JPH093109A - Visible-rays-induced polymerization initiator and visible-rays-polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a visible-rays-induced polymerization initiator having improved sensitivity to the visible rays and safety and giving a polymerizable composition excellent in adhesion to substrates by mixing a coumarin dye with a specified photic acid generator and an aryl borate compound. SOLUTION: This visible-rays-induced polymerization initiator is obtained by mixing 0.00001-50wt.% coumarin dye of formula I [wherein R1 to R3 are each H, a halogen, an alkyl, an alkoxyl, amino, an alkylamino or an alkenylamino; A is H, cyano or an alkyl; and B is H, an aryl, a 5-9C heterocyclic ring or a group of formula II (wherein Z is a 1-4C alkyl or alkenyl or 3'-coumarino)] with 0.005-95wt.% photic acid generator being at least either a halomethyl-substituted S-triazine derivative or a diphenyliodonium chloride and 0.01-95wt.% aryl borate compound. The visible-rays-induced-polymerizable composition is obtained by mixing 0.01-10 pts.wt., per 100 pts.wt total polymerizable monomer of the composition, this initiator and a polymerizable monomer containing a (meth)acrylate nonomer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel visible light polymerization initiator useful for photoresist materials, printing plate-making materials, hologram materials, especially dental materials, and a visible light polymerizable composition containing the same.

[0002]

2. Description of the Related Art Various proposals have been made for photopolymerization initiators which generate radicals or ions upon irradiation with visible light to polymerize a polymerizable unsaturated compound or cyclic compound. Generally, a compound that absorbs visible light and decomposes itself to form a polymerization active species, or a combination of a radical source or an acid source that does not absorb visible light and a dye that absorbs visible light. The dye-sensitized polymerization has been widely studied and used.

Examples of the former include acylphosphine oxide and α-diketone compounds, and examples of the latter include, for example, JP-A-5-27436, which is a visible light radical composed of a squalium sensitizing dye and an imidazole derivative. A polymerization initiator composition, a visible light radical polymerization initiator composition comprising a combination of a squaryl dye and a halomethyl group-substituted-s-triazine derivative in JP-A-5-5002, and a benzophenone group-containing compound in JP-A-60-76503. A visible light radical polymerization initiator composition comprising a combination of a peroxy ester and a pyrylium dye is disclosed. However, since these have low sensitivity to visible light, higher sensitivity has been required.

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 methods using a dye-borate complex, but the sensitivity is low. There is.
Further, JP-A-6-329712 discloses a polymerization initiator composed of a combination of an acid compound containing a photo-acid generator and a borate compound, but since it does not absorb visible light, the polymerization does not occur in visible light. In some cases, depending on the photoacid generator selected, polymerization may not be initiated at all.

In the field of dental materials, polymerization with visible light has been widely used in recent years from the viewpoint of safety and operability. As the visible light initiator, it is common to use a combination of α-diketones typified by aromatic ketones and camphorquinone and amines, but there was a problem in adhesiveness to tooth structure. .

[0006]

DISCLOSURE OF THE INVENTION The present invention has a sufficient sensitivity to visible light, high safety, and a polymerizable composition containing the same has excellent adhesiveness to a substrate such as tooth structure. It is intended to provide a photopolymerization initiator.

[0007]

As a result of intensive studies to solve the above problems, the inventor of the present invention achieved a composition comprising a specific sensitizing dye, a specific photoacid generator and an arylborate compound. The present invention was found to be useful as a novel visible light polymerization initiator to be obtained, and the present invention was proposed.

That is, according to the present invention, at least one photoacid generator selected from the group consisting of (A) a coumarin dye, (B) a halomethyl group-substituted-s-triazine derivative and a diphenyliodonium salt compound, and (C) ) A visible light polymerization initiator comprising an aryl borate compound is provided.

Further, in a visible light polymerizable composition containing a polymerizable monomer containing a (meth) acrylate-based monomer and the visible light polymerization initiator, the visible light polymerization initiator is visible. Provided is a visible light-polymerizable composition comprising 0.01 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers in the light-polymerizable composition.

