JPS62175412A - Restorative material composition for dental use - Google Patents

Abstract

PURPOSE:To provide the titled composition containing a radically polymerizable monomer and a specific ternary hardener, having high safety in clinical operation, resistant to discoloration, keeping excellent appearance, exhibiting high mechanical strength and giving strong and durable adhesive strength. CONSTITUTION:The objective composition contains (A) 100pts.(wt.) of a radically polymerizable monomer (e.g. monofunctional or bi-tetrafunctional (meth)acrylate with (B) a hardener consisting of (B1) 0.01-10pts. of an organic peroxide (e.g. succinic acid peroxide), (B2) 0.01-20pts. of an alkali metal salt, alkaline earth metal salt or amine salt of an aromatic sulfinic acid (e.g. sodium benzenesulfinate) and (B3) 0.01-20pts. of a barbituric acid derivative [e.g. the compound of formula (R1-R3 are H or residue of aliphatic, aromatic, alicyclic or heterocyclic compound)]. Preferably, the composition is further compounded with 0.1-30pts. of an organic acid, its acid anhydride or a phosphoric acid ester.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a dental restorative composition having adhesive properties.

More specifically, the present invention provides a dental implant that exhibits excellent aesthetics and high mechanical strength due to its hardening agent properties, and that firmly adheres to natural tooth enamel and dentin as well as various metal materials, ceramic materials, and polymeric materials. The present invention relates to restorative material compositions such as adhesives, floor resins, composite resins, cement, and veneer resins.

The composition according to the invention can also be applied to the field of adhesives for hard tissues of the human body and general industrial adhesives.

Conventional technology As resins for dental restorations, much research has been conducted on (meth)acrylic monomers due to their good aesthetics and ability to harden in a short time. provided. For example, U.S. Patent No. 30661
Specification No. 12, Specification No. 3629187, Special Publication No. 4
Publication No. 8-11156 and Japanese Unexamined Patent Publication No. 1983-103648
In the publications, renone is cured by a redox polymerization method using a polymerization initiator and an accelerator, an ultraviolet polymerization method, or a visible light polymerization method, and methacrylate or a modified urethane thereof is used as an aromatic polyfunctional acrylate. The main ingredients are dental composite resins, adhesives,
Pit and fissure sealants, etc. have been disclosed).

Recently, in the field of dentistry, the above-mentioned binder resins, especially methacrylate-based resins abbreviated as BIS-GMA resin, have been used instead of the conventional instant polymerization resins whose main components are (meth)acrylic threadworms. A viscous composite material made of acrylic monomer mixed with a large amount of inorganic filler is provided as a composite resin.

However, this type of dental composite resin generally has insufficient adhesion to the tooth structure, which may result in the restoration falling off, secondary caries caused by the invasion and leakage of bacteria, etc. at the adhesive periphery, and pulp irritation. , marginal fractures, marginal discoloration, etc. occur, which is a clinical problem in dentistry.

In order to solve such clinical problems, methods of improving the adhesion between composite resins and the stroma are attracting attention.

For example, the so-called acid etching method, in which enamel is treated with acid, has been known for a long time [Journal of Dental Research]
Research), Vol. 34(6), pp. 849-853 (1955)]. Bonding using this method is not due to chemical bonding between the tooth substance and the bonding resin, but is primarily a mechanical fit due to the resin entering the microstructure formed by demineralization of the enamel trabeculae and hardening and anchoring. Based on

In addition, proposals have been made to improve the adhesion between resin and tooth substance using methacrylic monomers containing phosphate ester residues or acid anhydride residues, but this type of monomer The class includes redox curing agents (benzoyl peroxide and tertiary
Depending on the amine), curing properties may be poor or adhesiveness may be insufficient due to a salt-forming reaction, and even when used in combination with other known curing agents, sufficient adhesion may not be exhibited.

On the other hand, recent research trends regarding dental resins have shifted to the development of resins that exhibit excellent adhesion not only to tooth structure but also to various metals, ceramic materials, and polymeric materials. However, these disclosed prior art techniques cannot be said to have sufficient adhesion to the above-mentioned adherends, and it is recognized that this is due to a serious defect in the conventional curing agent components.

Compositions containing benzoyl peroxide and aromatic tertiary amine as hardening agents have long been known as dental restorative compositions. Due to the product formed from intermediate products due to the reaction of ingredients, it is easy to discolor over time due to ultraviolet rays, heat, etc. (Not only does it have insufficient mechanical strength, but also has poor adhesion to tooth structure and metal. (approximately 0.5-0.6 Kgl'/cm2 for dentin without acid treatment).

In addition to the above curing agent system containing hensyl peroxide and an aromatic tertiary amine, 4-methacryloxyethyl trimellitic anhydride (JP-A-54-11149, JP-A-54-1999) is added.
In compositions containing A-12338 and 55-110171), a charge transfer complex is rapidly formed between the aromatic tertiary amine and the acid anhydride residue immediately after mixing, resulting in redox polymerization. In addition, the cured product becomes yellowish-brown and has low adhesiveness.

The above curing agent system containing benzoyl peroxide and an aromatic tertiary amine is further supplemented with Cl-l2=CH-PO(OH)
Q or CI, =CH-C,H, -CHtPO(OH)
Radically polymerizable organophosphorus compounds such as No. 2 (Journal of Dental Research, Vol. 53, pp. 878-8)
In the case of compositions containing the following compounds (see p. 88 and Vol. 56, pp. 543-952), polymerization is significantly delayed or does not cure, and the expected adhesion is not obtained. do not have.

Compositions containing peroxide and aromatic sulfinic acid as curing agents solve the problem of discoloration, but not only do they fail to cure sufficiently due to the effects of moisture and oxygen, but the cured product also deteriorates. Due to the hygroscopic nature of the residual sulfinic acid, water absorption becomes high in the oral cavity and tends to cause vitiligo and deterioration.

Japanese Patent Publication No. 56-33363 discloses that the curing speed of the resin and its adhesion to tooth structure are improved by blending diasilver oxide, aromatic tertiary amine, and metal salt of aromatic sulfinic acid as curing agents. The technology has been disclosed. However, in this case, although the curing speed is improved, it has been found that there is discoloration due to tertiary amines and the water-resistant adhesive strength to tooth tissue, especially dentin, is extremely low.

In the case of compositions containing barbylic acids, heavy metals and halogen ions as curing agents (West German Patent No. 14)
No. 95520), there are no problems with respect to discoloration or water resistance, but there is a problem in that the adhesion to tooth structure is poor, and in particular, it does not adhere to dentin.

Special Publication No. 42-14318 and No. 45-2919
57 - Publication FLA discloses a technique for improving adhesiveness to flesh, especially dentin, by using l-realkylborane as a hardening agent, but trialkylborane Borane, such as tri-n-butylborane, can only be used in combination with very limited radically polymerizable monomers such as methyl methacrylate, and is flammable, which poses storage and clinical safety problems. There are also difficulties in operability.

Problems to be Solved by the Invention The present invention solves all the problems of the prior art described above, and is highly safe in clinical operation, has no discoloration, has excellent aesthetics, exhibits high mechanical strength, and can be used for natural teeth. This was developed to provide a new dental restorative composition that exhibits durable and high adhesiveness not only to enamel and dentin, but also to various metal materials, ceramic materials, polymeric materials, etc. be.

