Photopolymerizable composition for dental restoration

[Detailed Description of the Invention]

[Industrial Application] The present invention relates to the photo polymerization constituent for dentistry restoration, especially, high sensitivity is shown also to the light source of which field of visible light and a purple outdoor daylight line, and a polymerization hardened material is related with the photo polymerization constituent for dentistry restoration excellent in color tone stability and physical properties. [Description of the Prior Art] Like common knowledge, what is called a chemicals polymerization type and a photo polymerization type of composite resin restoration material is used with dentistry. Chemicals polymerization type composite resin restoration material, It has the shape of a paste which comprises binder resin for the main ingredients to combine a detailed minerals filler and a minerals filler comrade, While divides this thing into two, a peroxide is contained in a paste and the paste of another side is made to have contained amine. The paste of this etc. is mixed at the time of use, and it is after restoration of this paste to Caval cavity etc., 9 which is that in which binder resin carries out polymerization hardening by the oxidation-reduction reaction of peroxide-amine into a definite period of time -- as this seed type of a fault, cure time is constant, between the states where a way person has the reversibility before a paste hardens, restoration operation needed to be completed and the operational difficulty has been pointed out. Since a hardening reaction does not advance unless it irradiates with light in the photo polymerization type composite resin restoration material which used the photo polymerization catalyst instead of the peroxide-amine system catalyst in a chemicals polymerization, Since operate time and cure time are substantially controllable according to a way person's will, there are many advantages, such as it being possible to obtain the optimal treating method and disposal time, and being, and the case of photo polymerization type restoration material use has been increasing with dentistry recently. Although many constituents of the restoration material for photo polymerization type dentistries are known, many visible light hardening type restoration material is especially used in respect of the safe use in the mouth. For example, the constituent indicated to the British patent No. 1408265 specification, JP,57-1.87377,A, JP,53-62394,A, JP,57-54107,A, JP,57-77609,A, JP,58-65704,A, etc. is known. The invention of this etc. relates to the method of using alpha-Diketone written in the British patent No. 1408265 specification, and a reducing agent, and the combination of camphor quinone and amine is used with the product of Mostly in fact. [Problem(s) to be Solved by the Invention] Visible light hardening type restoration material is hardened in 400~500 nm of wavelength bands, and a satisfactory hardened material is not obtained in the wavelength band below 400 nm. It is easy to be subject to the influence by the intensity of light, and the source of irradiation light to the Return part of a reaction is insufficient, there are many unreacted remains monomers, color tone stability is also inferior, and satisfactory physical properties are not necessarily acquired on clinical. The thing of the statement is known by JP,51-2235,B, JP,53-82088,A, etc. about the purple outdoor daylight line hardening type constituent for dentistries. Within the mouth, use is not directly carried out for the reason a purple outdoor daylight line with a wavelength of 300 nm or less is harmful to a human body. It is pointed out that hardening depth is also shallow as a fault. The two above-mentioned types are hardened in a wavelength band for exclusive use, respectively, and the photo polymerization constituent which has good hardenability in any wavelength band of a purple outdoor daylight line and visible light is not known now. [Means for Solving the Problem] The present invention is a photo polymerization constituent for dentistry restoration of high sensitivity nature new type which solved the above-mentioned fault. That is, if three sorts, a Ketar system compound of a photopolymerization initiator which is a composition ingredient of the present invention, a benzoin alkyl ether system