JPH05295013A - Polymerization initiator composition for controlling polymerization on interface and curable composition containing the same - Google Patents

Abstract

PURPOSE:To provide the polymerization initiator composition comprising a (thio)barbituric acid compound and a specific compound and controlling the polymerization on the interface, and to provide the curable composition comprising the polymerization initiator composition and a radically polymerizable monomer and suitable for dentinal adhesion. CONSTITUTION:(A) The polymerization initiator composition for controlling the polymerization on the interface comprises 100 pts.wt. of A1: a (thio)barbituric acid compound of the formula (R<1> is a 4-12C alkyl, allyl, etc.; R<2> is H, a 1-12C alkyl, etc.; R<3> is a 1-12C alkyl, allyl, etc.; X is O or S), preferably the compound wherein at least two of the R<1>, R<2> and R<3> are different each other, and 0.001-1 pt.wt. of A2: a cuprous halide or a ferric halide or A3: a combination of a halogen ion-forming compound (e.g. hydrohalogenic acid salt) with a cuprous ion or ferric ion-forming compound (e.g. cuprous acetate or ferric succinate). (B) The curable composition comprises 100 pts.wt. of a radically polymerizable monomer, 0.1-10 pts.wt. of the component A1, and 0.0001-0.5 pt.wt. of the component A2 or A3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polymerization initiator composition and a curable composition for controlling polymerization at an interface.

[0002]

2. Description of the Related Art In dental treatment, it is necessary to bond a tooth substance to a material such as a polymer and a metal, and various adhesives have been proposed for this purpose. The basic idea is to use a polymerizable monomer that has an affinity with the tooth substance. For example, 4-methacryloyloxyethoxycarbonylphthalic acid having a carboxyl group or its anhydride, 1
There are 0-methacryloyloxydecylmalonic acid, 10-methacryloyloxydecyldihydrodiene phosphate having a phosphoric acid group, and the like, and polymerizable monomers mixed with them include methyl methacrylate and bisphenol A-glycidyl methacrylate adduct. , Triethylene glycol dimethacrylate, etc. are exclusively used.

As a polymerization initiator for curing these polymerizable monomers, a benzoyl peroxide / amine system or a system to which a sulfinate is added is used as a system for curing radicals by a chemical reaction at room temperature. There are tributylborane and its oxide, and as a compound that generates a radical by photoreaction and cures it, there is a system of camphorquinone / N, N-dimethylaminoethyl methacrylate or other amine.

In the prior art, the emphasis is placed on the adhesion-promoting monomer, but even if the adhesion-promoting monomer exists at the dentin interface, the curing of the monomer is performed from the interface. Unless it is strong adhesive force cannot be obtained. That is, unless a specially devised polymerization initiator is used, the shrinkage caused by the polymerization of the monomer causes a strain at the interface at the time of final curing, causing the interface to become the weakest part and breaking at that point. Obviously it will be easier. Therefore, in the prior art, sufficient adhesion is not obtained even with the adhesion promoting monomer, except when tributylborane oxide is used in combination with ferric chloride.

Although tributylborane oxide and iron chloride are certainly effective for polymerization from the dentin interface, in an adhesive using tributylborane oxide, tributylborane oxide is contained in an amount of 10% or more of the monomer. A large amount has to be used, curing is slow, and most of the polymerizable monomers are limited to methyl methacrylate, and dimethacrylates cannot be used.

Further, a photopolymerizable dental material comprising vinyl monomer, camphorquinone and 5-alkylbarbituric acid is known (Japanese Patent Publication No. 59-28,569).
However, this material is insufficient for adhesion at the interface with the tooth substance because it must be irradiated with light.

On the other hand, the present inventor has previously found that polymerization at the interface is possible by blending 5-n-butylbarbituric acid and cupric chloride into methyl methacrylate [dental material Instrument Volume 8 Special Issue 14, 89
-90 (1989)].

However, 5-n-butylbarbituric acid is not only insufficient in its adhesive strength, but also has a drawback that it requires a large amount and a long curing time because it has a low solubility in a monomer. It was Further, the carbon number is 1 to 3.
Substituted (thio) barbituric acid (Japanese Patent Application No. 2-245,3)
No. 41) also had sufficient adhesive strength but insufficient solubility in the monomer.