Means for Solving the Problems The present inventors based on the philosophy that the properties of a curing agent are deeply involved in the adhesiveness and physical properties of the cured product. We conducted a thorough search for the relationship between organic peroxide, aromatic sulfinic acid metal salts, and barbylic acid derivatives as hardening agents in dental restorative compositions containing radically polymerizable monomers. When this ternary curing agent is used in combination with an organic acid, an acid anhydride, or a phosphoric acid ester compound, all of the problems of the prior art described above are solved, and it is highly safe in clinical operation and does not cause discoloration. It is aesthetically pleasing, exhibits high mechanical strength, and has strong and durable adhesion not only to natural tooth enamel and dentin, but also to various metal materials, ceramic materials, polymeric materials, etc. The present invention was achieved based on the discovery that

That is, the present invention provides a dental restorative material composition containing a radically polymerizable monomer, an organic peroxide, an alkali metal salt, an alkali metal salt, or an amine salt of an aromatic sulfinic acid, and a curing agent containing a barbylic acid derivative. , and radically polymerizable monomers and organic peroxides, alkali metal salts, supra-alkali metal salts or amine salts of aromatic sulfinic acids, barbylic acid derivatives and organic acids, such as acid anhydrides or phosphoric acid ester compounds. The present invention relates to a dental restorative material composition containing a hardening agent.

The present invention will be described in more detail below. In this specification, "floor resin" refers to floor lenone, repair resin, floor lining material, floor resin that can be attached to metal floors, etc. , "Dental composite resin" means a dental composite resin and abutment construction material, etc. whose composition contains an inorganic filler or an organic composite filler, and "dental adhesive material" means an orthodontic composite resin, etc. adhesive materials, pit and fissure sealants to prevent caries, dental bonding materials that can be used in conjunction with composite resin restorations, primers for pretreatment,
"Dental cement" refers to metal-adhesive resins and porcelain-repair adhesives that can be used in combination with front-mounting resins made by photopolymerization or heat polymerization, and "dental cement" refers to backing lining cements, crowns, inlays, It refers to resin cements that can be applied to inlays, bridges, fixed teeth, etc., and "resins for dental prefixes" refers to hard resins baked by heat polymerization, hard resins photopolymerized, and the like.

Furthermore, "(meth)acrylate" means acrylate or methacrylate, and "organic acid" means organic acids other than barbylic acid.

The radically polymerizable monomer used in the present invention includes radical polymers that have been conventionally used in dental restorative materials such as floor resins, dental composite resins, dental adhesives, resin cements, and veneer resins. In addition to polymerizable monomers,
Examples include radically polymerizable monofunctional and di- to tetrafunctional acrylates and methacrylates.

These (meth)acrylates may have a fluorine atom, an aryl group, or a urethane bond in the molecule.

Such compounds include: methyl (meth)acrylate, propyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate.
Acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-hydroxy-3-(p-methyl)phenoginepropyl methacrylate, neopentyl glycol di(meth)acrylate , Monoethylene glycol di(meth)acrylate, Diethylene glycol di(meth)acrylate, Triethylene glycol di(
meth)acrylate, tetraethylene glycol di(meth)acrylate, dodecaethylene glycol di(meth)acrylate, glycerin di(meth)acrylate,
Bisphenol A-di(meth)acrylate, 2.2'
-bis[(meth)acryloxy-ethoxyphenyl]propane, 2,2'-bis[(γ-(meth)acryloxy-β-hydroxypropoxy)phenyl]propane, trimethylolpropane tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate, glycidyl(meth)acrylate, t-butylaminoethyl methacrylate) HF salt, methyl-α-fluoroacrylate, 2,2.2-, trifluoroethyl-methacrylate, 2, 2.2-trifluoroethyl-α-
Examples of fluoroacrylate and urethane bond-containing compounds include reaction products of diisocyanates and hydroxyl group-containing (meth)acrylates, reaction products of diisocyanates and hydroxyl group-containing mono(meth)acrylates at a molar ratio of 1:2, and diisocyanates. Molar ratio of hydroxyl group-containing di(meth)acrylates to hydroxyl group containing di(meth)acrylates!
= 2 reaction product, reaction product of diisocyanate, hydroxyl group-containing mono(meth)acrylate, and hydroxyl group-containing di(meth)acrylate in a molar ratio of 1:1:1, diisocyanate having diisocyanate groups at both ends. Urethane prepolymers and hydroxyl group-containing mono(meth)
A reaction product with a molar ratio l:2 of acrylates, the urethane prepolymers and hydroxyl base a (meth)
Reaction product with acrylates in a molar ratio l:2, reaction product with the urethane prepolymer, hydroxyl group-containing mono(meth)acrylates and hydroxyl group-containing di(meth)acrylates in a molar ratio 1:l:I such as di((meth)acryloxyethyl)xylene diurethane, di((meth)acryloxyethyl)toluene diurethane, di((meth)acryloxyethyl)hexamethylene diurethane, di((meth)acryloxyethyl) (oxyethyl)trimethylhexamethylene diurethane, di((meth)acryloxyethyl)isophorone diurethane, bis[di((meth)acryloxy)glycerol]hexamethylene diurethane, bis[di((meth)acryloxy) Glycerol cotrimethylhexamethylene diurethane, bis[di(
(meth)acryloxy)glycerol coisophorone diurethane, etc., reaction of 1.1.3-trimethylhexamethylene diisocyanate, 2-hydroxyethyl (meth)acrylate, and glycerin di(meth)acrylate in a molar ratio of 1:l:1 Product, reaction product of isophorone diisocyanate and 2-hydroxyethyl (methane acrylate and glycerin di(meth)acrylate in molar ratio 1:l:l), molar ratio of (meth)acrylic acid and glycidyl methacrylate in l: l reaction product and 1.1
．． 3-trimedelhexamethylene diisocyanate and the reaction product of 2-hydroxyethyl methacrylate and glycidyl methacrylate in a molar ratio l, l in a molar ratio of 1:1:1, 2-hydroxyethyl The reaction product of methacrylate-1. and glycidyl methacrylate in a molar ratio l; l and the reaction product of isophorone diisocyanate in a molar ratio of 1:1, (
Molar ratio of the reaction product of meth)acrylic acid and glycidyl methacrylate l:1 and diphenylmethane diisocyanate! = 1 reaction product, etc. are exemplified.

Examples of the organic peroxide used in the present invention include the following compounds: benzoyl peroxide, 4゜4゛-dichlorobenzoyl peroxide, 2,4-)chlorobenzoyl peroxide, dilauryl peroxide, methyl ethyl ketone. peroxide, t-butyl peroxymaleic acid, succinic acid peroxide, etc. Among these peroxides, particularly preferred are L-butyl peroxymaleic acid, succinic acid peroxide, benzoalperoxide, and 4,4°-dichlorobenzoyl peroxide.

Note that two or more types of organic peroxides may be used in combination if desired.

When these organic peroxides are used in combination with tertiary amines, the cured product discolors over time and is recognized as having no adhesive properties, but if these organic peroxides are replaced with tertiary amines, When used in combination with salts of aromatic sulfinic acids and barbylic acids, acid anhydrides,
New findings have been obtained that when used in combination with organic acids or phosphoric acid esters, the cured product does not discolor and exhibits strong adhesion to tooth structure, dental metals, dental porcelain, etc.

The amount of organic peroxide blended is 100% of the radically polymerizable monomer.
About 0.01-10 parts by weight, preferably 0
．． It is 1 to 5.0 parts by weight. If it is less than 0.01 parts by weight, the polymerization reaction will be insufficient, and if it is more than 10 parts by weight, the polymerization reaction will be excessively accelerated.

In the present invention, a sulfinic acid salt is further used as a curing agent component. As the sulfinic acid salt, an aromatic sulfinic acid salt is used from the viewpoint of stability of the curing agent. As salts, alkali metal, alkaline earth metal and amine salts are used. Examples of sulfinic acid salts include sodium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, triethylammonium benzenesulfinate, and benzenesulfinic acid.N.

Examples include N-dimethyl-P-toluidine salt, salts of p-toluenesulfinic acid, β-naphthalenesulfinic acid, and styrenesulfinic acid.