compound, and a reducing agent, are made to live together, it will find out that the photo polymerization start capability to have excelled also in which field of a purple outdoor daylight line and visible light by the synergistic effect is shown. When it is used, having made a Ketar system compound coexist with independence or a reducing agent, to a purple outdoor daylight line of a 400-nm non-drop, it is effective, but to visible light of 400 nm or more, Mostly does not have photo polymerization start capability. When it is used, being independent or having made a benzoin alkyl ether system compound coexist with a reducing agent, Mostly does not have photo polymerization start capability to visible light of 400 nm or more, Although photo polymerization nature is accepted as for some constituents which comprise a mixed system of two sorts of photopolymerization initiators with a Ketar system except a reducing agent and a benzoin alkyl ether system which are not obtained by this as for a satisfactory hardened material, the hardened material is insufficient in 1 intensity, when using as a restoration thing for dentistries, and it is impractical. However, especially a constituent that used together the composition ingredient by the present invention, i.e., a Ketar system compound, a benzoin alkyl ether system compound, and a reducing agent is excellent in polymerization start capability to 300~500-nm light, Since the hardened material was excellent in intensity, hardness, etc., character desirable as an object for dentistries was acquired, and also it found out having the characteristic excellent also in color tone stability to which importance is attached with dentistry. Namely, a compound in which the present invention contains at least one (a) ethylenic unsaturated double combination and which can be polymerized. (b) General formula [1] R O 0R H and CQ, as for A, in [, however X in a formula, R is a Alkyl machine with 1~10 carbon atoms, an aralkyl group with 7~9 carbon atoms, or size about an aromatic series machine of six shellfishes in a Alkyl machine with 1~5 carbon atoms, or an alkoxy group with 1~5 carbon atoms. A photopolymerization initiator, the (C) general formula [2] which are chosen from a Ketar system compound showing a basis denoted by hand CnCnH2n0-' (however, inside n of a formula expresses an integer of 2~5, an integer of 1~5 is expressed 1 m, and R' expresses a Alkyl machine with 1~5 carbon atoms.) shown by] one or more sorts, and change Inside R of [, however a formula is a Alkyl machine, and R' is chosen from a hydrogen atom, a Alkyl machine, a halogen atom, and an alkoxy group. As for R#, one piece or more than it can exist by a case on each phenyl ring in a formula, and R' is a Alkyl machine and an alkoxy group. It is chosen out of a halogen atom and an alkylamino group. A photopolymerization initiator which is chosen from a benzoin alkyl ether system compound shown by Co one or more sorts, and changes. (d) Contain 5 composition acid content of a reducing agent and the (e) filler ,. About an ethylenic compound which is the 1st composition ingredient in a constituent of the present invention, It is a compound which has at least one ethylenic unsaturated double combination in the chemical structure, and has chemical forms, such as copolymers, such as it, in mixture ifepsilon Facial expression, such as a monomer, pre polymer (namely, a dimer, a trimer, and other oligomer), and it. As a monomer which specifically has one ethylenic unsaturated double combination, it is a methylmetaacrylate. Ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate. Acrylate, such as tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and this; as a monomer with two ethylenic unsaturated double combination, At an aromatic series system, they are 2,2-bis(methacryloxy-phenyl)propane and 2,2-screw C4-(2-hydroxy 3-methacryloxy-phenyl)] propane, 2,2-bis(4-methacryloxy-ethoxy phenyl)propane, 2, and 2-bis(4-methacryloxydiethoxy phenyl)propane, There is acrylate, such as 2,2-bis(4-methacryloxy-propoxy phenyl)propane and this, and it is ethylene glycol dimethacrylate 2 diethylene-glycol dimethacrylate at; fatty series system, To triethylene glycol dimethacrylate and petit Chinese milk vetch recall Dimethacrylate- 1, There is acrylate, such as neopentyl glycol dimethacrylate, 1.3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, 