JPH09263604A - Photopolymerization initiator for adhesive and photopolymerizable adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerization initiator for an adhesive usable as a dental adhesive composition, extremely high in sensitivity to visible light and excellent in curability, comprising a specific sensitized coloring matter, a photo-acid generator and an aryl borate compound. SOLUTION: This photopolymerization initiator comprises (a) preferably 0.0005-30wt.% of a sensitized coloring matter having 350-680nm maximum absorption wavelength, such as 4-trifluoromethyl-7-aminocoumarin, (b) preferably 0.01-90wt.% of a photo-acid generator such as 2,4,6-tris(trichloromethyl)-s-triazine and (c) preferably 0.05-90wt.% of an aryl borate compound such as a trialkylphenyl borate. A polymerizable monomer comprising (meth)acrylate-based monomer containing >=5wt.% of an acidic group-containing (meth)acrylate-based monomer in an amount of 100 pts.wt. is mixed with 0.01-10 pts.wt. of the photopolymerization initiator for an adhesive to give a photopoylmerizable adhesive.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable adhesive preferably used in the field of adhesives, particularly dental adhesives, and a photopolymerization initiator used therein.

[0002]

2. Description of the Related Art In recent years, adhesives have been widely used in various fields such as automobiles, electronic industries, construction, and medical care. Among them, polymer adhesives that adhere by polymerization and curing of monomers include urethane-based, acrylic-based monomers, and the development of polymerization catalysts, as well as high adhesive strength, durability, heat resistance, water resistance, Many features such as photocurability, thermosetting, and adhesion to various materials have been found. As a result, polymer adhesives provide adhesives with characteristics that meet their requirements in various fields.

Photopolymerization initiators which generate radicals or ions upon irradiation with visible light to polymerize polymerizable unsaturated compounds or cyclic compounds are particularly useful in the field of dental adhesives, and the photopolymerization initiators are particularly useful. Regarding, various proposals have been made. Conventionally, it is general to use a combination of aromatic ketones and α-diketones represented by camphorquinone and amines. However, since adhesives using these photopolymerization catalysts have a problem in the adhesiveness with the tooth substance, it is necessary to improve the adhesive strength by treating the tooth surface with a pretreatment material called a primer or conditioner. There is. Therefore, an adhesive that strongly adheres to the tooth surface without any pretreatment is desired.

On the other hand, as a polymerization method using a borate compound as an initiator, JP-A-62-143044 and JP-A-1-111402 disclose a method using a dye-borate complex, but there is a problem that sensitivity is low. . Further, JP-A-6-329712 discloses a polymerization initiator composed of a combination of an acid compound containing a photoacid generator and a borate compound, but since it does not absorb visible light, polymerization does not occur with visible light. In some cases, depending on the photoacid generator selected, the polymerization may not be initiated at all.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an adhesive material having a sufficient sensitivity to visible light, a polymerizable composition containing the same and having excellent adhesiveness to tooth structure and high safety. The present invention aims to provide a polymerization initiator for use as well as a photopolymerizable adhesive containing the same.

[0006]

As a result of intensive studies to solve the above problems, the present inventor has found that a composition containing a specific sensitizing dye, a photoacid generator and an aryl borate compound achieves the above objects and achieves adhesion. It was found that there is a novel photopolymerization initiator that can be suitably used for the material, and the present invention has been proposed.

That is, according to the present invention, (A) a sensitizing dye having a maximum absorption wavelength of 350 to 680 nm, (B) a photoacid generator, and (C) an aryl borate compound are contained. A photopolymerization initiator for an adhesive is provided.

Furthermore, in a photopolymerizable adhesive containing a polymerizable monomer containing a (meth) acrylate-based monomer and the photopolymerization initiator as a main component, the photopolymerization initiator is photopolymerizable. Provided is a photopolymerizable adhesive characterized by comprising 0.01 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers in the adhesive composition.

The sensitizing dye as the component (A) used in the polymerization initiator for adhesives of the present invention has a maximum absorption wavelength of 350 to 68.
It is a dye having a wavelength of 0 nm and capable of generating an active species effective for polymerization by energy transfer or electron transfer with a monomer or a third substance upon irradiation with visible light, and in the present invention, (B) It is a dye that can sensitize and decompose the photoacid generator represented by the component.

The sensitizing dye has a maximum absorption wavelength of 35.
The sensitizing dye existing in 0 to 650 nm can be used without any limitation. Suitable sensitizing dyes include coumarin dyes, cyanine dyes, merocyanine dyes, thiazine dyes, azine dyes, acridine dyes, xanthene dyes, squalium dyes, and pyrilinium salt dyes. Among them, the sensitizing dye which is particularly effective in the present invention is a coumarin-based dye among the above-mentioned sensitizing dyes, and a small amount of the photoacid generator represented by the component (B) can be highly efficiently irradiated under visible light. Decomposes and has high activity.

Typical examples of the coumarin-based dye are represented by the following general formula (1).