Note that, if desired, two or more salts of aromatic sulfinic acids may be used in combination.

Conventionally, for example, Japanese Patent Publication No. 56-33363 discloses that the curing speed and adhesion of renon to tooth structure can be improved by blending dian ruberoxide, aromatic tertiary amine, and metal salts of aromatic sulfinic acid as curing agents. Techniques for improving this are disclosed. However, in this case, although the curing speed has been improved, it has been found that the discoloration caused by tertiary amines and the bone bonding force against tooth tissue, especially dentin, are extremely low.

The present inventors added a radically polymerizable monopolymer as a curing agent.
When this aromatic sulfinic acid salt, organic peroxide, and barbylic acid derivative are used together, or when this ternary curing agent is used together with an organic acid, an acid anhydride, or a phosphoric acid ester compound, the composition of the present invention It has been found that it does not discolor, has high mechanical strength, and strongly adheres to enamel, dentin, metal, and porcelain.

The amount of these sulfinic acid salts used is 10% of the polymerizable monomer.
The amount is 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight. If the amount is less than 0.01 parts by weight, polymerization of the single polymer will be insufficient, and if it exceeds 20 parts by weight, the weight reaction will be too rapid, and elution from the cured product will increase, causing material deterioration. .

A barbylic acid derivative is further used as a component of the curing agent in the present invention. A combination of only an organic peroxide and a metal salt of an organic sulfinic acid has problems in that it does not cure or takes an extremely long curing time, and has insufficient adhesion. However, in the present invention, due to the curing agent composition of the present invention in which a barbylic acid derivative is added to these curing agent systems,
Appropriate curing time can be obtained, as well as high adhesive strength and mechanical strength.

Most of the barbylic acid derivatives used in the present invention are of the following formula: It is represented by an aliphatic, aromatic, or a heterocyclic residue or a hydrogen atom which may have a substituent such as a ring.

Examples of such barbylic acid derivatives include the following compounds: Barbylic acid, 1,3-dimethylbarbituric acid, 1-methylbarbituric acid, ■, 3-diphenylbarbituric acid, 5- Butylbarbituric acid, 1.
5-dimethylbarbituric acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3.5-)-dimethylbarbituric acid , 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-5-n-butylbarbituric acid, 1,3-dimethyl-5-sec-butylbarbituric acid, l,3-dimethyl- 5-isobutylbarbituric acid, 1.3-dimethyl-5-tert-butylbarbituric acid, 1.3-dimethyl-5-cyclopentylbarbituric acid, 1.3-dimethyl-5-cyclohexyl Barbyric acid, I+3-dimethyl-5-phenylbarbituric acid,! -benzy-5-phenylbarbituric acid, 1
-cyclohexyl-5-ethylbarbituric acid, their salts (especially alkali metal salts or alkaline earth metal salts), etc.

Examples of other barbyric acid derivatives include 5-aminobarbylic acid, 2-thiobarbylic acid, 5-chlorobarbylic acid, and salts thereof (particularly alkali metal salts or alkaline earth metal salts).

Particularly preferred barbylic acid derivatives are 5-butylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1.
These are 3-dimethyl-5-isobutylbarbituric acid, -benzyl-5-phenylbarbituric acid and 1-cyclohexyl-5-ethylbarbituric acid.

Note that two or more types of barbylic acid derivatives may be used in combination if desired.

Conventionally, it has been proposed that this barby acid derivative does not discolor and has good water resistance when used in combination with heavy metals and halogen ions, but it has the drawbacks of low adhesion to tooth structure and insufficient mechanical strength. However, the curing agent according to the present invention, i.e., the combination of aromatic sulfinic acid metal salts, organic peroxides and barbylic acid derivatives, or the addition of organic acids or acid anhydrides or phosphoric acid ester compounds thereto. It has been found that by blending it, not only can all of the above-mentioned drawbacks be improved, but also it can firmly adhere to metals and porcelain.

The amount of the barbylic acid derivative to be blended is about 0.01 to 20 parts by weight, preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the radically polymerizable monomer, and if it is less than 0.01 part by weight, the polymerization reaction is If the polymerization reaction is not carried out sufficiently and the amount of polymerization exceeds 20, the polymerization reaction will be excessively accelerated.

A second aspect of the dental restorative composition according to the present invention comprises the radically polymerizable m-form, an organic peroxide, an alkali metal salt of an aromatic sulfinic acid, an alkali metal salt, an amine salt, and a barbylic acid derivative. It is a composition in which an acid anhydride or a phosphoric acid ester compound is further blended with a hexagonal acid.

When these organic acids, acid anhydrides, or phosphoric acid ester compounds are used in combination with organic peroxides and metal salts of aromatic sulfinic acids, they have the advantage of improving adhesion, but the surface hardening of the cured product is Unfortunately, it wasn't as strong as K11l. However, the curing agent system of the present invention,
In other words, when an organic acid, an acid anhydride, or a phosphoric acid ester compound is used in combination with a ternary curing agent consisting of an organic peroxide, a metal salt of an aromatic sulfinic acid, and a barbylic acid derivative, there is On the other hand, it has been found that higher adhesive strength can be obtained, surface hardening properties are better, and mechanical strength is also increased.

Examples of organic acids include monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids, and preferred organic acids are acids having an unsaturated group capable of radical polymerization,
For example, acrylic acid, methacrylic acid, 4-methacryloxyethyltrimethic acid, 4-acryloquinethyltrimethic acid, 6-methacryloxyethylnaphthalene 1,
2.6-tricarboxylic acid, N,0-dimethacryloxydyrosine, 0-methacryloxytyrosine, N-methacryloquinophenylalanine, l,4-dimethacrylic [
One example is quinoethylpyromellitic acid.

As an acid anhydride, it has an unsaturated group capable of radical polymerization,
Compounds in which an acid anhydride residue is bonded to an aryl group are preferred, and particularly suitable acid anhydrides include the following:
4-Methacryloxyethyltrimethic anhydride, 4
-Acryloquine ethyltrimethic anhydride, 6-methacryloxethylnaphthalene 1.2.6-tricarboxylic anhydride, 6-methacryloquinethylnaphthalene 2,
3.6-tricarboxylic anhydride, 4-methacryloxyethoxycarbonylpropionoyl 1.8-naphthalic anhydride, 4-methacryloxyethylnaphthalene 1.8
-Tricarboxylic acid anhydride, etc.

In the present invention, organic acids or acid anhydrides are useful in that they have the effect of controlling the polymerization reaction when combined with the above-mentioned curing agent system, and also have the effect of improving adhesion to metals and tooth structure.

Conventionally, monomers containing these acid anhydride groups, for example, when benzoyl peroxide and aromatic tertiary amine are used in combination in a curing agent system, immediately after mixing, monomers containing these acid anhydride groups rapidly exhibit C-T in the composition. A complex formation reaction occurred, and the cured product exhibited a yellow-brown discoloration, and the curing time was delayed and the adhesive strength was low. However, the present inventors found that by using these acid anhydrides in combination with organic peroxides, metal salts of aromatic sulfinic acids, and barbylic acid derivatives, the curing speed was stabilized, there was no yellowish-brown discoloration, and high mechanical strength was achieved. It was discovered that it not only provides strong adhesion to natural tooth esters, dentin, metals, ceramics, etc.

The amount of organic acid or acid anhydride is usually about 0.01 to 30 parts by weight per 100 parts by weight of the radically polymerizable monomer.
Preferably it is 1 to 20 parts by weight.

When the amount exceeds 30 parts by weight, the mechanical strength of the cured product decreases.