Typical coumarin dyes used in the present invention are represented by the following general formula (1).

[0011]

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[Wherein R ₁ , R ₂ and R ₃ are the same or different hydrogen atom, halogen atom, alkyl group, alkoxy group, substituted or unsubstituted amino group, substituted or unsubstituted alkylamino group, and A substituted or unsubstituted alkenylamino group, wherein three R ₁ ,
At least two of R ₂ and R ₃ may combine with each other to form a condensed 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

[0013]

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(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). ].

Specific examples of coumarin dyes that are preferably used include 3-thienoylcoumarin, 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-methoxybenzoyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 7-diethylamino-
3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4-dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylaminocoumarin,
3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-carboxy-7-diethylaminocoumarin, 3- (4-carboxybenzoyl) -7-diethylaminocoumarin, 3,3 '-Carbonylbiscoumarin,
3,3′-carbonylbis (7-diethylamino) coumarin, 2,3,6,7-tetrahydro-1,1,7,7
-Tetramethyl-10- (benzothiazoyl) -11-
Oxo-1H, 5H, 11H,-[1] benzopyrano [6,7,8-ij] quinolidine, 3,3′-carbonylbis (5,7-) dimethoxy-3,3′-biscoumarin, 3- ( 2'-benzimidazoyl) -7-diethylaminocoumarin, 3- (2'-benzoxazoyl)-
7-diethylaminocoumarin, 3- (5'-phenylthiadiazoyl-2 ')-7-diethylaminocoumarin,
3- (2'-benzthiazoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (4-cyano-7)
-Diethylamino) coumarin, 4-fluoromethyl-7-
Aminocoumarin, 4-trifluoroethyl-7-diethylaminocoumarin, 3-phenyl-7-aminocoumarin,
3-phenyl-7- (2H-naphtho [1,2d] triazol 2'-ylcoumarin, 3-ethoxycarbonyl-
5,6-benzocoumarin, 4-trifluoromethylpiperidino [3,2-g] coumarin, 2,3,6,7-tetrahydro-11-oxo-1H, 5H, 11H,-[1]
Benzopyrano [6,7,8-ij] quinolozine-11-
On, 3- (2'-benzothiazoyl) -4-cyano-
7-diethylaminocoumarin and the like can be mentioned.
Among these, particularly preferred coumarin dyes include those in which a benzene ring in a coumarin compound is substituted with a dialkylamino group or an alicyclic amino group and a 3-position is substituted with a heterocycle or a ketocoumarino group. Used 400 ~
It is particularly sensitive to 500 nm visible light.

The coumarin-based dye may be appropriately selected and used depending on the wavelength and intensity of light used for polymerization, and may be used alone or in combination of two or more kinds. Further, the addition amount varies depending on other components to be combined and the type of the polymerizable monomer, but usually, it is 0.00
001 to 50% by weight, more preferably 0.00005 to
It may be selected from the range of 30% by weight. Addition amount is 0.000
When the amount is less than 01% by weight, the sensitivity to visible light is significantly reduced, which is not preferable. When the amount is more than 50% by weight, the coloration of the cured product is increased, and the light is all near the surface. There is a problem that the curing depth cannot be obtained due to absorption.

The photoacid generator used in the visible light polymerization initiator of the present invention is a halomethyl group-substituted-s-triazine derivative and / or a diphenyliodonium salt compound.
The photo-acid generator is one that produces a Bronsted acid or a Lewis acid by irradiation with light.

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

[0019]

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(Wherein R ₄ , R ₅ and R ₆ are the same or different substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted alkenyl groups, and substituted or unsubstituted An alkoxy group, and at least one of R ₄ , R ₅ and R ₆ is a halomethyl group). .

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

[0022]

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(However, 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,
Alkoxy group, M ^- is halogen ion, HS
O ₄ ⁻ , 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 will be given below. 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.

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 visible light polymerization initiator. If the addition amount is less than 0.005% by weight, the polymerization does not proceed, and if it exceeds 90% by weight, various physical properties of the polymer, that is, weather resistance and hardness of the cured product are deteriorated, which is not preferable. .

