JP2896192B2 - Primer composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a primer composition. More specifically, the present invention is applied to a dental cement restorative material such as a resin cement, a bonding material, a composite resin or a PMMA resin to a substrate such as enamel or dentin of natural teeth, glass ionomer cement, etc. The present invention relates to a primer composition suitable for imparting strong adhesion and durability between the two.

2. Description of the Related Art Dental restorative resins generally have insufficient adhesion to the tooth material, so that restorations may fall off or secondary caries or pulp irritation caused by infiltration and leakage of bacteria and the like at the periphery of the restoration. ,
Fracture of the margin, coloring of the margin, and the like occur, and this is a clinical problem in dentistry.

In order to solve such a clinical problem, as described in detail below, methods for improving the adhesiveness between the restoration and the tooth have been conventionally proposed.

Adhesion to enamel is proposed by the so-called acid etching method [Journal of Dental Research (Jour
nal of Dental Research), 34 (6), 849-
853 (1955)]. Adhesion by this method is not due to the chemical bond between the dentin and the binding resin, but is mainly due to the hardening and mooring of the resin that has penetrated into the microstructure formed by the demineralization of the enamel trabeculae. Based on mating.
However, the enamel surface without acid etching does not have such a microstructure, and the adhesion in this case remains insufficient.

Recently, there has been a great deal of interest in dentin bonding, with many proposals being made and some progress being made. However, these are methods in which dentin is pre-treated with an inorganic acid, an organic acid, an organic acid and a certain metal chloride, EDTA or a salt thereof, and in some cases, is reformed and strengthened.In the case of enamel, anyway Regarding dentin, clinical problems have been pointed out. In particular, the etching treatment of dentin with phosphoric acid has been discussed in Europe and the United States, including Japan, and the American Dental Association has made recommendations against the treatment of dentin with phosphoric acid. Nevertheless, citric acid and oxalic acid, which are considered to have less etching action than phosphoric acid, are being studied as dentin acid treatment materials (AIDR / AADR Abstracts No.915,
276, 1985 or U.S. Pat.
No. 538,990). A treatment method using EDTA (see U.S. Pat. Nos. 4,553,941 and 4,593,054) has also been proposed. However, a strong desire of the dental world or dentist is a strong adhesion to dentin without acid treatment and its durability.

On the other hand, remarkable progress has recently been made in dentin adhesive strength. Journal of Dental Research (Jour
nal of Dental Research) Volume 63 (8) pp. 1087-1089
(1984), Scandinavian Journal of Dental Research (Scand. J. Dent. Res.), Vol. 93, pp. 463-466 (1985), and the International Dental Journal. 35
Vol. 160-165 (1985), dentin is pre-treated with an EDTA-Na salt solution, and then a mixed solution of glutaraldehyde, water and 2-hydroxyethyl methacrylate [Glomer (Gl
uma)], and it was described that the value reached 100 kgf / cm ² or more with a normal bonding material + composite resin. However, in fact, EDTA
Without Na treatment, it shows about 50.8 kgf / cm ² and has been found to remain low.

In addition, the 7th Annual Meeting of the Japan Society of Adhesive Dentistry, pages 121-122 and 123-124 (1989), or the 1st International Society of Dental Materials (= International Congress on Dental Materials: (International Congress
on Dental Materials) 236-237 (1989) and Dental Engineering
From page 31 to page 38 (1987), after dentin is acid-treated, solution A [70% 2-HEMA +
6% O-methacryloxytyrosinamide (MTYA)] and B
Solution (2% glutaraldehyde aqueous solution) with a primer, and cold water (4%) with MMA / TBBO resin
C.) and hot water (55.degree. C.) after 2000 thermal cycles. For example, it describes that after the treatment with 40% phosphoric acid, the mixed primer treatment of the solution A and the solution B exhibits 164 kgf / cm ² . However, the dentin adhesion without acid treatment is 48kg at 0 cycle
It shows f / cm ² , which is not only insufficient in terms of essential adhesive strength, but also has not attained an adhesive durability to dentin without acid treatment. That is, although this method has progressed in terms of adhesion, strictly speaking, the adhesion to dentin without acid treatment is low, and in this sense, the essential adhesion to dentin has not yet been reached. Not. The proponent of the above technology has acknowledged this in the disclosure.

Furthermore, relatively recently, a primer composition which does not require a pretreatment such as an acid treatment, that is, a primer composition for hard tissues containing water, a water-soluble film-forming agent and a salt of an acid has been proposed. (See Japanese Patent Application Laid-Open No. 1-113057).

However, when the primer composition is used for adhesion between the dentin of a tooth and a composite range, the adhesive strength is greatly affected by the type and amount of the acid salt, and in some cases, when the primer composition is not used. Not only are the adhesive strengths lower than the above, but also the adhesion durability is not obtained.

Problem to be Solved by the Invention This invention solves the above-mentioned conventional problems, and provides a resin cement, a bonding material, a composite resin to a substrate such as enamel or dentin or glass ionomer cement of a living hard tissue, particularly a natural tooth. When bonding a dental adhesive restorative material such as PMMA resin, it was made to provide a primer composition capable of imparting strong adhesiveness and durability between the two without performing treatment such as acid treatment. is there.

