butyl peroxyisopropyl carbonate, and the like. Examples of the dialkyl peroxides include dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, and the like. Examples of peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and the like. Examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, and methyl acetoacetate peroxide. Examples of hydroperoxides include t-butyl hydroperoxide, cumene hydroperoxide, p-diisopropylbenzene peroxide, and the like.

The photopolymerizable composition of the present invention comprises the above components (a) to (c) or (a) to (d) as essential fillers such as inorganic and organic fillers, solvents, modifiers, thickeners, Dyes, pigments, polymerization regulators, polymerization inhibitors, and the like may be appropriately blended.

For example, as filler, polymethyl methacrylate, polyethyl methacrylate, copolymer of methyl methacrylate and ethyl methacrylate, organic polymer powder such as polystyrene, thermosetting resin cured product or cured thermosetting resin containing inorganic filler, etc. Organic filler or pulverized organic filler (kaolin, talc, quartz, silica, colloidal silica, alumina, aluminosilicate silicon nitride, barium sulfate, calcium phosphate, barium sulfate, glass powder, fluoroaluminosilicate glass, etc.), inorganic filler And fillers (PRG fillers) produced by pre-reacting a pre-reaction of a composite filler of an agent with an organic filler, fluoroaluminosilicate glass and acid-reactive glass, polyalkenoic acid and water, forming a gel, and the like, The composition is Strike like, it is suitable for use in slurry. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene and the like, which are suitable for stabilizing the shelf life of the composition.

Examples of the solvent include water, alcohols such as ethanol, methanol, 1-propanol, and isopropyl alcohol; ketones such as acetone, methyl ethyl ketone, pentanone, and hexanone; esters such as ethyl acetate, methyl acetate, and ethyl propionate; Ethers such as 2-dimethoxyethane, 1,2-diethoxyethane and tetrahydrofuran, hydrocarbons such as heptane, hexane, octane and toluene, and halogenated hydrocarbons such as chloroform and dichloromethane are preferably used. Of these, ethanol, isopropyl alcohol, acetone, water and the like are preferably used.

As an embodiment for carrying out the present invention in the dental field, the photopolymerizable composition comprises a dental photopolymerization type bonding agent, a composite resin, a fisher sealant, an orthodontic adhesive, a teeth coating agent, and a composite for crown and bridge. It may be used for resins and opaque agents.

Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, this invention is not limited to these Examples at all.

Examples 1 to 3 and Comparative Examples 1 to 11
In carrying out the present invention, bisphenol A-diglycidyl methacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and a photopolymerization initiator are configured as radically polymerizable monomers of the photopolymerizable composition ( a) As component coumarin compounds, 3,3′-carbonyl-7-dimethylaminocoumarin-7′-bis (butoxyethyl) aminocoumarin (KM-1), 3,3′-carbonylbis (7-dibutylaminocoumarin) ) (KM-2), (b) component acylphosphine oxide as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TBDPO) and (c) component polymerization accelerator as 4-N, N- Photocurability comprising dimethylaminobenzoic acid ethyl ester (4-MABE) It was evaluated photocurable formed product. The photocurable composition was prepared by adding the radical polymerizable monomer Bis-GMA / TEGDMA (= 60/40% by weight) to the amount of the photopolymerization initiator shown in Table 1 and mixing to 100% by weight. did. Focusing on decolorization of the photocured product (yellow), the amount of the coumarin compound was set to 0.005 and 0.05% by weight.

As a photocuring evaluation method, a sample of about 25 mg of the photopolymerizable composition was taken on a white paper board for dental cement, and an irradiation distance of 2.0 mm and an irradiation time of 30 seconds using three types of light irradiators. Photopolymerized. Here, the light irradiator is Matsukaze Grip Light II (Hal) using a halogen lamp [manufactured by Matsukaze Co., Ltd.], and a light emitting diode (LED) irradiator is Eliper Free Light 2 (LED) (3M, manufactured by Esper) And Xenon lamp Apollo Elite 95E (Xe) (manufactured by DMD). The illumination intensity of each light irradiator was used at Matsukaze Grip Light II: 650 mW / cm 2, Eliper Free Light 2: 635 mW / cm 2, and APPOLLOELITE 95E: 1330 mW / cm 2. The illuminance measurement wavelength region of these irradiators was set to 400 to 515 nm.