[0009]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and by devising the initiation of curing from an interface with a large amount of water, A polymerization initiator that exhibits excellent adhesion to the dentin of many teeth, is used in a small amount, cures quickly, and can use a wide range of monomers as well as methyl methacrylate as a polymerizable monomer. And to provide a composition containing the same.

[0010]

[Means for Solving the Problems] These various purposes are represented by the general formula (1).

[0011]

[Chemical 2]

(In the formula, R ¹ has 4 to ¹ carbon atoms.
2, preferably 4 to 6 alkyl group, allyl group or cycloalkyl group, R ² is hydrogen atom, and has 1 to 1 carbon atoms
2, preferably 1 to 4 alkyl group, allyl group or cycloalkyl group, R ³ is an alkyl group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atom, allyl group or cycloalkyl group, and X is oxygen. Atom or sulfur atom), (thio) barbituric acid compound, (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric or ferric ion forming compound It is achieved by a polymerization initiator composition that controls the polymerization at the interface.

The present invention also includes R ¹ and R ² of the general formula (1).
At least two of R ³ and R ³ are different from each other (thio) barbituric acid.

These various objects are achieved by the following formula: (thio) barbituric acid compound represented by the general formula (1), (a) cupric halide or ferric halide, or (b) halogen ion forming compound and cupric acid. Alternatively, it is achieved by a curable composition comprising a ferric ion forming compound and a radically polymerizable monomer.

The present invention also provides a radically polymerizable monomer 10
0 parts by weight of the (thio) barbituric acid compound 0.1
10 parts by weight and (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric ion or ferric ion forming compound 0.0
This is a curable composition containing 001 to 0.5 part by weight. The present invention is further a curable composition in which the curable composition is for dentin adhesion.

[0016]

In order to initiate the polymerization from the dentin interface with high water content, it is considered to use a redox initiator with a substance that is easily incorporated into the interface. Examples of redox components that are easily incorporated into the interface include copper chloride and iron chloride. As a result of various searches for components to be combined with it, it was found that the (thio) barbituric acid compound is optimal.

The redox components which are easily incorporated into the dentin used in the present invention include cupric halides such as cupric chloride and cupric bromide, ferric chloride and ferric bromide. There are ferric halides and the like, and cupric halide is preferable. Also, a combination of a halogen ion forming compound and a cupric or ferric ion forming compound, preferably a cupric ion forming compound can be used as a redox component. Examples of the halogen ion-forming compound include halogenated salts of amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, isopropylamine, butylamines, pyridines and hydrobromide. Examples thereof include hydrates, methacryloyl choline colloids, acryloyl choline chloride and the like. As the cupric or ferric ion forming compound, copper acetate, copper propionate,
Organic acids such as copper succinate, copper acrylate, copper methacrylate, copper maleate, copper fumarate, iron acetate, propionate, iron succinate, iron acrylate, iron methacrylate, iron maleate, iron fumarate Salt, copper acetylacetonate, iron acetylacetonate and the like.

The (thio) barbituric acid compound is preferably one in which the substituent is asymmetric from the viewpoint of solubility in the monomer. For example, the substituent R ^{1 in} the general formula (1) is an n-butyl group, Isobutyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, phenyl group, n-heptyl group,
Isoheptyl group, cycloheptyl group, n-octyl group,
Isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, etc., wherein R ² is hydrogen atom, methyl group, ethyl group, propyl group Group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, phenyl group,
n-heptyl group, isoheptyl group, cycloheptyl group,
n-octyl group, isooctyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, etc., and R ³ is methyl group, ethyl group , Propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, phenyl group, n-heptyl group, isoheptyl group, cycloheptyl group Group, n-octyl group, isooctyl group, n-nonyl group,
These are asymmetrically substituted with an isononyl group, n-decyl group, isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, etc. (thio)
Barbituric acid, more preferably 5-n-butyl-1
-Methyl (thio) barbituric acid, 5-n-butyl-1-
Ethyl (thio) barbituric acid, 5-n-butyl-1-ethyl-3-methyl (thio) barbituric acid, 5-isobutyl-1-methyl (thio) barbituric acid, 5-isobutyl-1-ethyl-3-methyl (Thio) barbituric acid, 5-
Isopentyl-1-methyl (thio) barbituric acid, 5-
Cyclopentyl-1-methyl (thio) barbituric acid, 5
-Cyclohexyl-1-methyl (thio) barbituric acid,
Examples thereof include 1,3-dimethyl-5-phenyl (thio) barbituric acid.