[0012]

Embedded image

[Wherein R ₁ , R ₂ and R ₃ are the same or different hydrogen atom, halogen atom, alkyl group,
An alkoxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted alkenylamino group and an alicyclic amino group, R
_At least two of ₁ , R ₂ and R ₃ may combine with each other to form a ring, A is a hydrogen atom, a cyano group and a substituted or unsubstituted alkyl group, and B is a hydrogen atom, a substituted or unsubstituted group. A substituted aryl group, a heterocyclic group having 5 to 9 carbon atoms, or

[0014]

Embedded image

(However, Z is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted 3'-coumarino group. It is). ] The compound represented by this is mentioned.

Specific examples of coumarin dyes that are preferably used include 4-trifluoromethyl-7-aminocoumarin (maximum absorption wavelength 382 nm), 4-trifluoroethyl-7-dimethylaminocoumarin (maximum absorption wavelength). 397
nm), 3-phenyl-7-aminocoumarin (maximum absorption wavelength 380 nm), 3- (4'-acetylaminophenyl) -7-acetylaminocoumarin (maximum absorption wavelength 36)
4 nm), 3-phenyl-7- (2H-naphtho [1,2
d] triazol-2′-yl) coumarin (maximum absorption wavelength 375 nm), 3-ethoxycarbonyl-5,6-benzocoumarin (maximum absorption wavelength 375 nm), 4-trifluoromethylpiperidino [3,2-g] Coumarin (maximum absorption wavelength 406 nm), 2,3,6,7-tetrahydro-
11-oxo-1H, 5H, 11H,-[1] benzopyrano [6,7,8-ij] quinolizine-10 ethyl ester (maximum absorption wavelength 436 nm), 10-acetyl-
2,3,6,7-tetrahydro-1H, 5H, 11H-
[1] Benzopyrano [6,7,8-ij] quinolidine-
11-one (maximum absorption wavelength 452 nm), 3,3′-carbonylbis (7-diethylamino) coumarin (maximum absorption wavelength 461 nm), 3- (2′-benzimidazoyl) -7-diethylaminocoumarin (maximum absorption wavelength 45)
6 nm), 3- (2'-benzthiazoyl) -7-diethylaminocoumarin (maximum absorption wavelength 458 nm), 3-
(2′-benzothiazoyl) -4-cyano-7-diethylaminocoumarin (maximum absorption wavelength 464 nm), 2,
3,6,7-tetrahydro-1,1,7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1
H, 5H, 11H- [1] benzopyrano [6,7,8-
ij] quinolidine (maximum absorption wavelength 480 nm) and the like.

Specific examples of other sensitizing dyes that can be preferably used in the present invention include 3,3'-diethyl-2,2'-thiacyanine iodide (maximum absorption wavelength 375 nm) as a cyanine dye. , 1, 3, 3, 1 ', 3', 3'-
Hexamethyl-2,2'-indocyanine perchlorate (maximum absorption wavelength 433 nm), 1,3'-diethyl-
2,2'-quino-thiacyanine iodide (maximum absorption wavelength 485 nm), 1,3'-diethyl-2,2'-quino-selenacyanine iodide (maximum absorption wavelength 491)
nm), 1,1'-diethyl-2,2'-quinocyanine iodide (maximum absorption wavelength 523 nm), 1,1'-
Diethyl-2,4'-quinocyanine iodide (maximum absorption wavelength 559 nm), 1,1'-diethyl-4,4 '
-Quinocyanine iodide (maximum absorption wavelength 590n
m) monomethine cyanine dyes such as 3,3′-diethyl-2,2′-thiazolinocarbocyanine iodide (maximum absorption wavelength 445 nm), 3,3′-diethyl-
2,2'-oxacarbocyanine iodide (maximum absorption wavelength 483 nm), 3,3 ', 9-triethyl-5
5'-diphenyl-2,2'-oxacarbocyanine iodide (maximum absorption wavelength 502 nm), 1, 3, 3,
1 ', 3', 3'-hexamethyl-2,2'-thiacarbocyanine iodide (maximum absorption wavelength 545 nm),
3,3'-diethyl-2,2'-thiacarbocyanine iodide (maximum absorption wavelength 557 nm), 3,3'9-
Triethyl-2,2 '-(6,7,6', 7'-dibenzo) thiacarbocyanine iodide (maximum absorption wavelength 5
78 nm), trimethine cyanine dyes such as 1,1′-diethyl-2,4′-quinocarbocyanine iodide (maximum absorption wavelength 608 nm); 3,3′-diethyl-2,
2'-Oxadicarbocyanine iodide (maximum absorption wavelength 580 nm), 3,3'-diethyl-9,11-neopentylene-2,2'-thiadicarbocyanine iodide (maximum absorption wavelength 653 nm), 3,3 Examples include pentamethine cyanine dyes such as'-diethyl-2,2'-selena dicarbocyanine iodide (maximum absorption wavelength 662 nm).

A preferred specific example of the merocyanine dye is 3-ethyl-5- [2- (3-methyl-2-thiazolidinylidene) ethylidene] -2-thio-2,4-oxazolidinedione ( Maximum absorption wavelength 453nm), 1,3
-Diethyl-5- [2- (3-ethyl-2-benzothiazolinylidene) ethylidene] -2-thiohydantoin (maximum absorption wavelength 519 nm), 3-carboxymethyl-
5- [2- (3-Ethyl-2-benzothiazolinylidene) ethylidene] rhodanine (maximum absorption wavelength 520n
m), 3-ethyl-5- [2- (3-ethyl-2-benzothiazolinylidene) ethylidene] rhodine, 3-ethyl-5- [2- (3-ethyl-4-methyl-2-thiazolinylidene) ) Ethylidene Rhodanine (Maximum absorption wavelength 5
40 nm) and the like.