[Photocurability and score method]
The evaluation of the photocured product was scored by the following evaluation method on the curability and visual color tone of the cured product pressed with a dental vicker needle immediately after each light irradiation.
5: Sufficient curability is exhibited and there are very few unpolymerized portions on the surface layer.
4: Sufficient curability is exhibited and there are few unpolymerized portions of the surface layer.
3: Sufficient curability is exhibited, but a little unpolymerized portion remains on the surface layer.
2: Although cured, the cured product is colored (not decolorized), and many unpolymerized portions remain on the surface layer.
1 ... It is colored (not decolorized) only by gelation.
0 ... Uncured

Using the photopolymerizable compositions of Examples 1 to 4, photopolymerization time was determined by a photo DSC method as a photocuring evaluation method, and the photopolymerization rate was evaluated. The results are shown in Table 1.

[Optical DSC method]
About 10 mg of a sample of the photopolymerizable composition was collected in an aluminum pan dedicated to DSC, and a differential heat calorimeter (DSC: manufactured by Horiba, Ltd.) connected with a tip glass cable of Matsukaze Griplight II (Hal) (manufactured by Matsukaze Co., Ltd.). ), The arrival time from light irradiation to the maximum polymerization exotherm was measured and used as the photopolymerization time. Here, the illuminance at the tip of the optical cable in contact with the aluminum pan in the DSC was 80 mW / cm 2. The illuminance measurement wavelength region of the irradiator was 400 to 500 nm.

As is clear from the results in Table 1, the photopolymerizable composition containing (a) a coumarin compound, (b) an acylphosphine oxide, and (c) a polymerization accelerator constituting the photopolymerization initiator of the present invention is halogen light. , LED and xenon lamps showed high photo-curing property when irradiated with light. On the other hand, as is clear in Comparative Examples 1 to 11, when there was no component of any of (a) to (c), a high level of photocurability could not be obtained with the above three types of irradiators. Further, as in Comparative Example 10 and Comparative Examples 4 and 7, acyl phosphine oxide alone or a polymerization initiator composed of acyl phosphine oxide and a coumarin compound has good photocurability by halogen light, but light from LED or xenon lamp. Curability was significantly reduced.

In addition, from this example, the coumarin compound is excellent in the photopolymerization initiation effect because the photocuring property is increased in a very small amount of 0.005% by weight, and since there is little coloring, in the dental field that strictly requires aesthetics. This suggests that the application of is effective.
On the other hand, the photopolymerizable composition of the present invention has a high polymerization rate and high polymerization activity even in the photo DSC method. Moreover, when the photocurability by halogen light of Example 1 and 2 or 3 and 4 and the photopolymerization time by optical DSC are contrasted, the tendency of photopolymerization time and photocurability is in agreement with high precision. Since the photocurability of Example 1 indicates that the polymerization activity of the photopolymerizable composition is effective as an evaluation method in the same manner as the photo DSC method, the evaluation method using three types of light irradiators is Example 1. It carried out according to the photocurability of.

Examples 5-7, Comparative Examples 12-15
Bis-GMA and TEGDMA are used as radical polymerizable monomers of the present invention, KM-1, KM-2, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TBDPO) and bisacyl as acylphosphine oxides IC819 of bis (2,4,6-trimethylbenzoyl) acylphosphine oxide as phosphine oxide and IC1800 containing bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (IC819 and IC1800 manufactured by Ciba Specialty Chemicals), and 1,3,5-trimethylbarbituric acid (TMBA), di-n-octyltin dilaurate (Tin-Lau), di-n-butyltin as polymerization accelerators Dilaurate The Butyl-Tin) photopolymerizable composition consisting of was prepared with the composition of Table 3 was evaluated photocurable according to the method of Example 1.