Typical aryl borate compounds used for the visible light polymerization initiator of the present invention are represented by the general formula:
The following general formula (4)

[0029]

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(Wherein R ₁₁ , R ₁₂ and R ₁₃ are the same or different substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, substituted or unsubstituted alkenyls, respectively) Group, R
₁₄ or R ₁₅ is the same or different hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted phenyl group and nitro group, L ⁺ is a metal cation Quaternary ammonium ion, quaternary pyridinium ion, quaternary quinolinium ion and phosphonium 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,
It is not preferable because it easily reacts with oxygen in the air to decompose.

Specific examples of the aryl borate compounds that are preferably used include trialkylphenylboron, trialkyl (p-chlorophenyl) boron and trialkyl (boron compounds having one aryl group in one molecule. 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-octyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron (wherein the alkyl group is an n-butyl group, an n-octyl group) , N-dodecyl group) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
Tetraethylammonium salt, methylpyridinium salt,
Examples thereof include ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt.

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-octyloxy) triphenylboron, (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 salt, methylquinolin Examples thereof include aluminum salts, ethylquinolinium salts and butylquinolinium salts.

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

When the visible light polymerization initiator of the present invention is used in the presence of an acidic group-containing polymerizable monomer, an unsubstituted or aryl group is used in order to prevent rapid decomposition of the borate compound by an acid. It is preferable to use a tetraaryl borate compound in which an alkoxy group is substituted at the m-position, or a tri- or tetraaryl borate compound in which an electron withdrawing group such as a fluorine atom is substituted.

The amount to be added cannot be determined unconditionally depending on the kind and amount of the polymerizable monomer and the blending ratio of other components, but is usually 0.01 to 9% by weight in the visible light polymerization initiator.
It is selected in the range of 5% by weight, more preferably from 0.05% by weight to 90% by weight. When the addition amount is less than 0.01% by weight, the polymerization does not proceed, and when it exceeds 95% by weight, various physical properties of the obtained polymer, that is, the hardness of the cured product deteriorates, which is not preferable.

(A) in the visible light polymerization initiator of the present invention,
The components (B) and (C) are essential components.
The types and addition ratios of the respective components can be used without any problem as long as they are within the above-mentioned ranges, but particularly when used as a visible light polymerization initiator for dental use, as the types and the addition ratios of the three particularly preferable components, Component (A) has a maximum absorption wavelength of 400 to 100 parts by weight of the total amount of visible light polymerization initiator.
0.00005% to 30% by weight of a coumarin type dye at 500 nm, and component (B) is a trichloromethyltriazine type in which two or three trichloromethyl groups are substituted or tetrafluoroborate or hexafluorophosphate as a counter anion. , A hexaphenylantimonate, a diphenyliodonium salt-based photoacid generator having a trifluoromethanesulfonate ion of 0.05 to
80% by weight, and the component (C) is unsubstituted, or a tetraarylborate compound having an aryl group substituted with an alkoxy group at the m-position, or a tri- or tetraarylborate having an aryl group substituted with a fluorine or trifluoromethyl group. The compound may be 0.05 to 90% by weight.

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 coumarin-based 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.

Further, when other dyes are used in place of the coumarin type dye as the component (A), the polymerization does not proceed at all, or the sensitivity becomes extremely low and it takes a long time to cure, so that it is used in a large amount. Need to do. The use of a large amount of dye gives rise to the drawback of causing coloration of a cured product obtained by polymerizing a polymerizable composition containing the dye.
Further, halomethyl group substitution used as the component (B)-
Known photoacid generators other than s-triazine derivatives or diphenyliodonium salt photoacid generators, such as triphenylsulfonium salt or sulfonic acid ester photoacid generators, hydrochloric acid, sulfuric acid, and acid group-containing monomers Polymerization does not proceed at all even with an acid, or it is extremely slow,
The hardness of the cured body is not sufficient.