Specific examples of thiazine dyes include methylene blue (maximum absorption wavelength 655 nm), 3,
7-diamino-1,2 benzophenoxazonium perchlorate (maximum absorption wavelength 601 nm) and the like, and examples of azine dyes include 5-acetoxybenzophenazine (maximum absorption wavelength 404 nm) and 1-amino-4-nitrophenazine. (Maximum absorption wavelength 360 nm) and the like.

Further, if the acridine dye is specifically shown, 1-aminoacridine (maximum absorption wavelength 480n
m), 9- (2′-hydroxystyryl) acridine (maximum absorption wavelength 410 nm), acridine orange (maximum absorption wavelength 493 nm) and the like.

Other specific examples of xanthene dyes include rhodamine 110 (maximum absorption wavelength 510 nm),
Rhodamine 6G (maximum absorption wavelength 500 nm), tetramethylrhodamine perchlorate (maximum absorption wavelength 548n
m) and the like, and a specific example of a squarylium dye is 2-[[3-[(1,3-dihydro-1-ethyl-3,3,5-trimethyl-2H-indole-2-
Ilidene) methyl] -2-hydroxy-4-oxo-2
-Cyclobutene-1-ylidene] methyl] -1-ethyl-3,3,5-trimethyl-3H-indolium, internal salt (maximum absorption wavelength 643 nm), {4- [3- [4-
(N, N-Diethylamino) -2-hydroxyphenyl] -2-hydroxy-4-oxo-2-cyclobutene-1-ylidene] -3-hydroxy-2,5-cyclohexadiene-1-ylidene} -N-ethyl -N-octadecyl ammonium hydroxide, an internal salt (maximum absorption wavelength 626 nm), etc. are mentioned.

Further, as preferable specific examples of the pyrilinium salt dye, 2,6-diphenyl-4- (4-methylphenyl) thiopyrylium perchlorate (maximum absorption wavelength 404 nm), 2,6-bis (4 -Methylphenyl)
-4- (4-phenylthiopyrylium perchlorate (maximum absorption wavelength 436 nm), 2,4,6-triphenylthiopyrylium perchlorate (maximum absorption wavelength 415
nm).

The sensitizing dye to be used may be appropriately selected and used depending on the wavelength and intensity of light used for polymerization or the type and amount of the photo-acid generator represented by the component (B), and may be used alone or in combination of two or more. Can be used as a mixture. Further, the addition amount also varies depending on other components to be combined and the kind of the polymerizable monomer, but when a coumarin-based dye is used, it is usually 0.00001 to 50% by weight, more preferably 0% by weight in the polymerization initiator for an adhesive. In the range of 0.0005 to 30% by weight, and in the case of other dyes, it may be selected from the range of 0.1 to 50% by weight, more preferably 1 to 30% by weight in the polymerization initiator for adhesives. If the addition amount is less than the above range, it is not preferable because the sensitivity to visible light significantly decreases.
On the other hand, when the amount exceeds the above-mentioned range, coloring of the obtained cured product is increased, and further, since light is absorbed in the vicinity of the surface, there is a problem that a curing depth cannot be obtained.

The photoacid generator of the component (B) used in the polymerization initiator for adhesives of the present invention produces a Bronsted acid or a Lewis acid upon irradiation with light and is represented by the component (A) of the present invention. Any known substance can be used without limitation as long as it decomposes with a sensitizing dye under irradiation of visible light to generate an acid.

Examples of the photoacid generator include halomethyl group-substituted-s-triazine derivatives, diphenyliodonium salt compounds, sulfonium salt compounds, sulfonic acid ester compounds, disulfone compounds and diazonium salt compounds.

In the present invention, among the above-mentioned photoacid generators, the use of a halomethyl group-substituted-s-triazine derivative or a diphenyliodonium salt-based photoacid generator,
Energy is transferred with the sensitizing dye represented by the component (A) of the present invention to generate an acid with high efficiency by irradiation with visible light.

A typical halomethyl group-substituted-s-triazine derivative is represented by the following general formula (2).

[0028]

Embedded image

(Wherein R ₄ , R ₅ and R ₆ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted alkoxy group, R ₄ , R ₅ and R
_At least one of ₆ is a halomethyl group. ) And a halomethyl group-substituted-s-triazine derivative represented by .

Further, when a typical diphenyliodonium salt compound is represented by the general formula, the following general formula (3)

[0031]

Embedded image

(Wherein R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkenyl group,
An alkoxy group, M ⁻ is a halogen ion, BF ₄ ⁻ ,
PF ₆ ⁻ , AsF ₆ ⁻ , CF ₃ SO ₃ ⁻ and SbF ₆ ⁻ . ) The diphenyl iodonium salt compound shown by these is mentioned. .