From the results of Comparative Examples 12 to 13 in Table 2, the acylphosphine oxide and the photopolymerization accelerator showed high photopolymerization activity in the LED irradiator, but the xenon lamp significantly decreased. From the results of Comparative Examples 14 to 15, the combination of bisacylphosphine oxide and the tin compound showed high photopolymerizability with a halogen lamp, but the photocurability was greatly lowered or completely photocured with an LED irradiator and a xenon lamp. There was a case not to do. However, as shown in Examples 5 to 7, a photocurable composition containing (a) a coumarin compound, (b) an acylphosphine oxide, and (c) a polymerization accelerator constituting the photopolymerization initiator of the present invention. Exhibited high photocurability and little coloration in any light irradiation of halogen light, LED, and xenon lamp.
Examples 8-12
Bis-GMA and TEGDMA are used as radically polymerizable monomers of the present invention, KM-1, KM-2 as coumarin compounds, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide (TBMPO as acylphosphine oxide). ), Benzoyldiphenylphosphine oxide (BDPO) and a polymerization accelerator comprising 5-butyl barbituric acid (BBA) and 1-cyclohexyl-5-ethylbarbituric acid (CEBA). The photocurability was evaluated in accordance with the method of Example 1.

As is apparent from the results in Table 3, (a) a coumarin compound constituting the photopolymerization initiator of the present invention, (b) TBMPO as an acylphosphine oxide, and (c) a TMBA of a barbituric acid derivative as a polymerization accelerator. , BBA, CEBA, and the photopolymerizable composition showed high photocurability in any light irradiation of halogen light, LED, and xenon lamp.

Examples 13-21
As the radical polymerizable monomer of the present invention, Bis-GMA and TEGDMA are used, KM-1, KM-2, TBDPO as acylphosphine oxide, IC819, IC1800 as bisacylphosphine oxide, and MABE as reducing agent. A photopolymerizable composition comprising TMBA, Tin-Lau, and Butyl-Tin was prepared with the composition shown in Table 4, and the photocurability was evaluated according to the method of Example 1.

As is apparent from the results in Table 4, (a) a coumarin compound, (b) an acylphosphine oxide, a bisacylphosphine oxide constituting the photopolymerization initiator of the present invention, and (c) an aromatic amino acid as a polymerization accelerator. The photocurable composition containing the compound, the barbituric acid derivative, and the tin compound showed high photocurability even when irradiated with halogen light, LED, or xenon lamp.

Examples 22-32
As the radical polymerizable monomer of the present invention, Bis-GMA and TEGDMA are used as KM-1, KM-2, acylphosphine oxide is TBDPO, bisacylphosphine oxide is IC819, IC1800, and polymerization accelerator is MABE. A photopolymerizable composition comprising TMBA, Tin-Lau, Butyl-Tin, and in addition to these, D, L-camphorquinone (CQ) 2-chlorothioxanthen-9-one (CTQ) is shown in Table 5. It prepared with the composition and evaluated photocurability according to the method of Example 1.

As is apparent from the results in Table 5, (a) a coumarin compound, (b) an acyl phosphine oxide, a bisacyl phosphine oxide constituting the photopolymerization initiator of the present invention, and (c) an aromatic amino acid as a polymerization accelerator. A photocurable composition containing (d) D, L-camphorquinone or 2-chlorothioxanthone in addition to a compound, a barbituric acid derivative and a tin compound is extremely high in any light irradiation of halogen light, LED, and xenon lamp. It showed photocurability.

Example 33 and Comparative Examples 17-19
The photopolymerizable composition of the present invention was examined in the form of a photopolymerizable bonding agent. As radical polymerizable monomers, Bis-GMA (62 parts by weight), TEGDMA (30 parts by weight), 4-acryloxyethyl trimellitic acid (4-AET) (3 parts by weight), 2-hydroxyethyl methacrylate (5 Parts by weight) and butylated hydroxytoluene (300 ppm) were mixed to prepare Resin Composition A. On the other hand, KM-2 of a coumarin compound as a photopolymerization initiator, TBDPO as an acylphosphine oxide, and 4-MABE as a polymerization accelerator were mixed in the composition shown in Table 7, and the resin composition A was added thereto. A photopolymerization bonding agent was prepared by mixing to a weight percent.