Means for Solving the Problems The present inventors have conducted intensive research on a primer that imparts adhesiveness and its durability, and as a result, the following components,
(I) 0.5 to 90% by weight of water, (ii) 5 to 90% by weight of a polymerizable compound having a hydroxyl group, (iii) 0.1 to 90% by weight of a polymerizable compound having an acid group, and (iv) amino having an acid group. A primer composition containing 0.01 to 30% by weight of a compound solves the problems of the prior art, and is particularly suitable for a substrate such as enamel, dentin, or glass ionomer cement of a living hard tissue.
When bonding dental adhesive restoration materials such as resin cement, bonding material, composite resin, PMMA resin, etc., they found that strong adhesion and durability between them can be imparted without any treatment such as acid treatment. The present invention has been accomplished based on this finding.

The water used in the present invention is clinically acceptable as a storage stability and medical ingredient, and preferably contains essentially no ingredients harmful to the components of the composition and the adhesive effect. Distilled water (or purified water) or ion-exchanged water (or deionized water) is preferred. The amount of water is usually 0.5-9
The content is 0% by weight, preferably 5 to 80% by weight, more preferably 10 to 50% by weight. When the content is 0.5% by weight or less and 90% by weight or more, the adhesiveness decreases.

The polymerizable compound having a hydroxyl group used in the present invention is a polymerizable monomer, oligomer or polymer having an unsaturated group polymerizable with the hydroxyl group, for example, an acryloyl group, a methacryloyl group, a vinyl group or an allyl group, Monomers are particularly preferred.

Examples of this type of compound include 2-hydroxyethyl (meth) acrylate [this abbreviation means 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and the following notation is used according to this], 2 -Or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6
-Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, dialkylene glycol mono (meth) acrylates, for example, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) ) Acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and further 1,2- or 1,3
-And 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth)
Acrylate, N-methylol (meth) acrylamide, N- (meth) acryloyl-1,2-dihydroxypropylamine, N- (meth) acryloyl-1,3-dihydroxypropylamine, addition of phenols and glycidyl (meth) acrylate Products such as 1-phenoxy-2-hydroxypropyl (meth) acrylate,
Examples thereof include 1-naphthoxy-2-hydroxypropyl (meth) acrylate and bisphenol A diglycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are particularly preferable.

In addition, these compounds having a hydroxyl group may be 2
More than one species may be used in combination.

The compounding amount of the compound having a hydroxyl group is usually 5 to 90% by weight, preferably 10 to 70% by weight, more preferably 20 to 90% by weight.
It is 60% by weight, and when it is 5% by weight or less and 90% by weight or more, the adhesiveness decreases.

The polymerizable compound having an acid group used in the present invention is an acid group such as a carboxyl group, a phosphoric acid group, an acid anhydride residue, an unsaturated group polymerizable together with an acid amide group, such as an acryloyl group, a methacryloyl group, and a vinyl group. It is a polymerizable monomer, oligomer or polymer having a group or an allyl group, but a monomer is particularly preferred.

Examples of the polymerizable monomer having a carboxyl group include monocarboxylic acid, dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid or derivatives thereof such as acrylic acid, methacrylic acid, 1,4-di (meth) acryloxyethyl pyromellitic acid, 6- (meth) acryloxyethylnaphthalene 1,2,6-tricarboxylic acid, N, O-di (meth) acryloxytyrosine, O- (meth) acryloxytyrosine, N- (meth) acryloxytyrosine, N- (Meta)
Acryloxyphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-5
-Aminosalicylic acid, N- (meth) acryloyl-4-
Aminosalicylic acid, 4- (meth) acryloylethyl trimellitic acid, 4- (meth) acryloxybutyl trimellitic acid, 4- (meth) acryloxyhexyl trimellitic acid, 4- (meth) acryloxydecyl trimellitic acid, 4-acryloxybutyl trimellitic acid, 2- (meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, 2-hydroxyethyl (meth) acrylate and maleic anhydride Acid addition products, p-vinylbenzoic acid, O-methacryloxytyrosinamide, N-phenylglycine-glycidyl (meth) acrylate, N- (p
-Methylphenyl) glycine-glycidyl (meth) acrylate, 11-methacryloxy-1,1-undecanedicarboxylic acid, 4-[(2-hydroxy-3-methacryloyloxypropyl) amino] phthalic acid, 5-[(2-hydroxy -3-methacryloyloxypropyl) amino] isophthalic acid, 3- [N-methyl-N- (2-hydroxy-3-methacryloyloxypropyl) amino]
Phthalic acid, 4- [N-methyl-N- (2-hydroxy-
Examples thereof include [3-methacryloyloxypropyl) amino] phthalic acid and maleic acid, and particularly preferred are 4-acryloxyethyl trimellitic acid and 4-methacryloxyethyl trimellitic acid.

In addition, as the polymerizable monomer containing an acid group, particularly a carboxyl group, as described above, a radical polymerizable monomer containing a hydroxyl group and a carboxyl group in one molecule is also included.

As the polymerizable monomer containing a phosphoric acid group, a polymerizable monomer containing a phosphoric acid and a phosphonic acid group is preferable. For example, (2- (meth) acryloxy) ethyl-3-phosphonopropionate, (3- ( (Meth) acryloxy) propyl-3-phosphonopropionate, (4
-(Meth) acryloxy) butyl-3-phosphonopropionate, (5- (meth) acryloxy) pentyl-3
-Phosphonopropionate, (6- (meth) acryloxy) hexyl-3-phosphonopropionate, (10-
((Meth) acryloxy) decyl-3-phosphonopropionate, (4- (meth) acryloxy) butyl-phosphonoacetate, (5- (meth) acryloxy) pentyl-phosphonoacetate, (6- (meth) acryloxy) )
Hexyl-phosphonoacetate, (10- (meth) acryloxy) decyl-phosphonoacetate, bis (2- (meth) acryloxyethyl) phosphoric acid, (2- (meth) acryloxyethylphenyl) phosphoric acid,
(10- (meth) acryloxydecyl) phosphoric acid,
Vinyl phosphoric acid, para-vinylbenzylphosphonic acid and the like are preferred. In addition, polymerizable monomers containing a thiophosphate group are also included.