As the halogen atom substituting the halomethyl group in the above general formula (2), halogen atoms of chlorine, bromine and iodine are preferably used, but a compound having a trichloromethyl group substituted with three chlorine atoms is Is generally used.

Hereinafter, specific examples of the halomethyl group-substituted-s-triazine derivative are 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-tris (tribromomethyl) -s. -Triazine, 2-methyl-
4,6-bis (trichloromethyl) -s-triazine,
2-Methyl-4,6-bis (tribromomethyl) -s-
Triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl ) -4,6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)-
s-triazine, 2- (2,4-dichlorophenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-Bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (p-methoxyphenyl) -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- (p- Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (o-methoxystyryl-4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-butoxystyryl) -4,6-
Bis (trichloromethyl) -s-triazine, 2-
(3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-
Examples thereof include trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the diphenyliodonium salt compound represented by the general formula (3) include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium and bis (p-tert-butylphenyl) iodonium. , Bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium and the like chlorides, bromides, tetrafluoroborate,
Hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate and the like can be mentioned. Particularly, from the viewpoint of solubility of the compound, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate. , And trifluoromethanesulfonate salt are preferably used.

Specific examples of other photoacid generators preferably used in the present invention include sulfonium salt compounds.
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphinate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, p-methoxyphenyldiphenylsulfonate hexafluoroantimonate, p-methoxyphenyldiphenylsulfonate tri Fluoromethane sulfonate, p-toluene diphenyl sulfonate hexafluoroantimonate, p-toluene diphenyl sulfonate trifluoromethane sulfonate, mesitylene diphenyl sulfonate trifluoromethane sulfonate, p-
(T-butyl) phenyl diphenyl sulfonate trifluoromethane sulfonate etc. are mentioned.

Specific examples of preferable sulfonic acid ester compounds include benzoin tosylate, α-methylol benzoin tosylate, and pyrogallol trimesylate.

Further, specific examples of the disulfone compound include diphenyldisulfone and di (p-tolyl) disulfone, and specific examples of the diazonium salt compound include naphthoquinone (1,2) diazide (2) -4-. Examples thereof include sodium sulfonate, sodium naphthoquinone (1,2) diazide (2) -5-sulfonate, naphthoquinone (1,2) diazide (2) -5-sulfonic acid tosyl ester and the like.

The above-mentioned photo-acid generator may be used alone or in combination of two or more kinds. Further, the addition amount is preferably 0.005 to 95% by weight, and more preferably 0.01 to 90% by weight in the polymerization initiator for adhesives. When the addition amount is less than 0.005% by weight, the polymerization does not proceed, and when it exceeds 90% by weight, various properties of the obtained cured product, for example, weather resistance and hardness of the cured product are deteriorated. Not preferable.

The aryl borate compound as the component (C) used in the photopolymerization initiator for an adhesive of the present invention is represented by the following general formula (4).

[0041]

Embedded image

(Wherein each of R ₁₁ , R ₁₂ and R ₁₃ is
They may be the same or different, and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
A substituted or unsubstituted aralkyl group or a substituted or unsubstituted alkenyl group, wherein R ₁₄ and R ₁₅ are a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or It is a substituted or unsubstituted phenyl group, and L ⁺ is a metal ion or an organic base ion. ),
Examples thereof include those having at least one boron-aryl bond in one molecule.

A borate compound having no boron-aryl bond has extremely poor storage stability and is easily undesirably decomposed by reacting with oxygen in the air.

Specific examples of the aryl borate compounds that are preferably used include trialkylphenylboron, trialkylboron and trialkyl (p-chlorophenyl) boron as borate compounds having one aryl group in one molecule. , Trialkyl (p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2- Methoxy-2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, Trialkyl (m-butyloxyphenyl) boron, trialkyl (m- Chi oxy phenyl) boron, trialkyl (p- octyloxyphenyl) boron (alkyl group is n- butyl group, n- octyl group, n-
Dodecyl group) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl Examples thereof include quinolinium salts and butylquinolinium salts.

The borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron and dialkyldi (3,5-bistrifluoro). Methyl) phenylboron, dialkyldi [3,5-bis (1,1,1,3,3,3-
Hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, Dialkyldi (m-butyloxyphenyl) boron, dialkyldi (m-octyloxyphenyl) boron, sodium salt, lithium salt, potassium salt, magnesium salt of dialkyldi (p-octyloxyphenyl) boron (alkyl group is the same as above), Tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt Salts and the like.

Further, examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron and monoalkyl. Tri (3,5-bistrifluoromethyl) phenylboron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, mono Alkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p
-Butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (m-octyloxyphenyl) boron, monoalkyltri (p-
Octyloxyphenyl) boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium Examples thereof include salts, methylquinolinium salts, ethylquinolinium salts and butylquinolinium salts.

Examples of the borate compound having four aryl groups in one molecule are tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron and tetrakis (3,5-bistrifluoromethyl). Phenylboron, tetrakis [3,5-
Bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) boron, tetrakis (p- Butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (m-butyloxyphenyl) boron,
Tetrakis (m-octyloxyphenyl) boron, tetrakis (p-octyloxyphenyl) boron, (p
-Fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron,
(P-Nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron, (p-octyloxyphenyl) Triphenylboron sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
Tetraethylammonium salt, methylpyridinium salt,
Ethyl pyridinium salts, butyl pyridinium salts, methyl quinolinium salts, ethyl quinolinium salts, butyl quinolinium salts and the like.