[Shear adhesion test]
The tooth quality was changed to human teeth and freshly extracted bovine anterior teeth were used. The roots were removed and the pulp removed, and then embedded in epoxy resin. After removing the enamel on the lip surface of the bovine tooth, the dentin is polished with water-resistant polishing paper No. 600 under water pouring and a double-sided tape with a diameter of 4 mm is applied to define the adhesive surface. Dentin primer manufactured by Matsukaze Co., Ltd. was applied to the dentin with a microbrush, allowed to stand for 20 seconds, and dried with compressed air containing no oil. A trial bonding sword was applied to the primer-treated surface and irradiated with light for 20 seconds. Thereafter, a plastic mold having a diameter of 4 mm and a height of 2 mm was fixed, and a photopolymerizable composite resin “Beauty Fill” [manufactured by Matsukaze Co., Ltd.] was filled in the mold and irradiated with light for 30 seconds. Here, for the light irradiation of the bonding agent and the composite resin, three types of Matsukaze Griplight II (Hal), Eliper Freelight 2 (LED), or Apollo Elite 95E (Xe) were used. The illuminance of each light irradiator was used at the illuminance according to Example 1. After photocuring, the mold was removed to prepare an adhesion test body. After the test specimen was immersed in distilled water at 37 ° C. for 24 hours, the shear bond strength was measured at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, Instron), and n = 7 The average value was obtained. The results are shown in Table 6.

As is apparent from the results in Table 6, in the conventional techniques of Comparative Examples 17 and 19, the adhesive strength by halogen light tended to be high, but in the case of a xenon lamp, the adhesive strength was low. Moreover, in Comparative Example 18, all the irradiators showed extremely low adhesion strength. On the other hand, in the embodiment using the photopolymerizable composition of the present invention as a photopolymerization bonding agent, (a) a coumarin compound constituting the photopolymerization initiator, (b) an acylphosphine oxide (c) a polymerization accelerator. Due to the photopolymerization activity effect, it became clear that the dentin bond strength was high in any light irradiation of halogen light, LED, and xenon lamp.

Examples 34 and 35
In examining the photopolymerizable composition of the present invention in the form of a photopolymerizable bonding agent, as a radical polymerizable monomer, Bis-GMA (60 parts by weight), TEGDMA (30 parts by weight), 6-methacryloxy Hexyl-3-phosphonoacetate (MHPA) (2 parts by weight), 4-acryloxyethyl trimellitic acid (4-AET) (3 parts by weight), 2-hydroxyethyl methacrylate (5 parts by weight) and butylated hydroxytoluene (300 ppm) was mixed to prepare Resin Composition B. On the other hand, KM-2 of a coumarin compound as a photopolymerization initiator, TBDPO as an acylphosphine oxide, Tin-Lau as a polymerization accelerator, and CQ were mixed in the composition shown in Table 8, and the resin composition B was added thereto. The composition was mixed so as to be 100% by weight to prepare a photopolymerization bonding agent composition. Using these bonding agents, dentin bond strength was measured according to the adhesion test of Example 37. The results are shown in Table 7.

As is clear from the results in Table 7, the photopolymerization bonding agent as an embodiment of the photopolymerizable composition of the present invention comprises (a) a coumarin compound and (b) an acylphosphine constituting the photopolymerization initiator of the present invention. Due to the photopolymerization activity effect of fin oxide and (c) polymerization accelerator, it became clear that the dentin bond strength was high in any light irradiation of halogen light, LED and xenon lamp.