Examples of the polymerizable monomer containing an acid anhydride group include the following: 4- (meth) acryloxyethyl trimellitic anhydride, 6- (meth) acryloxyethylnaphthalene 1,2,6- Tricarboxylic anhydride, 6- (meth) acryloxyethylnaphthalene 2,3,6-tricarboxylic anhydride, 4- (meth) acryloxyethylcarbonylpropionoyl 1,8-naphthalic anhydride, 4- (meta) ) Acryloxyethylnaphthalene 1,8-tricarboxylic anhydride is preferred.

Two or more of the above-mentioned polymerizable compounds having an acid group may be appropriately used in combination, if desired.

The compounding amount of the polymerizable compound having an acid group is usually 0.1 to 90% by weight, preferably 0.5 to 60% by weight. When the amount is less than 0.1% by weight, the adhesiveness decreases. Problems or poor adhesion.

The amino compound having an acid group means an amino compound having an acid group such as a carboxyl group, a sulfonic acid group, an acid amide group, and a carbaldehyde group. Amino compounds having an acid group are primary, secondary and tertiary amino compounds of fatty acids, aromatic and heterocyclic amines, each of which substitutes a hydroxyl group, an alicyclic group, a nitro group, a halogen, a thiol group, etc. It may have a group, and may further have an ester bond, a peptide bond, a urethane bond, a urea bond, a thiourea bond, an ether bond, a thioether bond, a Schiff bond, and the like. When the amino compound having an acid group is an amino acid, all of them are included. For example, basic, neutral, acidic amino acids, or zwitterionizable compounds and non-zwitterionable compounds or D-
All the optical isomers including the isomer, L-isomer and DL-isomer are included. In addition, an amino compound having an acid group, to which various protecting groups as an intermediate conventionally used as a peptide synthesis technique are bound, is also included. Examples of protecting groups include benzyloxycarbonyl, substituted benzyloxycarbonyl, tert-butoxycarbonyl, diisopropylmethyloxycarbonyl, formyl, nitrofluoroacetyl, phthalyl, tosyl, diphenylphosphinothioyl , O-nitrophenylsulfenyl group, benzoyl group, chloroacetyl group, trityl group, benzylidene group, trimethylsilyl group and the like. Further, an amino compound in which a hydrogen atom of an acid group is substituted with an alkali metal or an alkaline earth metal, a compound in which a hydrogen atom of an amino group is substituted with a hydrogen halide, and a peptide or polypeptide having an acid group in the molecule. Also included are proteins or enzymes.