The borate compounds may be used alone or in combination of two or more.

The amount to be added is not generally decided depending on the kind and amount of the polymerizable monomer and the mixing ratio of other components, but it is usually 0.01 to 95 in the photopolymerization initiator for adhesives.
%, More preferably 0.05 to 90% by weight
It is blended in the range. If it is less than 0.01% by weight, the polymerization does not proceed sufficiently, and if it exceeds 95% by weight, various properties of the obtained cured product, for example, the hardness of the cured product, are not preferable.

(A) in the photoinitiator for adhesives of the present invention,
The types and addition ratios of the components (B) and (C) can be used without any problem as long as they are within the ranges described above. However, particularly when it is used as a photopolymerization initiator for adhesives for dentistry, particularly preferable types of the three components and their addition ratios are the sensitizing dye of the component (A) in 100 parts by weight of the total amount of the photopolymerization initiator. Has a maximum absorption wavelength of 400 to 600
Coumarin-based dye in the range of 0.00005% by weight to 3
0% by weight, or the maximum absorption wavelength is 400 to 600 nm
As a photoacid generator of the component (B), a trichloromethyltriazine system having two or three trichloromethyl groups substituted, or tetrafluoroborate, hexafluoro as a counter anion. Phosphate, hexafluoroantimonate,
The diphenyliodonium salt-based photoacid generator having a trifluoromethanesulfonate ion is 0.05 to 80% by weight, and the aryl borate compound as the component (C) is a tri- or tetraaryl borate compound of 0.0
5 to 90% by weight is included.

Among the visible light polymerization initiators of the present invention (A)
When only the components (B) and (C) excluding the components, that is, when there is no sensitizing dye, there is no absorption in visible light, and therefore polymerization does not occur in visible light. In addition, sufficient sensitivity cannot be obtained only with the components (A) and (B), and the components (A) and (C), and irradiation with a polymer for a long time is required before curing. Can't get enough hardness.

The photopolymerization initiator for adhesives of the present invention can be used in combination with other known polymerization initiators used for thermal polymerization, ultraviolet rays or visible rays. There is no limitation on other polymerization initiators, but if other polymerization initiators that are preferably used are exemplified, the thermal polymerization initiators include benzoyl peroxide, p-chlorobenzoyl peroxide, and tert.
-Butylperoxy-2-ethylhexanoate, te
Peroxides such as rt-butyl peroxydicarbonate and diisopropyl peroxydicarbonate, azo compounds such as azobisisobutyronitrile, tributylborane,
Examples thereof include boron compounds such as tributylborane partial oxidation.

Further, as an ultraviolet or visible light polymerization initiator, diacetyl, acetylbenzoyl, benzyl,
2,3-pentadione, 2,3-octadione, 4,
Α-diketones such as 4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether. ether;
2,4-Diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone and other thioxanthone derivatives; benzophenone, p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone and other benzophenone derivatives; 4,6-Trimethylbenzoyldiphenylphosphine oxide, bis (2,6-
Acylphosphine oxide derivatives such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are preferably used.

Particularly preferred are α-diketone / tertiary amine type and acylphosphine oxide type photopolymerization initiators. Among them, α-diketone is camphorquinone and benzyl, and tertiary amine is dialkylaminobenzoic acid. Acid derivatives and N, N-dialkylaminoethylmethacrylate are preferable, and acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6).
-Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide is preferred.

The above-mentioned polymerization initiators may be used alone or in combination of a plurality of types, if necessary.

These other polymerization initiators are used in an amount of 0 to 200 relative to 100 parts by weight of the total amount of the photopolymerization initiator for adhesives of the present invention.
It is desirable to add parts by weight, preferably 0 to 150 parts by weight.

The photopolymerization initiator of the present invention is blended with a polymerizable monomer and is useful as a photopolymerization initiator for an adhesive material by irradiation with visible light. Particularly, the polymerizable monomer in the adhesive composition is used. When combined with a (meth) acrylate-based monomer, it is preferable from the viewpoint of curing speed. The (meth) acrylate-based monomer is an acrylate-based monomer or a methacrylate-based monomer, and known ones can be used without particular limitation.

Examples of (meth) acrylate type monomers which are generally used preferably include methyl (meth) acrylate, ethyl (meth) acrylate and glycidyl (meth).
Acrylate, 2-cyanomethyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono. Mono (meth) acrylate monomers such as (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2'-
Bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,
2'-bis [4- (meth) acryloyloxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2'-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy]
Phenyl} propane, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, etc. Examples thereof include (meth) acrylate-based monomers. These (meth) acrylate monomers can be used alone or in combination of two or more.

When the polymerization initiator for adhesives of the present invention is used in a dental adhesive, a (meth) acrylate monomer containing an acidic group in the molecule is used as a (meth) acrylate monomer. It is preferred to use the body.