Although the polymerization initiation mechanism of the visible light polymerization initiator of the present invention has not been fully clarified, it is considered as follows. That is, the coumarin-based dye represented by the component (A) absorbs the energy of visible light and is excited from the ground state to the excited state, and the trihalomethyl group-substituted-s-triazine derivative or diphenyliodonium salt represented by the component (B). Energy transfer occurs to the photoacid generator. Then, this energy decomposes the photo-acid generator to generate an active acid excited by light. Further, this is considered to generate a trivalent boron compound by decomposing the aryl borate compound represented by the component (C). It is presumed that the trivalent boron compound easily reacts with oxygen in the system to generate a polymerizable radical species, and polymerization of the polymerizable monomer occurs.

Therefore, as described above, it may be difficult for the polymerization to proceed with the combination of the dye and the photo-acid generator, which cannot perform efficient energy transfer. In addition, it can be considered that the acid alone, such as hydrochloric acid or an acid group-containing monomer, does not have sufficient activity and the polymerization does not proceed sufficiently.

The visible light polymerization initiator of the present invention can be used in combination with other known polymerization initiators used for thermal polymerization, ultraviolet light or visible light. There is no limitation on other polymerization initiators, but if other polymerization initiators that are preferably used are exemplified, examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, and tert-
Butyl peroxy-2-ethyl hexanoate, ter
Examples thereof include peroxides such as t-butyl peroxydicarbonate and diisopropyl peroxydicarbonate, and azo compounds such as azobisisobutyronitrile.

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 and acylphosphine oxide type photopolymerization initiators, among which camphorquinone, 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 parts by weight based on 100 parts by weight of the total visible light polymerization initiator.
It is preferable to add 0 to 150 parts by weight.

The visible light polymerization initiator of the present invention is useful as a polymerization initiator upon irradiation with visible light by blending it with a polymerizable monomer. Among the polymerizable monomers, a (meth) acrylate-based monomer is also useful. (Meth) acrylate-based monomer containing 5 parts by weight or more of an acidic group-containing (meth) acrylate-based monomer as a polymerizable monomer, which gives a fast curing speed and high strength of the cured product when combined with When used in combination with, it is preferable because the adhesiveness to the tooth substance is further excellent. As the acidic group-containing (meth) acrylate-based monomer and the (meth) acrylate-based monomer, known ones can be used without particular limitation.

The acidic group-containing (meth) acrylate-based monomer that is generally preferably used is a (meth) acrylate-based monomer having an acidic group such as a carboxyl group or its anhydride or a phosphoric acid group in the molecule. The body is not particularly limited, and known compounds can be used. A typical acidic group-containing (meth) acrylate-based monomer is represented by the following general formula (5).
Indicated by

[0050]

[Chemical 6]

(In the above general formula, 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, an anhydrous carboxyl group, a phosphoric acid group, or a phosphoric acid ester group.) In the general formula (5), X represents a carboxylic acid group, an anhydrous carboxylic acid group, a phosphoric acid group, or phosphorus. It is a group containing an acid ester group, and its structure is not particularly limited, but preferable specific examples are as follows.

[0052]

[Chemical 7]

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.

[0054]

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Preferred specific examples of the acidic group-containing (meth) acrylate-based monomer represented by the above general formula (5) are as follows.

[0056]

Embedded image

[0057]

Embedded image

[0058]

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[0059]

[Chemical 12]

(However, R ₁₆ is a hydrogen atom or a methyl group.) When the visible light-polymerizable composition of the present invention is used for dental purposes, it is specifically exemplified above from the viewpoint of adhesiveness to the tooth. Among the acidic group-containing (meth) acrylate-based monomers, those having a carboxyl group and a phosphoric acid group are particularly preferably used.

The acid group-containing (meth) acrylate-based monomer is required to be blended in an amount of 5 parts by weight or more based on 100 parts by weight of the total (meth) acrylate-based monomer when adhesiveness to tooth structure is desired. It is preferable to mix 10 to 80 parts by weight.