Suitable phosphoric acid ester compounds for use in the present invention are phosphorus compounds having radically polymerizable groups, such as bis(2-(meth)acryloquinethyl)phosphoric acid, (2(meth)acryloquine ethyl)phosphoric acid, Examples include loxethylphenyl)phosphoric acid, his(2-(meth)acryloquinethyl)phosphoric acid, and the like.

Phosphate esters are useful in improving tooth adhesion.

Conventionally, these phosphoric acid ester compounds have had the disadvantage of significantly retarding polymerization but not curing when used in combination with a curing agent system using benzoyl peroxide and a tertiary amine, but the organic peroxide of the present invention, When used in combination with aromatic sulfinic acid salts and barbylic acid derivatives,
It was found that the curing speed was stable, resulting in high adhesive strength.

The blending amount of the phosphoric acid ester compound is approximately 0.1 to 30 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the radically polymerizable monomer. If the amount exceeds 30 parts by weight, the polymerization reaction will be suppressed.

Incidentally, a mixture of two or more of the organic acids, acid anhydrides, and phosphoric ester compounds may be used as desired. Mafko,
Each of them is the same type, and two or more types may be used in combination if desired.

When the composition according to the present invention is cured by photopolymerization, a photopolymerization initiator and a photopolymerization accelerator may be appropriately added as desired.

Examples of photopolymerization initiators include benzoin methyl ether, penzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, 2-chlordiogisanthone, 9. Examples include ultraviolet sensitizers or visible light sensitizers such as to-anthraquinone, camphorquinone, benzyl, 4°4°-dichlorobenzyl, and diacetyl. Two or more types of photopolymerization initiators may be used in combination.

As the photopolymerization accelerator, N,N-dimethyl-p-toluidine, toluethylamine, trihexylamine, 2-methylaminoethanol, N-methylgetanolamine, N,N-dimethylaminoethyl methacrylate, N
, N-diethylamino methacrylate and the like.

Two or more types of photopolymerization accelerators may be used in combination.

The amount of photopolymerization initiator or photopolymerization accelerator is radically polymerizable! The amount is about 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of 11 bodies.

The compositions according to the invention may optionally contain secondary or tertiary amines.
Amines may be included to accelerate the rate of cure. Preferred amines are aromatic secondary or tertiary amines, such as N-methyl-p-toluidine, N,N-dimethyl-1
)-toluidine, N, N(β-hydroxyethyl)-p
-) Luizin et al.

These amines are preferably used in the coexistence of aromatic sulfinic acid salts.

The amount of amine blended is approximately 0.00 parts by weight per 100 parts by weight of the radically polymerizable monomer. O1 to 5.0 parts by weight.

The composition according to the invention may further optionally include fillers,
Polymers, stabilizers, etc. may be blended as appropriate.

Examples of the filler include α-quartz powder, glass beads, silica powder, silicon nitride, alumina silicate, aluminum oxide, barium sulfate, barium glass, strondium glass, colloidal silica, and apatite powder. The surface of these inorganic fillers is coated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane or vinylchlorosilane (coating amount: 0.1 to 20 parts by weight per 100 parts of inorganic filler), and then coated with a binder resin. It is also possible to increase the bonding strength of Also useful are organic composite fillers prepared by kneading these inorganic fillers with radically polymerizable monomers in advance, polymerizing them, and then pulverizing them.

Examples of the polymer include polymethyl methacrylate, polyethyl methacrylate, and a copolymer of methyl methacrylate and ethyl methacrylate.

The particle size and blend m of these fillers and polymers may be appropriately selected depending on the application. For example, the composition according to the invention may be used as an adhesive, cement, composite resin, etc.)111
When used in crown resin, etc., the particle size should be 0. O1～
200μ, preferably 0.5 to 60μ, especially 0.5 to 3
0μ, and the blending amount is 0.3 to 5.0 parts by weight, preferably 2.0 to 46 parts by weight per 1 part of radically polymerizable monomer.
It is 0 parts by weight.

Two or more fillers and polymers may be used in combination, if desired. In addition, when the composition according to the present invention is used in a floor resin, it is preferable to blend a polymer, and the particle size of the polymer is 1 to 500μ, preferably 30 to 300μ, and the blending amount is based on the radically polymerizable monomer. 0 per part of body weight
．． 3 to 4.2 parts by weight, preferably 1. O~4.0 parts by weight.

Further, examples of stabilizers include hydroquinone, hydroquinone momomethyl ether, hydroxymethoxybenzophenone, butylated hydroxytoluene, and the amount thereof is 0 per 100 parts by weight of the radically polymerizable monomer.
．． O1 to 3.0 parts by weight.

Examples of ways in which the composition according to the invention may be used in dental cement include various multi-packaging forms. A powder component unit in which the filler or polymer described above is mixed with an aromatic sulfinic acid salt and a barbylic acid derivative, and a liquid component unit in which a polymerizable monomer is blended with an organic peroxide stabilizer are stored as one set. (In this case, the aromatic sulfinic acid salt or barbylic acid derivative may be blended into the liquid component unit, and the organic peroxide may be blended into the powder component unit.) . In addition, in the case of compositions containing acid anhydrides or phosphoric acid esters such as organic acids, these components should, in principle, not coexist with the aromatic sulfinic acid salts in the polymerizable monomers. preferable. There are no particular restrictions on other blending methods. For example, these components are blended into a powder component unit in which a filler or polymer is mixed with a salt of an aromatic sulfinic acid and a barbylic acid derivative, and a liquid component unit is blended with an organic peroxide in a polymerizable monomer. It may also be a combination of two packaging forms. In addition, when cement kneading mud is applied as a pretreatment agent to the adherend to increase adhesive strength, in addition to the above two packaging forms, a liquid component containing at least one component of the hardening agent is used. Units may be prepared and stored and sold as a set of three packaging forms (in this case, organic peroxides, organic acids, acid anhydrides, and phosphoric esters are the aromatic sulfine in the polymerizable monomers). It is preferable not to coexist with acid salts, and there are no particular restrictions on the method of blending other than that). Furthermore, an organic peroxide, a salt of barbylic acids, and an aromatic sulfinic acid are added to each of the powder component unit + powder component unit + liquid component unit or powder component unit + liquid component unit + liquid component unit, respectively. It may also be prepared as a three-packaged form, and when used, the required amount of each component is taken from each unit and mixed (in this case, pulpic acid derivatives, organic peroxides, and organic acid derivatives). Alternatively, it is preferable that neither the acid anhydride nor the phosphoric acid ester be allowed to coexist with the aromatic sulfinic acid salt in the polymerizable monomer, and there are no particular restrictions on the method of blending other than that. In the case of this embodiment as well, the above-mentioned pretreatment agent unit may be added to prepare the product in a four-pack form.

Further, the pretreatment agent may be prepared in two packaging forms: monomer and monomer or volatile solvent and monomer, and both may or may not be cured when mixed. In this case as well, the above-mentioned restrictions apply to the coexisting components with the organic aromatic sulfinic acid salt, but there are no restrictions to other combinations.

When the composition according to the invention is used as a composite, it is preferred that it be in at least two packaging forms. For example, one unit contains monomers, fillers, organic peroxides, and barbylic acid derivatives, and the other unit contains monomers, fillers, and salts of aromatic sulfinic acids. Organic acids, acid anhydrides, or phosphoric esters can be appropriately blended into these units.

The combination of components contained in these units is not particularly limited, but there are similar restrictions as in the case of the cement described above regarding components that coexist with the salt of aromatic sulfinic acid.