Examples of the amino compound having an acid group as described above include the following compounds: aminobenzoic acid derivatives such as p
-, M-, o-aminobenzoic acid, p-, m-, o-monomethylaminobenzoic acid, p-, m-, o-dimethylaminobenzoic acid,
p-, m-, o-, (N-phenyl) aminobenzoic acid, 4-
Nitroanthranilic acid, 3-hydroxyanthranilic acid, 2-amino-5-methylbenzoic acid, 3-amino-4
-Methylbenzoic acid, 4-amino-3-methylbenzoic acid,
2-amino-3-methylbenzoic acid, 2-amino-5-chlorobenzoic acid, 2-amino-4-chlorobenzoic acid, 3,4
-Diaminobenzoic acid, 3,5-diaminobenzoic acid, p-, m
-, O-Diethylaminobenzoic acid, p-, m-, o-acetamidobenzoic acid or the like, or an aminophthalic acid derivative such as 4-aminophthalic acid, 3-aminophthalic acid, 5-aminoisophthalic acid, 4- (N-methyl) Aminophthalic acid, 3
-(N-methyl) aminophthalic acid or the like, or an aminosalicylic acid derivative such as p-aminosalicylic acid, p-dimethylaminosalicylic acid, N-benzoyl-p-aminosalicylic acid, p-diethylaminosalicylic acid, 5-iodoacetamidosalicylic acid, or an amino acid And amino acid derivatives (however, L-form and D-form as optical isomers)
All of the isomers and DL-isomer are included, but these optical isomer notations are omitted. ) Eg glycine, glycyl-glycine, N
-Methyl glycine, N-phenyl glycine, alanine, phenyl alanine, alanyl alanine, glycyl alanine, alanyl phenylalanine, glutamine, lysine, siltrin, proline, hydroxyproline, tryptophan, tyrosine, 3,5-diiodo Tyrosine / thyroxine, isoleucine, valine, arginine,
Serine, cysteine, glutamic acid, aspartic acid,
Asparagine, histidine, hydroxylysine, methionine, threonine, N-acetyl cysteine, acetyl methionine, kynurenine, leucyl glycine, leucyl glycyl glycine, methyl alanine, 3-
Methylcysteine, 1-methylhistidine, p-aminohippuric acid, 4-amino-n-butyric acid, 2-aminoisobutyric acid, ω-aminocaprylic acid, 2-amino-isocaproic acid, 2-amino-3-hydroxybutyric acid, 2-amino-n
-Caprylic acid, 12-amino-dodecanoic acid, 5-aminovaleric acid, p-aminophenylacetic acid, alanyl serine,
-Amino-n-butyric acid, 2-amino-4-methylvaleric acid (= leucine), N-benzoylglycine (= hippuric acid), S-benzyl cysteine, S-benzyl-N-
Carbobenzyloxy cysteine, β- (3,4-dihydroxy) phenylalanine, homocystine, homocystine, homoserine, N- (p-hydroxyphenyl)
Glycine, S-methyl cysteine, S-carboxymethyl cysteine, 3-methyl histidine, 5-methyl tryptophan, N-methyl tryptophan, α
-Methyltyrosine, nitroarginine, 2-phenylglycine, p-oxyphenylglycine, threonine,
L-canavaline, juncolic acid, trans-4- (aminomethyl) cyclohexanecarboxylic acid (= tranexamic acid), nitrilotripropionic acid, ethylenediaminetetraacetic acid, pyridine-2-carboxylic acid, pyridine-3-carboxylic acid, pyridine- 4-carboxylic acid, 2,5-, 2,6-, 3,4-,
3,5-pyridinecarboxylic acid, 3-indoleacetic acid, 3-
Indoleacrylic acid, 4- (3-indolyl) butyric acid (= 3-indolebutyric acid), indole-3-carboxaldehyde, indole-2-carboxylic acid (= proline), indole-5-carboxylic acid, 3-indolepropionic acid , 4-imidazoleacrylic acid, indazolone-4-carboxylic acid, 3,4-dioxyphenylalanine, tropionic acid, L-oxyglutamic acid, N- (4
-Aminobenzoyl) -glutamic acid, indole-3
-Pyruvate, 3-iodo-tyrosine, carbobenzoxy-aspartate, carbobenzoxy-arginine,
Carbobenzoxy asparagine, carbobenzoxy
Serine, carbobenzoxy isoleucine, carbobenzoxy phenylalanine, carbobenzoxy proline, carbobenzoxy tryptophan, carbobenzoxy valine, Nt-Boc valine, Nt-Boc alanine, N- t-Boc.proline, Ppt-alanine, Ppt-
Valine, Ppt / glycine, Ppt / tryptophan, Ppt /
Glutamine, Ppt / Asparagine, Ppt / Leucine, Ppt
Histidine, Ppt-proline, lysine monohydrochloride, lysine dihydrochloride, p-aminobenzenesulfonic acid, aminomethanesulfonic acid, 4-amino-2-methylbenzene-1-sulfonic acid, 7-amino-1,3-naphthalene Disulfonic acid, 4-amino-5-methylbenzene-1-sulfonic acid, 4-amino-3-methylbenzene-1-sulfonic acid, 4-methylaniline-2-sulfonic acid, 4-pyridineethanesulfonic acid, 3- Pyridinesulfonic acid, benzylidene-p-aminobenzoic acid, benzylidene lysine,
Benzylidene-p-aminosalicylic acid, anthranilamide, 3-amino-4-methylbenzamide, p-aminobenzamide, N-benzylsulfanylamide, p
Sodium aminobenzoate, potassium β-indoleacetate, and enzymes such as trypsin, pepsin, urease and the like as polypeptide acids having an acid group. Particularly preferred are p-aminobenzoic acid, Anthranilic acid, p-dimethylaminobenzoic acid, p-methylaminobenzoic acid, N-methyl-o-aminobenzoic acid, 4-nitroanthranilic acid, 2-amino-4-chlorobenzoic acid,
p-aminosalicylic acid, 4-dimethylaminosalicylic acid, 4-diethylaminosalicylic acid, L-glycine, DL
-Aspartic acid, L-glutamic acid, L-lysine, L
-Glutamine, L-proline, L-hydroxyproline, L-tryptophan, L-tyrosine, methyltyrosine, L-isoleucine, L-valine, L-arginine,
L-serine, L-alanine, L-phenylalanine, DL
-Alanyl-DL-alanine, L-phenylglycine, N
-Phenylglycine, glycylglycine, L-leucine, L-isoleucine, L-threonine, L-asparagine, L-cysteine, glycyl-L-alanine, L-
Homoserine, S-benzyl-L-cysteine, L-citrulline, L-cystine, L-methionine, ω-aminocaprylic acid, 12-aminododecanoic acid, p-aminohippuric acid, 4-amino-n-butyric acid, 2- Aminoisobutyric acid, 3-
Indolebutyric acid, p-aminophenylacetic acid, 3-amino-4-methylbenzamide, S-benzyl-L-cysteine, S-2-pyrrolidin-5-carboxylic acid, pyrrole-2-carboxylic acid, S-2-pyrrolidone- 5-carboxylic acid, indazolone-4-carboxylic acid, nitrilotripropionic acid, trans-4-aminomethyl-1-cyclohexanecarboxylic acid (tranexamic acid), S-carboxymethyl-L-cystine, carbobenzoxy-L-asparagine Acid, carbobenzoxy-L-tryptophan, p
-Sodium aminobenzoate, N- (4-aminobenzoyl) -L-glutamic acid, 3-amino-4-methylbenzamide, anthranilamide, p-aminobenzenesulfonic acid, lysine dihydrochloride, ethylenediaminetetraacetic acid,
Indole-3-carboxaldehyde, trypsin,
Pepsin and the like.

The amount of the amino compound having an acid group is usually 0.01 to 30% by weight, preferably 0.05 to 10% by weight, and more preferably 0.1 to 10% by weight.
If it is 1 to 5% by weight, and if it is 0.01% by weight or less, the adhesiveness will be reduced. If it exceeds 30% by weight, there will be a problem in solubility or the adhesiveness will be reduced.

In the present invention, a curing agent may be added as desired. As the curing agent, a polymerization initiator, an accelerator or a photopolymerization initiator and a curing agent conventionally used as a photopolymerization accelerator are suitable.