The amount of (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric or ferric ion forming compound relative to 100 parts by weight of the (thio) barbituric acid compound is 0. 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight.

The curable composition according to the present invention comprises a (thio) barbituric acid compound represented by the general formula (1), (a)
Cupric halide or ferric halide or (b)
It is composed of a halogen ion forming compound, a cupric or ferric ion forming compound, and a radical polymerizable monomer.

Radical-polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylates such as isopropyl (meth) acrylate and butyl (meth) acrylate, esters of (meth) acrylic acid having a carboxyl group or a phosphoric acid group in the side chain, ethylene glycol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate,
Diacrylic acid or dimethacrylic acid esters of diols such as triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, and hexanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, bisphenol A
-Glycidyl methacrylate adducts and the like.

The radical-polymerizable monomer may be a complete monomer or a syrup-like material partially containing a polymer.

The amount of the (thio) barbituric acid compound based on 100 parts by weight of the radical-polymerizable monomer is 0.1-1.
0 parts by weight, preferably 0.5 to 5 parts by weight, and (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric ion or ferric ion forming The amount of the compound is 0.0001 to 0.5 part by weight, preferably 0.0005 to 0.1 part by weight.

In order to improve the solubility of the polymerization initiator and to improve the wetting of the monomer at the interface with high water content, 2-hydroxyethyl (meth) which is a water-soluble monomer is used as the polymerizable monomer. ) Acrylate, N- (meth) acryloyloxyethylpyrrolidone, 2,3-dihydroxypropyl (meth) acrylate, N-vinylpyrrolidone, dimethylaminoethyl (meth) acrylate, diacetone (meth)
Acrylamide or the like is added to the radical-polymerizable monomer at 0.
It is also possible to add 5 to 50% by weight, preferably 1 to 10% by weight. In addition, the curable composition contains 0.1 to 50% by weight, preferably 1 to 10% by weight of a water-soluble organic solvent such as ethanol, isopropanol, acetone, or tetrahydrofuran with respect to the radical-polymerizable monomer. It may be added as necessary.

The curable composition according to the present invention may contain other polymers, fillers, stabilizers and the like.

In performing the adhesion of the tooth to the dentin,
Pretreatment of dentin with an aqueous solution of citric acid containing cupric chloride or ferric chloride and washing with water, or pretreatment with citric acid, ethylenediaminetetraacetic acid phosphate, etc., followed by washing with cupric chloride 0.001 to 0.1% aqueous solution is applied, and a monomer composition containing cupric chloride or iron and a (thio) barbituric acid compound is applied thereto. For adhesion to enamel, only acid etching is necessary.

By using the polymerization initiator composition according to the present invention, not only is it possible to adhere to dentin which contains water at room temperature, but it is also possible to adhere to the interface which contains water,
Polymerization or graft polymerization on the surface of materials such as water-containing films and fibers is possible.

[0028]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Examples.

Method of Measuring Adhesion Force Bovine anterior teeth were cut with a diamond cutter, and the dentin surface on the labial side was used as an adhesive sample as it was. After treatment with a 10% by weight citric acid aqueous solution containing 3% by weight cupric chloride for 30 seconds, washing with water and drying, a plastic adhesive tape having a hole with a diameter of 5 mm was attached to define the adhesion area. The curable composition was placed thereon and the acrylic rod was adhered thereto. After leaving it at room temperature for 30 minutes and further immersing it in distilled water at 37 ° C. for 24 hours, a tensile test was performed to measure the adhesive strength. The average value of five test pieces was obtained.

Example 1 0.0005% by weight of methyl methacrylate (MMA) containing 2% by weight of 2-hydroxyethylmethacrylate.
Copper acetylacetonate (CAA) and 0.04% by weight
Vinylbenzyltetradecyldimethylammonium chloride (VB14) is dissolved to form a liquid component, and 2% by weight of 5% is added to polymethylmethacrylate (PMMA) powder.
A mixture of n-butyl-1-methylbarbituric acid was used as a powder component. A 1: 1 mixture of this powder and liquid cured in 4.5 minutes. When dentin was adhered using this mixture, an adhesive force of 12.9 MPa was obtained.