As the acidic group-containing (meth) acrylate type monomer, a carboxyl group or its anhydride in the molecule,
Alternatively, a known compound can be used without particular limitation as long as it is a (meth) acrylate-based monomer having an acidic group such as a phosphoric acid group or a sulfonic acid group. A typical acidic group-containing (meth) acrylate-based monomer is represented by the following general formula (5).
Indicated by

[0061]

[Chemical 6]

(Wherein R ₁₆ is a hydrogen atom or a methyl group, R ₁₇ is an organic residue having 2 to 6 carbon atoms and optionally having an ether bond and / or an ester bond, X represents a group containing a carboxyl group, a carboxyl group, a phosphoric acid group, a phosphoric acid ester group, or a sulfonic acid group.) In the general formula (5), X represents a carboxylic acid group, a carboxylic acid anhydride group, or phosphoric acid. It is a group containing a group, a phosphoric acid ester group or a sulfonic acid group, and the structure thereof is not particularly limited, but preferable specific examples are as follows.

[0063]

Embedded image

In the above general formula (5), the structure of R ₁₇ is not particularly limited, and a known divalent to hexavalent organic residue having 1 to 20 carbon atoms having an ether bond and / or an ester bond is used. Although it can be adopted, it will be specifically exemplified as follows.

[0065]

Embedded image

The preferred specific examples of the acidic group-containing (meth) acrylate-based monomer represented by the above general formula (4) are as follows.

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

(However, R ₁₆ is a hydrogen atom or a methyl group.) When the adhesive of the present invention is used for dental purposes, the acidic group-containing (specifically exemplified above) from the viewpoint of dentin adhesiveness ( Meta)
Among the acrylate-based monomers, those having a carboxyl group or a phosphoric acid group are particularly preferably used.

The above acidic group-containing (meth) acrylate-based monomer is preferably blended in an amount of 5 parts by weight or more based on 100 parts by weight of the total (meth) acrylate-based monomer in terms of adhesion to the tooth structure. Particularly preferred is 10 to 80 parts by weight.

In the present invention, when the photopolymerizable adhesive is polymerized, the above-mentioned (meth) acrylate-based monomer is often used in order to facilitate the polymerization of the composition, control the viscosity, or control other physical properties. It is also possible to mix and polymerize other polymerizable monomers other than the monomer. Examples of these polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate;
Styrene, divinylbenzene, α-methylstyrene, α
Examples thereof include styrene such as methylstyrene dimer and α-methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate and allyl diglycol carbonate. These other polymerizable monomers may be used alone or in combination of two or more.

Further, in the present invention, since a photo-acid generator is used, a compound capable of initiating polymerization with an acid, that is, another cationically polymerizable polymerizable monomer can be used in combination. Examples of suitable cationically polymerizable monomers include diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether and 1,4-
Bis (2,3-epoxypropoxyperfluoroisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcin diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenylglycidyl ether , P-tert-butylphenylglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, dibromophenylglycidyl ether, 1,2,7,8-diepoxyoctane, 4,4 ′
-Bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, ethylene glycol-bis (3,4) -Epoxy compounds such as epoxycyclohexanecarboxylate); vinyl-2-chloroethyl ether, vinyl-n
-Butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolethane trivinyl ether,
Examples thereof include vinyl ether compounds such as vinyl glycidyl ether, and these may be used alone or in combination of two or more kinds.

The amount of these other polymerizable monomers to be blended may be selected according to the purpose, but it is used in the range of 0 to 200 parts by weight with respect to 100 parts by weight of the above-mentioned (meth) acrylate monomer. It is preferable.

Further, the preferable mixing ratio of the photopolymerization initiator in the photopolymerizable adhesive of the present invention is 0.01 to 10 parts by weight based on 100 parts by weight of all the polymerizable monomers in the composition. Yes, and more preferably 0.05 to 5 parts by weight.

When the amount of the photopolymerization initiator added is less than 0.01 parts by weight, the polymerization does not proceed sufficiently, and when it exceeds 10 parts by weight, various properties such as hardness and weather resistance of the cured product are obtained. Is decreased, which is not preferable.

Addition of water is effective when the photopolymerizable adhesive of the present invention is used as a dental adhesive. By adding water, the decalcification of hydroxyapatite in the tooth structure is promoted and the adhesive strength is further improved. Improvements are achieved. The addition amount may be appropriately determined depending on the type of composition and the type of polymerization initiator, but normally, the total amount of the above-mentioned polymerizable monomers is 10
A range of 2 to 30 parts by weight, more preferably a range of 4 to 25 parts by weight is suitable for 0 parts by weight. If the amount of water added is less than the above range, the effect of improving decalcification is small, and if it exceeds the above range, the strength of the cured product decreases, which is not preferable.