In addition, monomers, fillers, and organic peroxides are placed in one unit, monomers, fillers, and aromatic sulfinic acid salts are placed in another unit, and adhesives and monomers are placed in another unit. (The monomer in the adhesive may be replaced with a volatile solvent, and the amount of organic acid, acid anhydride or phosphate ester may be They may be blended as appropriate under the condition that they are not allowed to coexist with salts of aromatic sulfinic acids). In this embodiment, the adhesive itself does not cure, but if the adhesive is applied to the tooth cavity in advance and then filled with the composite, the barbylic acid derivative in the adhesive will bind to the organic peroxide and aromatic sulfine in the composite. in contact with acid salts,
Cure the composite and adhesive. As the filler, it is preferable to use the same filler as in the case of cement, particularly an inorganic filler and an organic composite filler. The viscosity of the composite binder resin is 500 to 50,000
cps, particularly preferably adjusted to 2,000 to 8,000 cps.

When the composition according to the invention is used as a floor resin, it is preferably prepared in the form of two packages consisting of a monomer-containing liquid component unit as a powder component unit. For example, the aforementioned polymer particles such as polymethyl methacrylate (particle size: 1 to 500μ, preferably 30 to 300μ)
A combination of a unit containing a barbylic acid derivative and an organic peroxide and a unit containing a monomer and a salt of aromatic sulfinic acid; A combination of a unit containing polymer particles and an organic peroxide, a unit containing a polymer particle containing an organic peroxide and an aromatic sulfinic acid salt, and a combination of a unit containing a monomer and a barbylic acid derivative, etc. Can be mentioned. In this case, the organic acid or acid anhydride or phosphoric ester may be appropriately blended under conditions that do not allow the organic acid or acid anhydride to coexist with the salt of aromatic sulfinic acid in the monomer.

When the composition according to the present invention is used as a heat-polymerizing floor resin, in addition to the same embodiments as in the case of the room-temperature polymerizing floor resin described above, a unit in which a salt of an aromatic sulfinic acid is blended with polymer particles and It may be prepared in a three-pack form combining a pretreatment agent unit containing a monomer and a barbylic acid derivative (compounds may be substituted alternately within each unit. In this case, aromatic sulfinic acid Organic acids such as acid anhydrides or phosphoric acid esters may be appropriately blended under conditions that do not allow the salts to coexist with the polymerizable monomer.

When using the composition according to the invention as an adhesive,
Combinations of units containing organic peroxides and barbylic acid derivatives as monomers, combinations of units containing monomers and salts of aromatic sulfinic acids, and units and units containing alcohols and salts of aromatic sulfinic acids. Examples include a combination of a heavy substance and a unit containing an organic peroxide and a barbylic acid derivative. In this case, the organic acid or acid anhydride or phosphoric ester may be appropriately blended under conditions that do not allow the organic acid or acid anhydride to coexist with the aromatic sulfinic acid salt. When used, a predetermined amount of inclusions are collected from each unit and mixed.

When the composition according to the present invention is used as a resin for veneers, it is used in the form of a combination of a filler-containing powder component unit and a monomer-containing liquid component unit. As the filler, the same filler as described for the cement may be used, and the form of the unit may be prepared in the same manner as for the cement and composite described above. In addition, in the case of preparing a heat-polymerized type, it is sufficient to follow the above-mentioned case of floor resin, and an inorganic filler and an organic composite filler may be used in combination with the polymer powder, or may be substituted for the powder.

The present invention further provides that in all the forms of cements, composites, adhesives, etc. described so far, the above-mentioned photopolymerization initiator (preferably benzoin isopropyl ether, benzyl, camphorquinone, etc.) and the photopolymerization accelerator are included in the liquid component unit. agent (N-methyldiethanolamine, N,
(N-dimethylaminoethyl methacrylate etc. are preferred) may be blended as appropriate (the preferred blending amount is 10 monomers).
0.1 to 3 parts by weight per 0 parts by weight).

A secondary or tertiary amine may be added to the curing agent system of the composition of the present invention, if desired, and coexists with salts of aromatic sulfinic acids in all the forms of cement, composites, adhesives, etc. described above. They may be blended within the unit (the preferred blending amount is 0.01 to 5.0 parts by weight per 100 parts by weight of the polymerizable monomer).

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Examples Examples 1 to 4 and Comparative Examples 1 to 6 Main ingredients are silane-treated silica stone and barium sulfate as a powder, benzoyl peroxide, l-benzyl-5
-Phenylbarbituric acid, 5-butylbarbituric acid, sodium para-toluenesulfinate, sodium benzenesulfinate, 4-acryloxyethyl trimellitic anhydride, etc. were prepared in the formulations shown in Table 1.

The liquid agent is mainly composed of triethylene glycol dimethacrylate, a 1:2 (mol) reaction product of 1,1,3-trimethylhexamethylene diisocyanate and 2-hydroquine ethyl methacrylate, and L-butyl peroxymaleic. acid, succinic acid peroxide, N,N-di(β=hydroxyethyl)-p-toluidine, dilauryldimethylammonium chloride,
Butylated hydroquine toluene was prepared according to the formulation shown in Table 1.

The silane treatment of the filler was carried out using γ-methacryloxypropyltrimethoxysilane on silica stone or barium sulfate by the usual acetic acid method. That is, solution 1 in which γ-methacryloxypropyltrimethquine silane was dissolved in a 0.1% acetic acid aqueous solution to a concentration of 2.0% by weight.
A slurry prepared by adding 100 parts by weight of filler to 00 parts by weight was air-dried, then heated at 80°C for 2 hours, and then for 12 hours.
Surface treatment was performed by heat treatment at 0° C. for 30 minutes.

Further, the powder/liquid ratio of Examples 1 to 4 and Comparative Examples 1 to 6 was all 3.5:1, and the test items listed in Table 1 were tested. Adhesion test and strength test (test specimen: diameter 4 mm, height 8 mm) were measured after the specimen was cured and immersed in distillation at 37° C. for 24 hours.

The half teeth used in the adhesion test were freshly extracted and stored in a refrigerator in physiological saline. The metal is Shofu Smalloy Nickel (manufactured by Shofusha Co., Ltd.) for crowns and suffudges.
was cast using a Shofu argon caster (manufactured by Shofu Co., Ltd.) under specified conditions.

As is clear from Table 1, the cases of conventional benzoyl peroxide and tertiary amine, which are Comparative Examples 1 and 3, and the cases of 5-
For both hardener systems, substituted barbituric acid and ammonium chloride, curing times are relatively slow, metal-to-metal, enamel-to-metal and dentin-to-metal bond strengths are significantly low, and mechanical strength is also low. there were. In addition, in the conventional system using benzoyl peroxide, tertiary amine, and sodium para-toluene sulfinate in Comparative Example 5, the curing time was 4.2 minutes, and although no delay effect was observed, the adhesiveness to metal and tooth structure was poor. The adhesion force was low, especially to dentin.

In Comparative Example 6, the system using sodium and lithium para-toluenesulfinate and t-butyl peroxymaleic acid had a quick curing time of 2.5 minutes, suggesting high polymerization activity, but The adhesion strength was not high.

On the other hand, when using the curing agent system consisting of an organic peroxide, a barbylic acid derivative and a sodium salt of aromatic sulfinate, or adding an acid anhydride to the curing agent system, 4-
In the system containing acryloxyethyl trimellitic anhydride, superior results were obtained compared to all comparative examples.

In terms of curing time, Comparative Examples 1 to 4 had a significantly delayed curing time of 12 to 120 minutes, whereas Examples 1 to 4 had a significantly delayed curing time of 12 to 120 minutes.
~11 minutes, and considering the amount of the curing agent,
It is clear that the polymerization activity is poor. In particular, the blending of 4-acryloxyethyltrimellitic anhydride in Comparative Example 4 caused a salt-forming reaction between the acid anhydride and the tertiary amine, and the redox polymerization between benzoyl peroxide and the tertiary amine was significantly delayed. While the curing time was 100 minutes, in Examples 2.3 and 4, a stable curing time of 6.5 to 11 minutes was obtained. Furthermore, in Comparative Examples 1 to 4, the surface of the cured product was significantly inhibited in polymerization, whereas in Examples 1 to 4, the inhibition was slight. While the cured products of Comparative Examples 1, 2, and 4 exhibited a slightly pale yellowish brown color, Examples I to 4 exhibited no discoloration at all and exhibited excellent aesthetics.