1, and 6-hexane Ciel dimethacrylate and this. As a monomer which has three ethylenic unsaturated double combination, there is acrylate, such as trimethylolpropanetrimethacrylate, I-Limited roll ethane trimethacrylate, Penta erythritol trimethacrylate, trimethylolmethane trimethacrylate, and this. As a monomer which has four ethylenic unsaturated double combination, there is a monomer of a urethane system shown with pen Thaerythritol tea 1-lameter CREATE, Penta erythritol tetraacrylate, and the following structural formula (3) and (4). CH300CH. Ill l1lCH2=C-C-0-CH2CHCH2-O-C-C=CH2C=0 Mockery H (CH2%NH C=O C83000CH3 Ill l l1lCH2=C-C-0-CH2CHCH2-0-C-C=CH. C=O H phi CH. phi H C=0 In addition, there are methacryloxy-trimellitic acid and an acid anhydride. Acrylate and methacrylate, such as this, may use one of them, or may use it combining two or more sorts. As for a compound which has ethylenic unsaturated bonds, such as this, it is preferred to be blended to a filler in 90~1'O% of the weight of the range. When a compound which has an ethylenic unsaturated bond shifts a mentioned range in outside, formation good as restoration material for dentistries cannot be performed. Next, Benzyl dimethyl ketal to which a Ketar system compound shown by a general formula [1] as 2nd composition ingredient is expressed with a following formula CHl CH3 They are Benzyl diethyl ketal, Benzyl dipropyl cake tar, and Benzyl di (beta-phenylethyl) Ketar to of etc., Benzyl di (2-methoxy ethyl) Ketar, Benzyl di (2-ethoxyethyl) Ketar, Benzyl di (2-methoxy ethoxyethyl) Ketar, Benzyl di (2-ethoxy ethoxyethyl) Ketar, 4.4 '- dimethylbenzyl Dimethy Luke Taal and 2.2'-dimethoxybenzyl Diet Luke Taal, 4.4 '- dichloro Benzyl-Diet Luke Taal and 4.4'-dichloro Benzyl-Diprop Luke Taal, etc. are mentioned. Especially desirable Ketar system compounds are Benzyl dimethyl ketal, Benzyl diethyl ketal, Benzyl di (2-methoxy ethyl) Ketar, and 4.4'-dimethylbenzyl Dimethy Luke Taal. As a benzoin alkyl ether system compound which is the 3rd composition ingredient of the present invention, it is benzoin methyl ether, There are benzoin ethyl ether, benzoin iso-propyl ether, benzoin n-butyl ether, benzoin isobutyl ether, etc., and especially benzoin isobutyl ether is preferred in this etc. Photopolymerization initiators, such as this, may mix and use one sort or two sorts or more, respectively. As for the above-mentioned Ketar system and the amount of addition of a benzoin alkyl ether system photopolymerization initiator, it is preferred to use it in 0.01~5% of the weight of the range to a compound which has an ethylenic unsaturated bond, respectively. If this range is exceeded, hardenability 1 color-tone stability worsens and is unsuitable practically with dentistry. Although a feeling agent of Light increase is returned when a feeling agent of Light increase is in an excitation state as a reducing agent which is the 4th composition ingredient of the present invention, when a feeling agent of Light increase is not excited by active energy rays, it has the reduction capability that a feeling agent of Light increase cannot be returned. A reducing agent may be amine of the 1st class, the 2nd class, or the 3rd class, and a hydrogen atom may be sufficient as R' and R'. It can be bases R and R' and the same basis whose R' can be a hydrocarbon group beyond one piece or it. Alkyl, cycloalkyl, hydroxyalkyl, or an aralkyl group may be sufficient as a hydrocarbon group. They can be bases R and R' and a Alkyl machine in which R' has 1~16 carbon atoms suitably. As one piece or units R and R' beyond it, and an example of a suitable reducing agent whose R''' is hydrocarbon, they are propylamine, n-butylamine, pentylamine, hexyl amine, dimethylamine, and Diethyl amine. Dipro pill amine, a G n-butylamine, dipentylamine, trimethylamine, There are triethyl amine, tripropylamine, a tree n-butylamine, tripentylamine, dimethylaminoethyl methacrylate, diethylamino ethyl methacrylate, triethanol amine, dimethylamino ethanol, and long-chain aliphatic amine. an example of a reducing agent containing an aromatic series machine -- N and N'-Dimethyl aniline, N-methyldi phenylamine, 2-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid methyl, and 4-dimethylaminobenzoic acid butyl. 