Examples of the polymerization initiator include organic peroxides, examples of the polymerization accelerator include amines, and examples of the other curing agents include barbituric acid derivatives.

In addition, trialkylboron or an oxide thereof may also be used.

Examples of the photopolymerization initiator include ultraviolet polymerization or visible light polymerization initiator, and examples of the photopolymerization accelerator include organic nitrogen compounds, particularly amines.

The following compounds are exemplified as organic peroxides: benzoyl peroxide, 4,4'-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide, t-butyl peroxide. Oxymaleic acid, succinic acid peroxide and the like are exemplified, and particularly preferable ones are t-butyl peroxymaleic acid, succinic acid peroxide, benzoyl peroxide, and 4,4′-dichlorobenzoyl peroxide. It is.

The amines have the following general formula: [Wherein, R _{1 to} R ₃ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent (eg, a hydrogen group, a (meth) acryloyl group, or the like) or a carbon atom; A cycloalkyl group having 6 to 12 atoms or a phenyl group which may have a substituent (for example, halogen, an alkyl group having 1 to 10 carbon atoms, a hydroxyl group, a (meth) acryloyl group, etc.) is shown. However, R _{1 to} R ₃ do not simultaneously represent a hydrogen atom. ]
The compound represented by these is mentioned.

Other examples include cyclic amines or divalent or higher valent amines such as diamines.

Examples of such amines include n-butylamine, propylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, di-n
-Butylamine, dipentylamine, trimethylamine, triethylamine, tripropylamine, tri-n
-Butylamine, tripentylamine, trihexylamine, phenylethylamine, ethyleneamine, tetramethyleneamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
Monoethanolamine, N-methyldiethanolamine, triethanolamine, aniline, methylaniline, dimethylaniline, diphenylamine, toluidine, anisidine, N, N-dimethyl-m-anisidine, N, N
-Dimethyl-p-anisidine, N, N-dimethyl-m-aminophenol, N, N-diethyl m-aminophenol, N, N-diethyl-p-anisidine, p-propoxy-N, N-dimethylaniline, p -Hexyloxy-N, N-dimethylaniline, p-butoxy-N, N-dimethylaniline, chloroaniline, bromoaniline, dimethyl-p-
Toluidine, N, N-di (2-hydroxyethyl) -p-
Toluidine, p-aminophenyl methacrylate, N, N
-Dimethylaminophenyl methacrylate, N, N-di (2-hydroxyethyl) phenyl methacrylate, p
-(Β-hydroxy-γ-methacryloxypropoxy)
Phenylamine, N, N-di (2-hydroxyethyl) phenyl-glycidyl (meth) acrylate, N-methylmorpholine, imidazole, 1-methylimidazole,
2-methylimidazole, 2-methyl-4-methylimidazole, ethylenediamine, methylenedianiline, phenylenediamine, N, N-bis (hydroxyethyl) diethylenetriamine, N, N-bis (hydroxyethyl)
Diethylenetriamine, N, N-bis (hydroxyethyl) triethylenetetramine, 3-amino-1,2-propanediol, D, L-1-amino-2-propanol,
2-amino-4-phenylphenol, 2-amino-2
-Phenylethanol, L-2-amino-1-propanol, 3-amino-1-propanol, 2-anilino-
Ethanol, N, N-dihydroxyethylaniline, o-
Or p-aminophenyl alcohol, 5-amino-
1-pentanol, 5-amino-2-methylphenol, 2-amino-5-methylphenol, aminobenzoic esters such as methyl p-aminobenzoate, p-
Ethyl aminobenzoate, butyl p-aminobenzoate, p
Propyl aminobenzoate, isopropyl p-aminobenzoate, ethyl p-N, N (dimethyl) benzoate, p-N, N
Examples include isopropyl (dimethyl) benzoate,
Particularly preferred are N, N-di (2-hydroxyethyl)
-P-toluidine, N, N-dimethylaminoethyl methacrylate, p-aminophenyl methacrylate, p-
(Β-hydroxy-γ-methacryloxypropoxy) phenylamine, triethanolamine, monoethanolamine, p-N, N (dimethyl) isopropyl benzoate,
and ethyl p-aminobenzoate.

The barbituric acid derivative has the following formula: (R ₁ , R ₂ and R ₃ may be the same or different,
Each represents an aliphatic, aromatic, alicyclic or heterocyclic residue or a hydrogen atom which may have a substituent such as a halogen atom, an alkyl group, an alkoxy group, an aryl group or a cyclohexyl group). Things.

The following compounds are exemplified as such barbituric acid derivatives: barbituric acid, 1,3-dimethyl barbituric acid, 1-methyl barbituric acid, 1,3-diphenyl barbituric acid, 5-butyl barbituric acid Tool acid, 1,5-
Dimethyl barbituric acid, 5-ethyl barbituric acid,
5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethyl barbituric acid,
1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5-n-butyl barbituric acid, 1,3-dimethyl-5-sec-butyl barbituric acid, 1,3-dimethyl-5
-Isobutyl barbituric acid, 1,3-dimethyl-5-ter
t-butyl barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenyl barbituric acid, 1-benzyl- 5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, salts thereof (especially alkali metal salts or alkaline earth metal salts) and the like.

Examples of other barbituric acid derivatives include 5-aminobarbituric acid, 2-chlorobarbituric acid, and salts thereof (particularly, alkali metal salts or alkaline earth metal salts).

Particularly preferred barbituric acid derivatives are 5-butyl barbituric acid, 1,3,5-trimethyl barbituric acid, 1,3-dimethyl-5-isobutyl barbituric acid, 1-benzyl-5-phenyl barbituric acid and 1-cyclohexyl-5-ethylbarbituric acid.