Examples 2 to 6 The same procedures as in Example 1 were carried out using the concentrations of CAA, VB14 and the barbituric acid compound shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 2 The procedure of Example 1 was repeated except that 5-n-butylbarbituric acid was used. The results are shown in Table 1.

[0033]

[Table 1]

Examples 7 to 12 The same procedure as in Examples 1 to 6 was carried out except that iron acetylacetonate (FAA) was used instead of CAA. The results are shown in Table 2.
Shown in.

[0035]

[Table 2]

Examples 13 to 15 Example 1 was carried out using barbituric acid in the concentrations shown in Table 3.
I went the same way. The results of curing time and adhesive strength are shown in Table 3.

[0037]

[Table 3]

Example 16 0.003% by weight of cupric chloride was dissolved in methylmethacrylate (MMA) containing 2% by weight of 2-hydroxyethylmethacrylate to prepare a liquid component, and 2 parts of polymethylmethacrylate (PMMA) powder was added. A powder component was obtained by mixing 5% by weight of 5-n-butyl-1-methylbarbituric acid. A 1: 1 mixture of this powder and liquid cured in 4.5 minutes. When dentin was adhered using this mixture, an adhesive force of 12.9 MPa was obtained.

Example 17 10% containing 3% cupric chloride in the method for measuring adhesion.
Instead of treating dentin with 10% citric acid aqueous solution, treating with 10% citric acid aqueous solution, washing with water, drying, applying 0.01% cupric chloride aqueous solution, drying, and then the curable composition of Example 1. Then, the adhesive force of 13.5 MPa was obtained.

Example 18 In Example 1, methylmethacrylate was added to 5% by weight of 2-hydroxyethylmethacrylate, 0.01% by weight.
The same procedure was followed except that the liquid component was prepared by adding copper methacrylate and 0.05% by weight of methacryloylcholine chloride, and the adhesive strength was 9.
It was 5 MPa.

[0041]

As described above, the (thio) barbituric acid compound represented by the general formula (1), (a) cupric halide or ferric halide or (b) halogen ion forming compound and Since it is a polymerization initiator composition that controls the polymerization at the interface composed of dicopper or ferric iron-forming compound, by using the polymerization initiator composition, even a small amount quickly cure the monomer at room temperature, It is possible to obtain a strong adhesive force to the tooth substance.

Further, since the curable composition according to the present invention comprises the above-mentioned polymerization initiator and the radical-polymerizable monomer, it can be adhered to the dentin containing water at room temperature. Adhesion to an interface in a water-containing state, and polymerization or graft polymerization on the surface of a material such as a water-containing film or fiber are also possible.

Claims (6)

[Claims] 1. A general formula (1): (In the formula, R ¹ is an alkyl group having 4 to 12 carbon atoms, an allyl group or a cycloalkyl group, R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, R 1 ³ is an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, and X is
Is an oxygen atom or a sulfur atom) (thio)
Polymerization initiator composition for controlling polymerization at an interface consisting of a barbituric acid compound, (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric or ferric ion forming compound object. 2. The polymerization initiator composition according to claim 1, wherein at least two of R ¹ , R ² and R ^{3 in} the general formula (1) are different (thio) barbituric acid. 3. A (thio) barbituric acid compound represented by the general formula (1), (a) cupric halide or ferric halide or (b) halogen ion forming compound and cupric or ferric iron. A curable composition comprising an ion-forming compound and a radical-polymerizable monomer. 4. The curable composition according to claim ³ , wherein at least two of R ¹ , R ² and R ^{3 in} the general formula (1) are different (thio) barbituric acid compounds. 5. 0.1 to 10 parts by weight of the (thio) barbituric acid compound and (a) cupric halide or ferric halide or (b) relative to 100 parts by weight of the radical-polymerizable monomer. Halogen ion forming compound and cupric ion or ferric ion forming compound 0.0001-0.
The curable composition according to claim 3 or 4, which comprises 5 parts by weight. 6. The curable composition according to any one of claims 3 to 5, wherein the curable composition is for dentin adhesion.