Metal adhesion was measured in Examples 1 to 4 (235 to 413 Kgr/c
mri was superior to any of Comparative Examples 1 to 6 (120 to 210 Kgf/cm). For example, Example! and 2 had +84 Kgr/cm" and +194 Kgf/cm" compared to Comparative Example 6.
It showed an improvement in Kgf/cm', and showed the same level of improvement as compared to Comparative Examples 2 and 3. The results of Example 4 showed that the adhesion effect was particularly remarkable, with +293 Kgf/am compared to Comparative Example 1.
An improvement of +203 Kgf/cm" was observed compared to Comparative Example 4.

The results of Examples 1 to 4 were also superior to Comparative Examples 1 to 6 in adhesion and adhesion to natural tooth enamel without acid etching treatment. That is, Examples 1 to 4 were 39.7 to 9.
2.2 Kgf/cm”, whereas Comparative Examples 1 to 6
6,2 to 44,0 Kgf/cm", and it became clear that the adhesion to enamel was superior by using the curing agent system compared to the conventional technology. In particular,
The results of Example 4 showed a strong adhesive force of 92°2 Kgf/cm', which was about 2.1 times to about 15 times that of Comparative Examples 1 to 6.
Demonstrated twice the adhesion effect.

Sour Ding 11. Ki/W b Tanuki? r+ pressure? Prayer?
-1F eggplant↓Examples 1 to 4 were also extremely superior to Comparative Examples 1 to G in terms of adhesion. However, whereas the results of Comparative Examples 1 to 6 showed θ~2 and I Kgr/cm2, the results of Examples 1 to 4 showed 10. ．． 0-50
．． GKgr/'c m '', and it was revealed that there was a significant difference in improvement over each comparative example.Specifically, Comparative Example 1 (conventional system of benzoyl peroxide and tertiary amine) , 5 Kgf/cm2, Comparative Example 3
(Conventional system of 5-substituted barbylic acid and ammonium chloride) showed OKgf/cm2, and Comparative Example 5 (conventional system of benzoyl peroxide, tertiary amine, and sodium para-toluenesulfinate) showed OKgf/cm2. In contrast, Example 1 (system of organic peroxide, barbylic acid derivative, and sodium para-toluenesulfinate) showed lQ', OKgf/cm2, and Example 1 (system of organic peroxide and 5-substituted barbylic acid derivative) showed acid and para-
The system of sodium toluenesulfinate and acid anhydride) is 5
0.0,6 Kgf/cm2, and these exhibited target dentin adhesion effects that were 20 to 100 times greater than those of Comparative Examples 1, 3, and 5.

It was also revealed that the mechanical strength was excellent, with the compressive strength of Comparative Examples 1 to 6 ranging from 1368 to 2168 Kgf.
/am”, whereas Examples 1 to 4 showed 2403 to
2633 Kgf/cm', and comparative examples 1 to 6 showed a tensile strength of 256 to 415 Kgf/cm2, whereas Examples 1 to 4 showed a tensile strength of 442 to 488 Kgf/cm'.
are shown respectively. These strength properties are due to the excellent polymerization properties of Examples 1 to 4, and this is due to the excellent polymerization properties of Examples 1 to 3. This is thought to be due to the catalytic activity of the ternary curing agent or the system using the ternary curing agent and an acid anhydride, and it is clear that it is superior to any catalyst system based on the prior art. Became.

In addition, many of the excellent properties of Examples 1 to 4 satisfy the requirements for dental restoration composite materials and dental adhesive materials, such as dental adhesive composite resins, adhesive abutment construction materials, Applications include metal-adhesive opaque resin for photopolymerized or heat-polymerized resins for veneers, orthodontic adhesives and adhesive silane cements for crowns, inlays, onlays, etc.

Silane treatment - silica powder 75, O silane treatment - barium sulfate 23.8 para-toluenesulfinic acid sodium salt 0.65-butylbarbituric acid 0.6 Agent B
Part by weight 1.1.3-Trimethylhexamethylene 60.0 Reaction product of 1=2 (mol) of diisocyanate and 2-hydroxyethyl methacrylate Triethylene glycol dimethacrylate 34.8 t
-Butyl peroxymaleic assay 0.14-
Acryloxyethyl trimellitic acid 5.0 anhydride butylated hydroxytoluene 0.1C
Agent Part by weight 1.1.3
-) Limethylhexamethylene 60.0 Reaction product triethylene glycol dimethacrylate 36.8 [
-Butyl peroxymaleic acid 0.14-
Acryloxyethyl trimellitic acid 3.0 Butylated hydroxytoluene 0.1 The silane treatment was carried out by the acetic acid method of Examples 1 to 5 under the same conditions. When conducting the tests for the following items (1) to (4) using the above composition in combination of A and B, and A and C, The powder/liquid ratio of the agent was tested at 3.5:l in all of (1) to (4). In (3), the powder/liquid ratio was sometimes used at 3.8:1. Curing time is at a powder/liquid ratio of 3.5:l.
It took 5 minutes for agents A and B, and 4.5 minutes for agents A and C. In order to evaluate the durability of the adhesive force, a thermal cycle test was conducted, and the conditions were immersion in cold water at 11°C and hot water at 60°C for 1 minute each (1 → no cycle), and 0 cycles (no cycle). This was repeated 30 times, 300 times, and 1000 times.

Here, in the test implementation of sections (1) to (4), the case of a combination of agents A and B is referred to as Example 5, and the case of a combination of agents A and C is referred to as Example 6.

(1) Metal-metal adhesive strength (Kg[/cm): Metal-metal adhesive strength (Kg/cm) using the above agents A, B, and C.
The gf/am ratio is shown in Tables 2 and 3.

The metals used were Ni-Cr alloy for crowns and bridges, Shofu Sufro-nickel, Ni-Cr alloy for porcelain baking, and Shofu Unimetal (manufactured by Shofu Co., Ltd.). After sandblasting with aluminum oxide, the metal was heated for 5 minutes. The one that had been ultrasonically cleaned was used.

Table 2 When Shofu Sufronickel is used Table 3 When Shofu Unimetal is used (Note) In Tables 2 and 3, the number of thermal cycles of 0 indicates the measurement results after 24 hours in distilled water at 37°C.

(2) Tooth substance adhesiveness: Table 4 shows the tooth substance-metal bond strength (Kgf/cm'') using the above-mentioned agents A, B, and C.

Table 4 (a)'Enamel and dentin of natural teeth were polished with emery paper only, without acid etching treatment.

2 metal is aluminum oxide sandblasted Ni
-Cr-based alloy, Shofu Sufronickel round bar (diameter 4
, 7 mm) was used.

(3) Marginal sealability: A diameter of 3.0 mm and a depth of 2 m is placed on the labial surface of a freshly extracted anterior tooth.
A circular box-shaped cavity of m is formed, and then the enamel is etched with a 30% phosphoric acid aqueous solution for 60 seconds, washed with water,
After drying, add 3.8+ parts A and B or A and C each.
The mixture was kneaded for 1 minute at a powder/liquid ratio of 1, and then filled and hardened in a cavity. After that, the tooth leakage test specimen with the excess removed was made into 100 pieces.
After 0 thermal cycles, it was immersed in Tsukushin dye solution at 37°C for 24 hours, then cut open and the degree of dye leakage was observed.
In all cases where the agent was used, almost no dye leakage was observed, and it was found that the margin sealing properties were excellent.