Examples of trialkyl boron or its oxide include tri-n-butyl boron, tri-n-amyl boron, triisoamyl boron, tri-sec-amyl boron, triethyl boron, tripropyl boron, tripropyl boron, Examples thereof include isopropyl boron and partial oxides thereof.

As a photopolymerization initiator, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, 2-chlorothioxanthone, 9,10-anthraquinone, camphorquinone,
Examples thereof include ultraviolet sensitizers and visible light sensitizers such as benzyl, 4,4'-dicyclobenzyl and diacetyl.

Examples of the photopolymerization accelerator include N, N-dimethyl-p-toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, triethylamine, trihexylamine, 2-dimethylaminoethanol, N-methylethanolamine,
N, N-dimethylaminoethyl methacrylate, N, N-diethylaminomethacrylate and the like are exemplified.

Two or more of the above curing agents may be appropriately blended if desired.

The amount of the curing agent is usually 0.01 to 30% by weight, preferably 0.1 to 30% by weight.
The content is from 0.05 to 10% by weight, more preferably from 0.1 to 5% by weight. When the content is 0.01% by weight or less, the adhesiveness decreases, and when it is 30% by weight or more, the adhesiveness decreases.

The primer composition according to the present invention, if desired, in addition to the above components, organic solvents such as ethyl alcohol, isopropyl alcohol, alcohols such as propyl alcohol or ketones such as acetone, glutaraldehyde,
Aldehydes such as formaldehyde and tetrahydrofuran may be appropriately blended to adjust the viscosity of the composition or the solubility of the blended components. These organic solvents are incorporated in the composition of the present invention at 0 to 90% by weight. Further, as a shelf life stabilizer, hydroquinone, hydroquinone monomethyl ether, hydroxymethoxybenzophenone, butylated hydroxytoluene, or the like may be appropriately blended.

The composition of the present invention can be used by dividing its constituent part into two or more as necessary. For example, when the curing agent component is composed of an initiator and an accelerator, it may be divided into two or more so as to be used by mixing. Even if the curing agent component is one kind, it may be divided into two or more as necessary. It can be divided and used. When the dentist uses the mixture in a separate container such as a small dish, or when the dentist uses the mixture in the adhesive cavity of the patient's teeth, the method can be appropriately selected. The mode according to this division method can be appropriately selected from the combinations. That is, in (i) water, (ii) a polymerizable compound having a hydroxyl group, (iii) a polymerizable compound having an acid group, and (iv) an amino compound having an acid group, for example, (i) and (ii) , (Iii) and (iv) as solution B, (i) and (ii) as solution A, (ii), (iii) and (iv) as solution B or () and (i) as solution A
(i) and (iv), (ii) and (iii) as solution B or (i) as solution A, (ii) and (iii) and (iv) as solution B or (i) and (iii) as solution A , B liquids (ii) and (i
v) or solution A as (i), (ii) and (iii), solution B as (iv) or solution A as (i), (ii) and (iv);
Examples of the liquid B include (ii), (iii), and (iv).

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Examples 1 to 3 and Comparative Examples 1 to 9 As a primer, ion-exchanged water, 2-hydroxyethyl methacrylate (2-HEMA), 4-acryloxyethyl trimellitic acid (4-AET), 4-acryloxyethyl trimellit Acid anhydride (4-AETA), bis (2-methacryloxyethyl) phosphoric acid (BMEPA), 4
-Amino-n-butyric acid, glutaraldehyde and sodium chloride were mixed and adjusted according to the formulation shown in Table 1.

On the other hand, as a one-component photopolymerizable bonding composition,
3,5-trimethylhexamethylene diisocyanate and 2
50 parts by weight of a reaction product of 1: 2 (mol) of hydroxyethyl methacrylate, 35 parts by weight of triethylene glycol dimethacrylate, 10 parts by weight of ethylene glycol dimethacrylate
Parts by weight, 2-hydroxyethyl methacrylate 5 parts by weight, dl-camphorquinone 0.8 parts by weight, N, N-dimethylaminoethyl methacrylate 1.0 parts by weight, and butylated hydroxytoluene 0.05 parts by weight.

The adhesive strength was determined by a compression shear adhesion test between bovine dentin, photopolymerizable composite resin, and Shofu Lightfill-P (manufactured by Shofu Co., Ltd.). First, freshly extracted cow front teeth were frozen and stored in distilled water, and thawed before use. The bovine teeth were embedded in epoxy resin, and the dentin surface was polished smoothly with water-resistant abrasive paper No. 600. After the polished dentin surface is washed with water and dried, it is treated with each of the primers in Table 1 for 1 minute (treating with a small sponge while rubbing), and after drying, the one-part photopolymerizable bonding composition is applied with a small brush. Then, visible light was irradiated for 30 seconds using a Shofu Daylight Lamp II (manufactured by Shofu). Further, a resin mold (inner diameter: 4 mm, height: 2 mm) was placed, and Matsukaze Lightfill-P was charged, and visible light was irradiated from the upper surface for 30 seconds. Adhesion specimen without resin mold
After standing in water at 37 ° C. for 24 hours, the compressive shear adhesive strength was measured at a crosshead speed of 1 mm / min using a Shimadzu Autograph AG-5000B. Note that all of the above tests and the tests described below
Performed at room temperature of 23 ± 2 ° C.