The photopolymerizable composition for adhesives of the present invention may contain a cation-releasing filler for the purpose of improving the strength of the cured product. As the cation-eluting filler used in the present invention, known cation-leaving fillers can be used without limitation. Of these, as a preferable cation-eluting filler, when 1 g of the filler is immersed in 50 ml of an aqueous solution of acrylic acid having a pH of 2.2 at 37 ° C. for 24 hours, the amount of polyvalent metal ions eluted is from 2 mgeq / g to 60 mgeq / g. Cation-eluting fillers in the range of The more preferable range of the amount of the eluted polyvalent metal ion is 5 mgeq / g to
It is 30 mgeq / g. When the amount of the eluted polyvalent metal ions is in the range of 2 mgeq / g to 60 mgeq / g, the filler that does not elute is appropriately present to improve the strength of the cured product, and the coloring substance is present on the surface of the cured product. It becomes difficult to be adsorbed. The polyvalent metal ion is a divalent or higher valent metal ion capable of binding to the acidic group of the acidic group-containing (meth) acrylate monomer.
Metal ions such as calcium, strontium, barium, aluminum, zinc, and lanthanoids.

The cation-eluting filler is not particularly limited, but preferred examples include hydroxides such as calcium hydroxide and strontium hydroxide, oxides such as zinc oxide, silicate glass and fluoroaluminosilicate glass. There is. Among them, fluoroaluminosilicate glass is the most excellent and preferable in view of the coloring resistance of the cured product.

As the fluoroaluminosilicate glass, a known cement used for dental cement, for example, glass ionomer cement can be used. The compositions of commonly known fluoroaluminosilicate glasses are, in ionic weight percent, silicon, 10-33; aluminum, 4-30; alkaline earth metals, 5-36;
Alkali metals, 0 to 10; phosphorus, 0.2 to 16; fluorine, 2 to 40 and residual oxygen are preferably used.
Illustrating a more preferable composition range, silicon, 15 to 2
5; aluminum, 7 to 20; alkaline earth metal, 8 to
28; alkali metal, 0 to 10; phosphorus, 0.5 to 8; fluorine, 4 to 40 and residual oxygen. Part or all of the alkaline earth metal is magnesium, strontium,
Substitution with barium is also preferable, and strontium is often particularly preferably used because it gives the cured product radiopaque properties and high strength. In addition, sodium is most commonly used as the above-mentioned alkali metal, but it is also preferable that a part or all of the alkali metal is replaced with lithium, potassium or the like. Further, if necessary, part of the aluminum can be replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like. In addition, substituting the above components with other components as necessary can be selected as long as the physical properties of the obtained cured product are not significantly impaired.

The amount of the cation-eluting filler used in the present invention is not particularly limited, but is preferably 3 to 30 parts by weight, relative to 100 parts by weight of all the polymerizable monomers used.
It is more preferably 5 to 25 parts by weight. When the amount of the cation-eluting filler is within the above range, it becomes easy to uniformly mix the cation-eluting filler with the polymerizable composition.

The shape of the cation-eluting filler used in the present invention is not particularly limited, and may be pulverized particles obtained by ordinary pulverization or spherical particles, and if necessary, plate-like or fibrous particles. You can also mix.

The particle diameter of the above-mentioned cation-eluting filler is not particularly limited, but usually 500 μm or less, preferably 20 μm or less is suitably used.

Furthermore, it is possible to add an organic solvent, a thickener and the like to the photopolymerizable adhesive of the present invention within a range that does not deteriorate its performance. As the organic solvent,
Hexane, heptane, octane, toluene, dichloromethane, chloroform, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, pentanone, hexanone, ethyl acetate, propyl acetate, dimethyl sulfoxide, etc., and polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl as thickeners. Examples include polymer compounds such as alcohol and highly dispersible silica. Further, during polymerization, a filler, an ultraviolet absorber, a dye,
Various additives such as antistatic agents, pigments and fragrances can be selected and used according to need.

When the photopolymerizable adhesive of the present invention is polymerized and cured, a visible light source such as carbon arc, xenon lamp, metal halide lamp, tungsten lamp, fluorescent lamp, sunlight, helium cadmium laser or argon laser is used. It is used without any restrictions. The irradiation time varies depending on the wavelength and intensity of the light source, the shape and the material of the cured body, and may be determined in advance by a preliminary experiment or the like.
The photopolymerizable adhesive of the present invention is finally used by mixing all the components, and in order to prevent deterioration during storage, it can be packaged in two stable packages if necessary. For example, a package (A) containing an acidic group-containing (meth) acrylate-based monomer, a part of the (meth) acrylate-based monomer, a sensitizing dye and a photoacid generator, an aryl borate compound and a (meth) acrylate-based A combination of packaging (B) consisting of a part of the monomers is generally used.

[0087]

The photopolymerization initiator for adhesives of the present invention has excellent curability because it is extremely sensitive to visible light, and the photopolymerizable adhesive containing the polymerization initiator is for dental use. It can be used particularly preferably as an adhesive composition, and can achieve excellent adhesiveness to tooth structure.

When the adhesive is used as an adhesive between a tooth substance and a filling material called a composite resin, it overcomes the internal stress generated during curing of the composite resin, that is, the tensile stress generated at the interface between the composite resin and the tooth substance. Only adhesive strength is required. Otherwise, not only may it fall out due to long-term use in a harsh oral environment, but a gap may be created at the interface between the composite resin and the tooth structure, and bacteria may invade from there and adversely affect the pulp. is there. When the adhesive containing the novel photopolymerization initiator of the present invention is used, the adhesiveness of the composite resin to the tooth structure is significantly improved as compared with the generally used photopolymerization initiator. . Therefore, it is possible to develop sufficient adhesive strength to the dentin, that is, dentin and enamel, without using the pretreatment material for the tooth surface, which has been conventionally used in the dental adhesive field. As a result, it is possible to shorten the treatment time clinically and reduce the number of cases where the adhesive strength is insufficient due to an erroneous operation.