As the other (meth) acrylate-based monomer used in the present invention, known compounds can be used without any limitation. Specific examples of preferable (meth) acrylate-based monomers are methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol. Mono (meth) acrylate, allyl (meth) acrylate,
Mono (meth) acrylate-based monomers such as 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and glyceryl mono (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) acryloyloxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyphenyl] 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, Examples include polyfunctional (meth) acrylate monomers such as epoxy (meth) acrylate. These (meth) acrylate monomers can be used alone or in combination of two or more.

In the present invention, when the visible light-polymerizable composition is polymerized, often the composition is easily polymerized,
It is also possible to mix and polymerize a polymerizable monomer other than the (meth) acrylate-based monomer in order to adjust the viscosity or other physical properties. Examples of these polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene and α-methylstyrene dimer or 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 the photoacid 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.

The preferable blending ratio of the visible light polymerization initiator in the visible light polymerizable composition 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 visible light initiator added is less than 0.01 part by weight,
When the polymerization does not proceed sufficiently and exceeds 10 parts by weight,
Hardness of the cured product and various physical properties such as weather resistance are deteriorated, which is not preferable.

When the visible light-polymerizable composition of the present invention is used as an adhesive material for a tooth substance and a composite resin, it is effective to add water. It is presumed that the addition of water promotes the decalcification of hydroxyapatite in the tooth material and achieves a further improvement in adhesive strength.

The amount to be added may be appropriately determined depending on the type of composition and the type of polymerization initiator, but is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of all polymerizable monomers,
The range of 4 to 25 parts by weight is more preferable. When the amount of water added is less than the above range, the effect of improving decalcification is small, and when it exceeds the above range, the strength of the cured product is remarkably reduced, which is not preferable.

A cation-releasing filler can be further added to the visible light-polymerizable composition of the present invention, particularly for the purpose of improving the strength of the cured product.

As the cation-releasing filler used in the present invention, known cation-releasing fillers can be used without limitation. Among them, the preferable cation-releasing filler is 1 g of the filler at a temperature of 37 ° C. and a pH of 2.
When soaked in 50 ml of the acrylic acid aqueous solution of No. 2 for 24 hours, the amount of polyvalent metal ions eluted was 2 mgeq / g to 6
Cation-releasing fillers in the range of 0 mgeq / g are included. Preferably, 5 mgeq / g to 30 mge
q / g. The amount of the eluted polyvalent metal ion is 2
When it is in the range of mgeq / g to 60 mgeq / g, the insoluble filler is appropriately present and the strength of the cured product is improved. In addition, the polyvalent metal ion is the above-mentioned acidic group-containing (meta)
A metal ion having a valence of 2 or more and capable of binding to an acidic group of an acrylate monomer. Typical examples are calcium, strontium, barium, aluminum, zinc,
Metal ions such as lanthanoids.

The type of the cation-releasing filler is not particularly limited, but preferred examples include hydroxides such as calcium hydroxide and strontium hydroxide, oxidation of zinc oxide, silicate glass, fluoroaluminosilicate glass and the like. There is a thing. Among them, fluoroaluminosilicate glass is the most excellent in terms of the coloring resistance of the cured product,
It is suitable.

As the fluoroaluminosilicate glass, a known cement used for dental cement, for example, glass ionomer cement can be used. Commonly known compositions of fluoroaluminosilicate glass, in terms of ionic weight percent, are 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 preferred, and strontium is particularly often used because it gives radiopaque and high strength to the cured product. The most common alkali metal is sodium, but it is also preferred that the alkali metal is partially or entirely 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, if necessary, replacing the above component with another component can be selected as long as it does not significantly impair the physical properties of the obtained cured product.

The amount of the cation-releasing filler used is not particularly limited, but is preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the total polymerizable monomers to be blended. . When the amount of the cation-releasing filler is within the above range, it becomes easy to uniformly mix the cation-releasing filler into the polymerizable composition.

The shape of the cation-releasing 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 cation-releasing filler is not particularly limited, but is usually 50 μm or less, preferably 20 μm.
Those of m or less are preferably used.

Furthermore, it is possible to add an organic solvent, a filler, a thickener and the like to the composition of the present invention within the range where the performance is not deteriorated.