Further, the following test was conducted using Δ agent and B agent and A agent and C agent at a powder-liquid ratio of 3.5:1. Raw tooth enamel etched for 60 seconds with a 30% phosphoric acid aqueous solution, Ni-Cr alloy sandblasted with aluminum oxide, and Shofu Sufroi nickel in the above powder-liquid ratio (3.5/l).
A dye leakage test was conducted after adhesion with mixed mud of No intrusion was observed.

(4) Porcelain-metal adhesion; The adhesion between Shofu Unibond (manufactured by Shofusha Co., Ltd.), a dental porcelain, and Shofu Unimetal, a Ni-Cr alloy for porcelain baking, was determined by using the above agents A and B. Table 5 shows the results of the study using Agent A and Agent C.

Table 5 (Note) The powder/liquid ratio was 3.5:1.

2 The surface of the porcelain was polished with emery paper, and the surface of the metal was treated with sandblasting.

3 Both adhesive test specimens were left in distilled water at 37° C. for 24 hours and then measured.

As shown by the results of test items (1) to (4), by using the hardening agent system composed of organic peroxide, sodium aromatic sulfinate, barbylic acid derivative, and acid anhydride, metal, tooth It has been found that immersed adhesion can be obtained for both quality and porcelain materials. In this example, the composition exhibits excellent performance in applications such as dental composites, abutment construction materials, orthodontic adhesives, adhesive silane cements, and adhesives for porcelain repair materials. became clear.

Examples 7 to 13 Powder Part by weight Silane treatment - α-quartz powder 75.0 Silane treatment - Barium sulfate 23.5 Aerosil R
-972 (manufactured by Nippon Aerosil Co., Ltd.) 1.2 Sodium benzenesulfinate 0.11-Benzyl-5
-Phenylbarbituric acid 0.2 diisonanate l:2 (mol) reaction product of diisonanate 2-hydroxyethyl methacrylate triethylene glycol dimethacrylate 30.0 diethylene glycol dimethacrylate 9.8 succinic acid par Oxide 0.1 Butylated Hydroxytoluene 0.1 Pretreatment Agent The pretreatment agents used are shown in Table 6.

Note that the silane treatment was performed in the same manner as the acetic acid method in Examples 1 to 4. When conducting a metal-to-metal adhesion test using the above composition, the test was conducted at a powder-to-liquid ratio of 3°5:l. At this powder/liquid ratio, the curing time was 4.5 minutes. When using a pre-treatment agent, apply the pre-treatment agent to the adhesive surface of the metal using a small brush or small sponge before mixing the powder and liquid, and after the volatile components have evaporated, apply the pre-treatment agent. Both waves were compressed and hardened. The results showed strong adhesive strength. Table 7 shows these results.

Here, Example 7 is a case in which only the above-mentioned powder and liquid are used, and a pre-treatment agent used in combination with the powder and liquid,
Examples 8.9.1O111, 12 and 13 are cases in which agent H, agent H, agent G, agent H, and agent I are used, respectively.

Example 14 Agent J Heavy 1 part silane treatment - α-quartz powder 50.0 Silane treatment - Silicon nitride powder 25.0 N run treatment -
Barium sulfate 21.5 Aerosil [1
-972 (manufactured by Nippon Aerosil Co., Ltd.) 1.21-benzyl-
5-Phenyl 0.6 Barbiturate-butyl peroxymaleic acid 0.24
- Acryloxyethyl trimellitic acid 1.5 Excreted in anhydride Part by weight Reaction product of isophorone diisocyanate and 65.0 2-hydroxyethyl methacrylate l:2 (mol) Diethylene glycol dimethacrylate 10.0 Triethylene glycol Dimethacrylate 23.5 Sodium para-toluenesulfinate 1.4 Hydroquinone monomethyl ether 0.1 The silane treatment of the α-quartz powder was performed in the same manner as in Examples 1-4. J
When the agent and the agent were kneaded at a powder/liquid ratio of 3.8:■, the mixture hardened in about 4 minutes. There was no discoloration in the color tone of the cured products of Agent J and Agent N, which satisfied the requirements for an aesthetic restorative material. Furthermore, the results of measuring the mechanical strength of this cured product were as follows.

Compressive strength: 3104 Kgf/cm" tensile strength
: 487 Kgf/cm" Bending strength : 10
10 Kgr/ctn2 Knoop hardness = 71 The adhesion strength to natural tooth enamel (without acid etching treatment) obtained by mixing equal amounts of J agent and Ni agent was determined in distilled water at 37°C.
Measurement after 24 hours showed 83 Kgf/cm'.

In addition, a diameter of 3 mm and a depth of 2 was applied to the labial surface of a freshly extracted human tooth.
A cavity of 1.0 mm in diameter was formed, and then the enamel was etched with a 30% phosphoric acid aqueous solution, washed with water, and dried. The cavity was then filled with a paste prepared by kneading equal amounts of Agent J and Agent Ni. After the paste hardens, the tooth leakage test specimen with the excess removed was heated to 4°C and 6°C.
10 cycles of alternate immersion in 0°C water for 1 minute each
After repeating 00 times, it was immersed in an aqueous Tsukusin dye solution at 37°C for 3 days, then cut open and the degree of dye leakage was observed. Almost no dye penetration was observed, indicating excellent margin sealing properties. There was found.

Comparative Example 7 A product from which t-butyl peroxymaleic acid, a component of the J agent of Example 14, was removed (L agent) and Example 14
When the mixture was mixed with the glue, it did not harden within 30 minutes.

Comparative Example 8 One in which l-benzyl-5-phenylbarbituric acid, a component of Agent J of Example 14, was removed and L-butyl peroxymaleic acid was replaced with benzoyl peroxide (Agent M). Example! Powder-liquid ratio of powder to powder in 4 =
A 3.8:1 mix gave a cure time of about 5.5 minutes. The mechanical strength of this cured product was 2 to 3 times higher than that of Example 14.
This was a relatively low result. Further, when a pigment leakage test using freshly extracted human teeth was conducted in the same manner as in Example 14, pigment invasion was observed.

Comparative Example 9 When the agent prepared in Example I4 from which sodium para-toluenesulfinate was removed (agent N) and agent J of example 14 were kneaded, the mixture did not harden within 1 hour.

Example 15 When conducting a dye leakage test for examining tooth adhesion using the M agent and the agent of Comparative Example 8, 1.1.3-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate = 1:2 (mol) 40 parts by weight of reaction product, 10 parts by weight of bisphenol A diglycidyl methacrylate
Parts by weight, triethylene glycol dimethacrylate 20
Parts by weight, neopendel glycol dimethacrylate 15
Parts by weight, 815 parts by weight of 2-hydroxyethyl methacrylate, 0.2 parts by weight of t-butyl peroxymaleic acid, 5 parts by weight of 4-acryloquine ethyl trimellitic anhydride
A liquid component consisting of parts by weight and 0.1 parts by weight of butylated hydroquine toluene and 100 parts by weight of ethyl alcohol, l-
A liquid component consisting of 0.3 parts by weight of cyclohexyl-5-ethylbarbituric acid and 1.5 parts by weight of sodium benzenesulfinate was prepared and two tests were conducted.

After forming a cavity with a diameter of 3 mm and a depth of 2 mm on a freshly extracted human tooth, it was treated with acid etching, washed with water, dried, and then a mixture of equal amounts of the above two liquids was applied, and the volatile components were evaporated.Comparative Example 8 After filling and hardening the kneaded paste with a powder-liquid ratio of powder to M agent = 3.8:1, a dye leakage test was performed and the cavity and true wall margin were observed, and almost no dye penetration was observed. Ta.