[0089]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The compounds used in the text and in the examples and their abbreviations are shown below.

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

[0096]

Embedded image

[0097]

Embedded image

[0098]

[Chemical 21]

[0099]

Embedded image

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

The physical properties of the materials shown in the text and the examples were evaluated by measuring the tensile adhesion strength to the tooth structure.

Example 1 MAC as acidic group-containing (meth) acrylate-based monomer
-10 (30 parts by weight) and PM (20 parts by weight) were used, and bis-GMA (20 parts by weight) and HEMA (3 parts by weight).
0 parts by weight) to form a uniform solution. Furthermore, the coumarin-based dye CM- is added to 100 parts by weight of the total polymerizable monomer composition.
0.01 part by weight, 1 part by weight of TCT and PBNa
Was dissolved in 1 part by weight to obtain a photopolymerizable adhesive. 24 after slaughter
The bovine anterior tooth was removed within the time, and the enamel and dentin planes were carved out by pouring water on # 800 emery paper so as to be parallel to the labial surface. Next, compressed air is blown onto these surfaces for about 10 seconds to dry, and then a double-sided tape having a hole of 4 mm in diameter is fixed to this plane, and then paraffin wax having a hole of 1.5 mm in thickness and 6 mm in diameter is opened. Imitation cavities were formed by fixing them so that they would be in the same center on the circular holes. The adhesive composition was applied in the simulated cavity, left for 30 seconds, and irradiated with a visible light irradiator (White Light, manufactured by Takara Belmont Co., Ltd.) for 30 seconds to be cured. Further, a dental composite resin (Palfique Posteria, manufactured by Tokuyama Corporation) is filled on top of it,
A test piece was prepared by irradiating with a visible light irradiator for 30 seconds.

After the above adhesion test piece was immersed in water at 37 ° C. for 24 hours, a crosshead speed of 10 mm / min was measured using a tensile tester (Autograph, Shimadzu Corp.).
The adhesive strength with the tooth was measured by. The measurement results are shown in Table 1.

Examples 2 to 71 Adhesion tests on tooth structure were conducted in the same manner as in Example 1 except that the composition of the polymerization initiator shown in Table 1 was changed. The measurement results are shown in Table 1.

Comparative Examples 1 to 8 Adhesion tests on tooth structure were conducted in the same manner as in Example 1 except that the composition of the polymerization initiator shown in Table 1 was changed. The measurement results are shown in Table 1.

In each case, a decrease in adhesive strength was observed as compared with the examples.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

Comparative Examples 9 to 11 The same procedure as in Example 1 was carried out except that the known polymerization initiator for adhesives shown in Table 2 was used. The results are shown in Table 2.

In all cases, a decrease in adhesive strength was observed as compared with the examples.

[0114]

[Table 4]

Examples 72 to 87 (meth) acrylate monomer, water, and a cation-releasing filler (Tokuso ionomer powder, manufactured by Tokuyama Corp.) were uniformly mixed in a ratio shown in Table 3, and the whole mixture was added thereto. To 100 parts by weight of the polymerizable monomer composition, 1 part by weight of the cyanine dye CY-1, 1 part by weight of TCT and PBNa
Was dissolved in 1 part by weight to obtain a photopolymerizable adhesive of the present invention.

An adhesion test of the above polymerizable composition for adhesives to tooth structure was conducted in the same manner as in Example 1. Table 3 shows the measurement results.

Comparative Examples 12 to 13 In a mixed solution having the composition shown in Table 3, 1 part by weight of CQ and DMB were added to 100 parts by weight of the total polymerizable monomer composition.
1 part by weight of E was dissolved to obtain a photopolymerizable adhesive. The above-mentioned polymerizable composition for adhesives was subjected to an adhesion test with respect to tooth structure in the same manner as in Example 1. Table 3 shows the measurement results.

In all cases, a decrease in adhesive strength was observed as compared with the examples.

[0119]

[Table 3]

Claims (4)

[Claims] 1. A maximum absorption wavelength of 350 to 680 n
m having a sensitizing dye, (B) a photoacid generator, and (C)
A photopolymerization initiator for an adhesive, comprising an aryl borate compound. 2. A photopolymerizable adhesive comprising a polymerizable monomer containing a (meth) acrylate-based monomer and the photopolymerization initiator according to claim 1 as a main component. 0.01 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers in the photopolymerizable adhesive composition. 3. The photopolymerization according to claim 2, wherein the polymerizable monomer is a (meth) acrylate-based monomer containing 5% by weight or more of an acidic group-containing (meth) acrylate-based monomer. Adhesive material. 4. 2 to 100 parts by weight of all polymerizable monomers
The photopolymerizable adhesive according to claim 3, further comprising 30 parts by weight of water and 3 to 30 parts by weight of a cation-releasing filler.