As the organic solvent, hexane, heptane, octane, toluene, dichloromethane, chloroform, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, pentanone, hexanone,
There are ethyl acetate, propyl acetate, dimethyl sulfoxide and the like, and as the filler, glass, silicon oxide, titanium oxide, zirconium oxide, aluminum oxide, silicon-zirconia composite oxide, silicon-titanium composite oxide,
Inorganic fillers such as barium sulfate and calcium carbonate,
Examples thereof include organic fillers such as polymethylmethacrylate, polyethylmethacrylate, polyvinyl chloride, polystyrene, and inorganic-organic composite fillers.
Examples of thickeners include high molecular compounds such as polyvinylpyrrolidone, carboxymethyl cellulose, polyvinyl alcohol and highly dispersible silica.

In the polymerization, various additives such as a filler, a UV absorber, a dye, an antistatic agent, a pigment and a fragrance can be selected and used according to need.

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

[0080]

INDUSTRIAL APPLICABILITY The visible light polymerization initiator of the present invention is extremely sensitive to visible light, and the visible light polymerizable composition containing the polymerization initiator is particularly suitable as a dental adhesive polymerizable composition. It can be used for and achieves excellent adhesion to the tooth structure.

When the adhesive polymerizable composition is used as an adhesive between a tooth substance and a filling material called a composite resin, internal stress generated during curing of the composite resin, that is, it occurs at the interface between the composite resin and the tooth substance. Adhesive strength is required to overcome the tensile stress.
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.

In the above case, when the visible light-polymerizable composition containing the novel visible light polymerization initiator of the present invention is used as an adhesive, it is compared with a commonly used visible light polymerization initiator. As a result, the adhesion of the composite resin to the tooth structure is significantly improved. Therefore, it is possible to develop sufficient adhesive strength to dentin and enamel without using a pretreatment material (primer, conditioner) for the tooth surface which has been conventionally used in the dental adhesive field.

The presence of oxygen, acid and water present at the interface is considered as a factor that interferes with the adhesive force with the tooth structure. However, when the visible light polymerization initiator of the present invention is used, it is It is thought that it goes through a valent boron compound, and this is decomposed by oxygen existing at the dentin interface to generate a polymerizable radical, so that the polymerization at the interface progresses further,
It is presumed that high adhesive strength can be obtained.

[0084]

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.

[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

[Chemical 21]

[0094]

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[0095]

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[0096]

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[0097]

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Cation-releasing filler (FASG):
The filler of glass ionomer cement made by Tokuyama Co., Ltd. was used.

The methods for evaluating the physical properties of the materials shown in the text and in the examples are as follows.

(1) Gelation time 1 g of 3G (manufactured by Shin-Nakamura Chemical Co.) solution containing the visible light polymerization initiator of the present invention was put in a 5 ml sample tube bottle to give a cured film thickness of 7 mm. Then, from the irradiation distance of 1.5 cm, a visible light irradiator (COLD LIGHT, HOYA
-Made by SCOTT). At this time, the time when the fluidity of the monomer disappeared was measured as the gelation time.

(2) Curability and surface tackiness In the same manner as described above, the hardness of the cured product after visible light irradiation for 3 minutes and the surface tackiness were evaluated on a scale of 5 respectively. That is, those having sufficient hardness and no stickiness on the surface are ◎, those having sufficient hardness and only the surface are ○, jelly-like, unpolymerized monomer on the surface The one with a streak was marked with Δ, the one that was partly jelly-like was marked with X, and the one that was not cured at all was marked with XX.

(3) Adhesive strength of enamel and dentin Bovine anterior teeth were removed within 24 hours after slaughter, and under water injection, # 80.
The enamel and dentin planes were carved with 0 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 visible light-polymerizable composition of the present invention was applied in the simulated cavity, left for 1 minute, and then irradiated with a visible light irradiator (White Light, manufactured by Takara Belmont Co.) for 30 seconds to cure the composition. Further, a dental composite resin (Palfique Esterite, manufactured by Tokuyama Corp.) was filled therewith, and light was irradiated for 30 seconds with a visible light irradiator to prepare a test piece.