As is clear from the results in Table 1, acid etching was performed in Example 1 using a primer composed of ion-exchanged water, 2-HEMA, 4-AET and 4-amino-n-butyric acid, which are the components of the present invention. The compressive shear adhesion between untreated bovine dentin (hereinafter abbreviated as acid-free dentin) and Shofu Lightfill-P (light-cured composite resin) is 240.8 kgf.
/ cm ² indicates, with respect to 0～93.2Kgf / cm ² of Comparative Examples 1 to 9,
It shows a remarkably high adhesive strength. In the first embodiment,
Depending on the measurement sample, the maximum value is 446.6 kgf / cm ² (dentin cohesion failure), surprisingly exceeding the tensile strength of natural dentin [420 kgf / cm ² : Dental Engineering Vol. 70, p. 42 (1984)] Comparative Example 1
-9 all exhibited interfacial fracture. Further, Examples 1 to 3 showed significantly higher primer effects than Comparative Examples 6 to 8 which were the prior art. In addition, it was evident from Comparative Examples 1 to 5 that the adhesive strength was remarkably reduced even if any of the components of the present invention were missing. From the above results, the dentin without acid treatment was formed by the interaction of water, 2-HEMA, a polymerizable compound having an acid group (such as 4-AET) and 4-amino-n-butyric acid, which basically constitute the present invention. It became clear that excellent adhesive strength was obtained.

Examples 4 to 7 As a primer, 7 parts by weight of 4-acryloxyethyl trimellitic acid and 0.51 of p-dimethylaminobenzoic acid were used.
Ion-exchanged water / 2-hydroxyethyl methacrylate (2-HEMA) was mixed and prepared in the amount shown in Table 2 with respect to parts by weight. Using the primers of Table 2 in combination with a one-part photopolymerizable bonding composition (the one used in Examples 1 to 3 was used as is), dentin without acid treatment and Matsukaze as in Examples 1 to 3. The shear adhesive strength of Lightfill-P was determined and Table 2
It was shown to.

Examples 8 to 15 As a primer, 4-acryloxyethyl trimellitic acid (40 parts by weight of ion-exchanged water, 60 parts by weight of 2-hydroxyethyl methacrylate, and 0.21 part by weight of DL-aspartic acid) in the amount shown in Table 3 was used. 4-AET). Using the primers of Table 3 together with a one-part photopolymerizable bonding composition (the same ones used in Examples 1 to 3) as in Examples 1 to 3 without dentin and Matsukaze The shear adhesive strength of Lightfill-P was determined and Table 3
It was shown to.

Examples 16 to 20 L-hydroxyproline was used as a primer in an amount shown in Table 4 with respect to 40 parts by weight of ion-exchanged water, 60 parts by weight of 2-hydroxyethyl methacrylate, and 7 parts by weight of 4-acryloxyethyl trimellitic acid. A mixture was prepared. Using the primers of Table 4 and the one-part photopolymerizable bonding composition used in Examples 1 to 3,
In the same manner as described above, the shear adhesive strength between dentin without acid treatment, photopolymerizable composite resin, and Shofu Lightfill-P was determined and is shown in Table 4.

Examples 21 to 78 Examples 1 to 3 using the composition of the present invention as a primer
Using the one-component photopolymerizable bonding composition and Matsukaze Lightfill-P used in Example 1 as they were, the shear adhesion to dentin without acid treatment was determined according to the methods of Examples 1 to 3. As a primer, 40 parts by weight of ion-exchanged water,
With respect to 60 parts by weight of 2-hydroxyethyl methacrylate and 7 parts by weight of 4-acryloxyethyl trimellitic acid, the amount of the amino compound having an acid group is shown in Table 5 (however, the amount of water is 40 parts by weight / 2- HEMA: 0.307 mol% to 60 parts by weight
). Table 5 shows the shear adhesive strength when each primer was used. In the table, the shear adhesive strength (kgf / cm ² ) is shown as an average value ± standard deviation (highest value), and * D indicates that destruction of the dentin adherend was observed. The number of test pieces is N
= 6-7.

Examples 79 and 80 The one-component photopolymerizable bonding material composition and Matsukaze Lightfill-P used in Examples 1 to 3 were used as they were according to the formulations shown in Table 6 as primers. The shear adhesion to dentin without acid treatment was determined according to the method of Examples 1-3. Table 6 shows the results.

Example 81 Using the composition of the present invention as a primer, and further using the one-part photopolymerizable bonding composition of Examples 1 to 3 as it is, a dental composite resin, Shofu Light Fill-P [manufactured by Shofu Co., Ltd. ] And the adhesive strength to dentin or glass ionomer cement without acid treatment and its durability.

For bovine dentin without acid treatment (only # 600 polishing)
Using the liquid of Example 39 (water / 2-HEMA / 4-AET / L-alanine-based primer) as it was, an adhesion test body was prepared according to the method of Examples 1 to 3. Similarly, a glass ionomer cement without acid treatment was prepared.

After 1 day (0 cycle) in 37 ° C water, these specimens were subjected to a thermal cycle (1 minute in 4 ° C water, 1 minute in 60 ° C water) test.
Runs were performed at 2000 and 5000 cycles to determine shear adhesion. Table 7 shows the results.

Example 82 As a primer, 40 parts by weight of distilled water, 60 parts by weight of 2-hydroxyethyl methacrylate, 7 parts by weight of (6-methacryloxy) hexyl-3-phosphonopropionate,
0.64 parts by weight of 4-diethylaminosalicylic acid was blended and prepared. Using this primer, in combination with the one-component photopolymerizable bonding composition used in Examples 1 to 3, the shear adhesion between dentin without acid treatment, the photopolymerizable composite resin, and Matsukaze Lightfill-P was performed. As a result of a measurement according to the method of Examples 1 to 3, the result was 225.3 kgf / cm ² .