Example 36
The photopolymerizable composition of the present invention was examined in the form of a photopolymerizable composite resin. Resin composition C was prepared by mixing Bis-GMA (60 parts by weight) and TEGDMA (40 parts by weight) as a radical polymerizable monomer. On the other hand, KM-2 of a coumarin compound as a photopolymerization initiator, IC819 as a bisacylphosphine oxide, 4-MABE and CQ as a polymerization accelerator were mixed, and the resin composition C was added thereto to add 100% by weight. The matrix resin composition was prepared by mixing. Here, the concentration of the photopolymerization initiator of the present invention is 0.005% by weight of KM-2, 0.7% by weight of IC819, 0.7% by weight of 4-MABE, and 0.3% of CQ in the matrix resin composition. % By weight.
Next, fluoroaluminosilicate glass and acid-reactive glass and polyacrylic acid as a filler are pre-reacted in water to form a gel, dried and then silane-treated to obtain a surface-reactive prereacted glass ionomer filler (S-PRG filler) ) Manufactured.
Matrix resin composition (22 parts by weight), S-PRG filler (25 parts by weight), fluoroaluminosilicate glass (50 parts by weight) and ultrafine filler (Aerosil R-972: manufactured by Nippon Aerosil Co., Ltd.) (3 parts by weight) A prototype photopolymerized composite resin was prepared by uniformly kneading and defoaming with a kneader.

[Curing depth (mm)]
The prototype photopolymerization composite resin is inserted into a stainless steel mold with a diameter of 4 mm and a height of 15 mm, the upper and lower surfaces of the mold are pressed against each other with a thin slide glass, and placed on a white paper plate. Were directly contacted and irradiated with light for 30 seconds. Here, for the light irradiation of the composite resin, three types of Matsukaze Grip Light II (Hal), Eliper Free Light 2 (LED), or Apollo Elite 95E (Xe) were used. The illuminance of each light irradiator was used at the illuminance according to Example 1. After photocuring, the mold is removed and the photocured product is taken out. The backside of the light irradiation is wiped with an alcohol-impregnated surface to remove the uncured portion, and the length of the remaining cured product is measured to determine the photocuring depth. did.

[Hardness]
Insert the prototype photopolymerization composite resin into a stainless steel mold with a diameter of 4 mm and a height of 2 mm, press the upper and lower surfaces of the mold with a thin glass slide and place it on a white paper plate. Were directly contacted and irradiated with light for 30 seconds in the same manner as in the above-mentioned “depth of curing”. After photocuring, the mold was removed, the photocured product was taken out, and a hardness test body was produced. After the test specimen was immersed in distilled water at 37 ° C. for 24 hours, the irradiated surface (front surface) and the back surface Vickers hardness (MICRO HARDNESS TESTER: manufactured by Matsuzawa Seiki Co., Ltd.) of the cured product were measured.

[Compression strength]
The prototype photopolymerization composite resin is inserted into a stainless steel mold with a diameter of 3 mm and a height of 6 mm, and the upper and lower surfaces of the mold are pressed with a thin slide glass and placed on a white paper plate. The cable was brought into direct contact and irradiated with light for 30 seconds in the same manner as in the above “light curing depth”. Similarly, light irradiation was performed from the back surface for 30 seconds. After photocuring, the mold was removed and the photocured product was taken out to produce a compression test specimen. The test specimen was immersed in distilled water at 37 ° C. for 24 hours, and the compressive strength was measured at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, Instron). The average of n = 5 The value was determined.
Table 8 shows the results of the curing depth, Vickers hardness and compressive strength measured by the above method.

As is apparent from the results in Table 8, the photopolymerizable composite resin as an embodiment of the photopolymerizable composition of the present invention comprises (a) a coumarin compound and (b) an acylphosphine constituting the photopolymerization initiator of the present invention. Due to the photopolymerization activity effect of the fin oxide (c) polymerization accelerator and (d) α-diketone, the photocuring depth, Vickers hardness, compressive strength, etc. in any light irradiation of halogen light, LED, xenon lamp, etc. It was revealed that the physical properties were high.

Claims (3)

A photocurable composition comprising a radical polymerizable monomer and a photopolymerization initiator, wherein the photopolymerization initiator is (a) a coumarin compound,
(B) acylphosphine oxide and / or bisacylphosphine oxide,
(C) a polymerization accelerator,
A photopolymerizable composition comprising: The light according to claim 1, wherein the photopolymerizable composition is a dental photopolymerization type bonding agent and composite resin that can be photocured by a light irradiator such as a halogen lamp, a light emitting diode (LED), and a xenon lamp. Polymerizable composition. The photopolymerizable composition according to claim 1 or 2, wherein the photopolymerizable composition further contains (d) an α-diketone and / or a thioxanthone.