The above adhesion test piece was immersed in water at 37 ° C. for 24 hours, and then a crosshead speed of 10 mm / min was measured using a tensile tester (Autograph, manufactured by Shimadzu Corporation).
The adhesive strength with the tooth was measured by.

Example 1 To 100 parts by weight of 3G, 0.05 parts by weight of CDAC, 1 part by weight of TCT and 1 part by weight of FPBNa were added and dissolved in the dark to obtain a visible light polymerizable composition. It was Then weigh out 1 g of this solution into a 5 ml sample tube bottle,
Light irradiation was performed for 3 minutes. The gelation time at this time was 6 seconds, and the hardness of the cured product and the evaluation of the tackiness of the surface were evaluated as ◎.
Met.

Example 2-62 A 3G solution containing a coumarin dye, a photoacid generator and an aryl borate compound shown in Table 1 was used as a visible ray-polymerizable composition, and the same procedure as in Example 1 was carried out. The results of gelling time, curability and tackiness of the surface are shown in Table 1.

In all the examples, the gelation time was short, and the curability and surface tackiness were good.

Comparative Example 1-12 The procedure of Example 1 was repeated except that the ingredients shown in Table 1 were used. The gelation time, curability and surface tackiness are shown in Table 1.

In Comparative Examples 1 to 3, each one component was not added among the essential components in the present invention, and none of them polymerized with visible light. Comparative Examples 4 to 7
Is the case where a dye other than the coumarin-based dye is used, and because the energy transfer with the photo-acid generator (B) is not sufficient,
Those that did not gel, and gelation time became extremely long.
Comparative Examples 8 to 10 are examples using a photoacid generator other than a halomethyl group-substituted-s-triazine derivative or a diphenyliodonium salt-based photoacid generator, and none of them gelled. Comparative Examples 29 and 30 are examples in which concentrated hydrochloric acid or orthophosphoric acid was added as an acid, and it took an extremely long time to gel as compared with the Examples.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

Example 63 MTS as an acidic group-containing (meth) acrylate-based monomer
(50 parts by weight) and 3G (20 parts by weight) and HE
It was mixed with MA (30 parts by weight) to obtain a uniform solution. Further, 0.05 parts by weight of CDAC, 1 part by weight of TCT and 1 part by weight of FPBNa were dissolved in 100 parts by weight of the total polymerizable monomer composition to obtain a visible light polymerizable composition. When this was used as a tooth adhesive, the adhesive strength to dentin was measured, and it was a high adhesive strength of 15.2 MPa.

Examples 64-116 An adhesion test for dentin was conducted in the same manner as in Example 63 except that the polymerizable monomer composition and the visible light initiator composition shown in Table 2 were changed. The measurement results are shown in Table 2.

Comparative Examples 13 to 18 Comparative Example 13 to 18 was carried out in the same manner as in Example 63 except that the known visible light polymerization initiator shown in Table 2 was used. The results are shown in Table 2.

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

[0116]

[Table 4]

[0117]

[Table 5]

[0118]

[Table 6]

[0119]

[Table 7]

[0120]

[Table 8]

[0121]

[Table 9]

Claims (4)

[Claims] 1. At least one photoacid generator selected from (A) a coumarin dye, (B) a halomethyl group-substituted S-triazine derivative and a diphenyliodonium salt compound, and (C) an aryl borate compound. A visible light polymerization initiator characterized in that. 2. A visible light polymerizable composition comprising a polymerizable monomer containing a (meth) acrylate-based monomer and the visible light polymerization initiator according to claim 1, wherein the visible light polymerization is carried out. A visible light polymerizable composition comprising an initiator in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of all polymerizable monomers in the visible light polymerizable composition. 3. The visible light polymerizable according to claim 2, wherein the (meth) acrylate-based monomer is a (meth) acrylate-based monomer containing 5 parts by weight or more of an acidic group-containing (meth) acrylate-based monomer. Composition. 4. 2 to 30 per 100 parts by weight of the polymerizable monomer
The visible light polymerizable composition according to claim 3, further comprising 3 parts by weight of water and 3 to 30 parts by weight of a cation-releasing filler.