Example 83 PMMA-type dental restorative resin "ADFA" [manufactured by Shofu Co., Ltd.] and MMA-type dental adhesive "acryl bond"
[Effects of Shofu Co., Ltd.] were used to evaluate the dentin adhesion in accordance with these instructions. As primers, distilled water 40 parts by weight, 2-hydroxyethyl methacrylate 50 parts by weight, 1,2-dihydroxypropyl methacrylate 10 Parts by weight, 5 parts by weight of 4-methacryloxyethyl trimellitic acid and 0.37 parts by weight of L-cysteine are mixed and used, and the methods of Examples 1 to 3 are used (however, light irradiation is not performed).
The shear adhesive strength was determined according to.

As a result, in the case of "acrylic bond" + "adfa"
23.6 kgf / cm ² , whereas the primer of the present invention +
132.5kgf / cm ^{2 for} "acryl bond" + "adfa"
showed that.

Example 84 A primer was prepared by mixing 40 parts by weight of ion-exchanged water, 40 parts by weight of 2-hydroxyethyl methacrylate, 7 parts by weight of 4-acryloxyethyl trimellitic acid, and 0.4 part by weight of L-valine.

On the other hand, silane-treated silica 75 parts by weight, silane-treated barium sulfate 25 parts by weight, N, N-
0.1 parts by weight of di- (2-hydroxyethyl) para-toluidine and 1-benzyl-5-phenylbarbituric acid
It was mixed and prepared with 1.0 part by weight. As a liquid agent, a 1,2 (mole) reaction product of 1,1,3-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate was used.
Parts by weight, triethylene glycol dimethacrylate 28 parts by weight, 2-hydroxyethyl methacrylate 7 parts by weight,
Prepared with 5 parts by weight of 4-acryloxyethyl trimellitic acid, 0.3 parts by weight of benzoyl peroxide and 0.05 parts by weight of butylated hydroxytoluene, powder / liquid = 3.5 / 1.
A mixture of 0 was used.

The silane treatment of the filler was performed by using a normal acetic acid method on silica or barium sulfate using γ-methacryloxypropyltrimethoxysilane. That is,
0.1 g of γ-methacryloxypropyltrimethoxysilane
100 parts by weight of a filler dissolved in an aqueous solution of acetic acid at a concentration of 2.0% by weight was added and mixed with 100 parts by weight of a filler, and the slurry was air-dried.
Surface treatment was performed by heat treatment for 0 minutes.

The bond strength was determined by a shear bond test between bovine dentin and resin cement. The method was implemented according to Examples 1-3. However, light irradiation was performed without. as a result,
In the case of resin cement only (without primer),
Whereas showed 3.35kgf / cm ^2, when used in combination with the present invention primers showed 134.4kgf / cm ^2.

In addition, using this primer, the shear adhesion between bovine tooth enamel without acid etching and the prototype resin cement was evaluated.
It was determined in one day at 37 ° C in water. As a result, when the composition of Example 1 was used, it showed 191.6 kgf / cm ² . In the case where the bovine enamel instead of the present invention primed to phosphoric acid etching process shows the 208.0kgf / cm ^2, phosphoric acid etching treatment and comparable adhesion by the present invention a primer that is obtained revealed . The enamel adhesive strength without primer treatment or acid treatment was 56 kgf / cm ² . From the above results, it was found that the composition of the present invention is an effective primer that promotes adhesion to enamel without acid enamel treatment.

Example 85 As a primer, 40 parts by weight of ion-exchanged water, 60 parts by weight of 2-hydroxyethyl methacrylate, 7 parts by weight of 4-acryloxyethyl trimellitic acid, and 0.1 part of L-isoleucine were used.
40 parts by weight, 0.7 parts by weight of dl-camphorquinone and 0.6 parts by weight of N, N-dimethylaminoethyl methacrylate were mixed and prepared. In combination with this primer, the one-component photopolymerizable bonding composition and Shofu Light Fill-P used in Examples 1 to 3 were used as they were, and the shear adhesive strength to dentin without acid treatment was measured in Examples 1 to 3. It was determined according to method 3. As a result, it showed 208.6 kgf / cm ² .

Effect of the Invention The primer composition according to the present invention is generally a composition suitable as an undercoat when bonding an adhesive restorative material or the like, for example, hard tissue of a living body, particularly, enamel or dentin of natural teeth or glass ionomer cement Resin cement, bonding material, composite resin or PM
When a dental adhesive restoration material such as MA resin is adhered, strong adhesion between the two and its durability are imparted.

Although the present invention is mainly directed to the field of dentistry, the primer composition according to the present invention is a highly versatile one that can be used in other fields, for example, fields of surgery, orthopedics, plastic surgery, and the like. is there.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-240712 (JP, A) JP-A-1-144487 (JP, A) JP-A-60-4510 (JP, A) JP-A-63- 279851 (JP, A) JP-A-62-223289 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 6/00 A61K 25/00 C09J 5/02

Claims (3)

(57) [Claims] (1) 0.5 to 90% by weight of water, (ii) 5 to 90% by weight of a polymerizable compound having a hydroxyl group, (iii) 0.1 to 90% by weight of a polymerizable compound having an acid group, and (iv) A primer composition containing 0.01 to 30% by weight of an amino compound having an acid group. 2. The primer composition according to claim 1, wherein the components (i) to (iv) are divided into two or more arbitrary components. 3. The primer composition according to claim 1, further comprising an organic solvent and / or a shelf life stabilizer.