4-dimethylaminobenzoic acid 2-ethylhexyl. To settle Gia Min, such as 4-dimethylaminobenzoic acid iso Amir, has. However, an integer greater than or equal to 2, bases R and R', R', and R" may be the same or different, and n is a hydrogen atom or a hydrocarbon group, especially a Alkyl machine. As a reducing agent of this example, they may be N-hydrocarbon-group derivatives, such as ethylene diamine, trimethylene diamine, tetramethylen Diamine, pentamethylene Diamine, hexamethylenediamine, or it, especially N-alkyl derivative. As an example of a reducing agent in which element N has constituted a part of ring system, there is an N-hydrocarbon derivative of piperidine and piperidine, for example. As other reducing agents, it is triallyl amine. There is arylthio urea, aromatic series sulfinic acid salts, 5-Al kill-, or 5-Ally roux barbituric acid. In reducing agents, such as this, a dimethylaminoethyl Metari freight, triethanol amine, 4-dimethylaminobenzoic acid methyl, and 4-dimethylaminobenzoic acid ethyl are preferred. Concentration of reducing agents, such as this, is the color tone stability as an object for dentistries. 0.1~5% of the weight of concentration is preferred from hardenability to an ethylenic unsaturated substance. A polymerization prohibition agent, an ultraviolet ray absorbent, and organic peroxide which are usually used if needed besides the composition ingredient can be used. Which a filler organicity, inorganic matter or organicity, and compound [ inorganic ] may be sufficient as a filler which is the 5th composition ingredient, For example, the end of quartz powder, alumina powder, glass powder, kaolin, talc, calcium carbonate, There are what is called an organic compound filler etc. that hardened and ground barium alumino silicate glass, titanium oxide, borosilicate glass, colloidal silica powder, and colloidal silica by polymer, and it is as polymer powder, Polyacrylic acid methyl, poly methyl methacrylate, polymethacrylic acid ethyl, There are a methacrylic acid methyl ethyl methacrylate copolymer, crosslinked type poly methyl methacrylate, an ethylene-vinyl acetate copolymer, etc., or it can also mix and use 2nd grade polymer powder and the inorganic powder. Before the mineral filler performs mixture with a filler and binder resin, it is preferred to process using a coupling agent which can react to both a filler and by Cedar resin. As a coupling agent, the Silang coupling agent, a titanate coupling agent, an aluminum Nate coupling agent, etc. can be used. Or the surface of a minerals filler can be graft-ized and combination with binder resin can also be aimed at. As a Silang coupling agent, it is gamma-methacryloxpropyl trimethoxy silane, Vinyl trichlorosilane, vinyl tris (beta-methoxyethoxy) Silang, Gamma-methacryloxypropylmethyldimethoxysilane, gamma-glycidoxypropyltrimetoxysilane, Gamma-chloropropyltrimetoxysilane, beta-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane, Trimethylglurosilane, dimethyldi chloro Silane, hexamethyl Disilane, gamma-aminopropyl triethoxysilane, N-beta-(aminoethoxy)-gamma-aminopropyl 1-Remixthoxysilane, and gamma-Ureno -- an id -- propyltrimethoxysilane etc. are mentioned. A method in particular of carrying out a surface treatment using coupling agents, such as this, is not limited, but may use what kind of method. Although it changes with quality demanded and cannot generally be limited, if the amount of the finishing agent used generally chooses 0.1~20 % of the weight, preferably 1~10% of the weight of a range to an inorganic substance, it is preferred. Active energy rays which contain both visible light and a purple outdoor daylight line in visible light, a purple outdoor daylight line, or its spectrum may be sufficient as active energy rays used for the present invention. It is 240~600 nm in wavelength suitably. As a light source which can be applied to a constituent of the present invention, a carbon arc, Mercury lamp, a xenon lamp, a metal halide lamp, a fluorescence lamp, a tungsten lamp, argon ion laser, etc. can be used. [Function] As shown in Example 1~9, as compared with the method (comparative example 10) used conventionally, the constituent of the 1 present invention shows the hardenability excellent in any light source of visible light and a purple outdoor daylight line, and hardens it by irradiation for a short time, and, moreover, its hardening depth is also deep. 1 coloring tendency was not accepted as compared with the method (comparative example 10) by which the polymerization hardening object by composition of the present invention is known conventionally, but it is Mostly colorlessness and it was checked that excel in color tone stability and a value also with 1 high intensity is acquired. [Example] Although an example is given to below and the present invention is explained still more concretely, the present invention is not restricted to this etc. Example 1 2.2-screw (70 g of 4-(2-hydroxy 3-methacryloxy-phenyl)] propane) 30 g of triethylene glycol dimethacrylate, Benzyl dimethyl ketal 0.5g, 100 g of fine powder silica which carried out the surface treatment to benzoin isobutyl ether 0.5g and dimethylaminoethyl methacrylate 0.5 g by 3 g of gamma-methacryloxpropyl trimethoxy silane was kneaded under room temperature with a roll, and the constituent was produced. The paste was filled in the Teflon board which opened diameter 3 me and a 3-mm-thick circular hole, and it irradiated with visible light (the product made from one company of ICs, brand name; Luxor) from the 1-m upper part, and measured the color tone and resisting pressure intensity of the hardened material. Cure time investigated the degree of needle depth ON of the field of the side opposite to a visible light irradiation side (1 kg of load), and expressed it with the shortest visible light irradiation time from which the degree of needle ON is set to 0. The cure time similarly measured using the purple outdoor daylight line (the product made by GC, a brand name; permanent wave cure UC-1) was shown in (). The penetration circular hole of diameter 4 wr and thickness 10nvn was provided in the metallic mold made from stainless steel, and after filling the above-mentioned paste to this circular hole and covering the surface in cellophane paper, it irradiated with visible light (Brand-name: the product made by ICI, Luxor) for 45 seconds. Subsequently, after taking out the polymer from the circular hole and removing an unpolymerized thing, length was measured and it was considered as hardening depth. A result is shown in a table. Example 2~7. comparative example 1~10 The quantity which indicated to the table the Ketar system compound, the benzoin alkyl ether system compound, and the compound that indicated the reducing agent to the table in Example 1 was used, and also cure time 9 color tone of each composition, resisting pressure intensity, and hardening depth were investigated by the same method as Example 1. The example excluding only the reducing agent at comparative example 3 in the example excluding only the benzoin alkyl ether system compound at comparative example 2 in the example excluding only the Ketar system compound at comparative example 1 from the composition ingredient of the present invention was shown. The example of the camphor quinone widely used for the commercial item as comparative example 10 was given. A result is shown in a table. Example 8~9 In composition of Example 1, 30 g of 70g of fatty series urethane dimethacrylate + butanediol dimethacrylate is used as a monomer ingredient, Only the quantity indicated to the table used the compound which indicated the Ketar system compound, benzoin alkyl ether 5 compound, and the reducing agent to the table, and also it investigated cure time 9 color tone of each composition, resisting pressure intensity, and hardening depth by the same method as Example 1. A result is shown in a table. Following space [Effect of the Invention] If the photo polymerization constituent for dentistry restoration by the present invention is used, even if the thickness of a restoration thing is large, the hardening object which was excellent in physical properties by the light irradiation of operation for a short time will be acquired. Discoloration as which, as for the restoration thing by the constituent of the present invention, after two-year progress is regarded by the conventional products within the mouth, wear, breakage, etc. are [ in / the excelled clinical results from which Mostly observation was not carried out are shown, and / dentistry ] composite resin for restoration, pre-wearing hard resin, an inlay, and a Jacquela 822 artificial tooth. It was checked that it may be used for the objects, such as an object for floors, an object for repair, an object for Rebase for 2 individual trays, and an orthodontic material.