Example 16 Powder Part by weight Polymethyl methacrylate 50.0 Polyethylene methacrylate 43.71
-Benzyl-5-phenylbarbituric acid 1, O succinic and peroxide 0.34-Acryloxyethyl trimellitic acid 5.0 Anhydride Toho Part by weight Methyl methacrylate 94.0 Ethylene glycol dimethacrylate 4.6 Benzene Sodium sulfinate 1.0 UV absorber
0.3 Butylated hydroxytoluene 0.1 Using a mixture of the above powder and liquid at a weight ratio of 1.6/l in a Gutupeng glass, a Co-Cr alloy for metal floors, Shofu Sufrocobalt (( When measuring the tensile adhesive strength of an acrylic rod (manufactured by Shofusha Co., Ltd.) in distilled water at 37°C, it was found that 30
0 Kgf/am''.

Further, the mixture of the powder agent and the liquid agent was mixed with the Go-Cr alloy, Shofu Sufrocobalt and stainless steel (SUS30).
4) Or Shofu Sufrocobalt and polymethyl methacrylate board (all the above adherends are 10lOx10x3 boards)
After being pressure-cured on each of the plates, it was allowed to stand for 24 hours in a Tsukusin dye solution at 37° C., and the degree of dye penetration was observed. As a result, almost no dye penetration was observed.

The results of the above test using orthodontic stainless steel brackets and acid-treated enamel were also excellent.

Furthermore, the cured mixture of the powder and liquid does not change color at all,
It was also excellent in aesthetics.

According to this example, a floor resin using the hardening agent of an organic peroxide, a barbylic acid derivative, a salt of an aromatic sulfinic acid, and an acid anhydride can be cured in about 20 minutes by adjusting the composition. As a result, the usefulness of this resin as adhesive for metal floors, as a repair material, as a resin cement, and as an adhesive for orthodontics has been recognized.

Example 17 Shofu Super Lux Daylight (manufactured by Shofu Co., Ltd.) was used to perform a tooth adhesion test and a pigment leakage test using Shofu Super Lux Daylight (manufactured by Shofu Co., Ltd.) in accordance with its instruction manual. 40 parts by weight,
110,711 parts by weight of 2,2°-bis(γ-methacryloxyβ-hydroquine propoxyphenyl)propane, 429 parts by weight of triethylene glycol dimethacrylate, t
- 1.0 parts by weight of butyl peroxymaleic acid,
1.0 parts by weight of benzyl, 4-methacryloxyethyl trimeliftic anhydride hydroquinone monomethyl ether 0
．． A liquid consisting of 1 part by weight of liquid components, 100 parts by weight of ethyl alcohol, 0.3 parts by weight of 5-butylbarbituric acid, 1.0 parts by weight of sodium benzenesulfinate, and 2.0 parts by weight of N-methyljetanolamine. A liquid composition consisting of two components was prepared, and a cavity of 3 mm in diameter and 2 mm in depth was formed in a freshly extracted human tooth. After acid etching treatment, washing with water and drying, equal amounts of the above two components were prepared. After applying the mixed solution and evaporating the volatile components with air, it was filled with Super Lux Daylight and pressure-welded, and then photocured by irradiating visible light for 30 seconds with Shofu Daylight Lamp II (manufactured by Shofu Co., Ltd.). After that, a dye leakage test was performed and the cavity and true wall margins were observed, and almost no dye penetration was observed, indicating excellent margin sealing properties. In addition, the adhesive strength after 24 hours in distilled water at 37°C after applying Shofu Super Lux Delight to the enamel of a tooth that had been acid-etched using the above two liquid acids was yellow flame pressure welded and photocured. It showed 190 K gr/cm2. These dye leakage tests and adhesion tests showed no deterioration after 300 thermal cycles of immersion at 4°C and 60°C, demonstrating excellent durability of tooth adhesion and margin sealing properties. Ta.

In addition, another two-liquid acid was prepared by removing only sodium benzenesulfinate from the two-liquid acid, and the same test as above was conducted using Shofu Super Lux Daleite.

The results showed that the adhesive strength to acid-etched natural tooth enamel was as low as 120 Kgf/cm'', and in the dye leakage test, the dye leakage reached the dentin.

In addition, if 5-butylbarbituric acid or t-butylperoxymaleic acid is removed from the two liquid acids, or if all of these curing agents are removed, the photopolymerization curing agent and light Adhesion tests and dye leakage tests using liquid components containing only or consisting of a polymerization accelerator showed that the adhesive strength was low and the degree of dye leakage was deep. In particular, when it is composed only of benzyl and N-methyldiethanolamine, a so-called photo-curing agent, pigment leakage reaches the dental pulp, clinically suggesting serious pulp irritation and recurrence of secondary caries. .

As shown in the above results, the combination of conventional photopolymerizable adhesive and photopolymerizable combo knot has low tooth adhesion and poor margin sealing properties due to the combination of acid anhydride, peroxide, and Improvements have been made in photopolymerizable adhesives by the addition of such curing agent systems using salts of aromatic sulfinic acids and barbylic acids.

Example 18 Using the two-component composition of Example I7 as it was, a dye leakage test was conducted using Adabutiic (manufactured by Johnson & Johnson), a room-temperature curable composite resin, according to the instructions. As a result, no dye leakage was observed. I could barely see it. In comparison, when only Adabtiic was used, dye leakage was observed deep down.

From the above results, the two-component composition of Example 17 was able to improve the edge sealing properties of a room-temperature curing composite resin.

Effects of the Invention According to the present invention, as a curing agent for a dental restorative composition containing a radically polymerizable monomer, there are cases in which a barbylic acid derivative is used in combination with an organic peroxide and a metal salt of an aromatic sulfinic acid, and a case in which a barbylic acid derivative is used in combination with an organic peroxide and a metal salt of an aromatic sulfinic acid. When using oxides, metal salts of aromatic sulfinic acids, and barbylic acid derivatives together with organic acids, acid anhydrides, or acetone compounds, when conventional benzoyl peroxide and tertiary amines are used in combination, when diasilver Compared to cases where Oquindo, aromatic tertiary amine and metal salts of aromatic sulfinic acids are used together, cases where palpylic acids are used together with heavy metals and halogen ions, cases where trialkylborane is used, etc. Highly safe in clinical operation, no discoloration, aesthetically pleasing, high mechanical strength, natural tooth enamel and dentin, metal materials, ceramics + 4 materials, polymer 10000 21 etc. It is possible to obtain strong and durable adhesion against various types of adhesives, and is highly dedicated to this field.

Claims (1)

[Scope of Claims] 1. A, a radically polymerizable monomer and B, the following curing agent (a) an organic peroxide (b) an alkali metal salt, alkaline earth metal salt or amine salt of an aromatic sulfinic acid, and (c) A dental restorative material composition characterized by containing a barbituric acid derivative. 2. Dental use according to claim 1, wherein the radically polymerizable monomer is a mono-, di-, tri-, or tetra-functional acrylate or methacrylate, and may contain a fluorine or urethane bond in the molecule. Restorative material composition. 3. The dental restoration according to claim 1, wherein the organic peroxide is t-butyl peroxymaleic acid, succinic acid peroxide, benzoyl peroxide, or 4,4'-dichlorobenzoyl peroxide. material composition. 4. The dental restorative composition according to claim 1, wherein the aromatic sulfinic acid salt is an alkali metal or alkaline earth metal salt of benzenesulfinic acid or para-toluenesulfinic acid. 5. The dental restorative composition according to claim 4, wherein the aromatic sulfinic acid salt is sodium benzenesulfinate or sodium para-toluenesulfinate. 6. The barbituric acid derivative has the following general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the above formula, R_1, R_2 and R_3 are hydrogen atoms or aliphatic, aromatic, alicyclic, or heterocyclic The dental restorative composition according to claim 1, wherein these residues can further contain substituents such as halogen, alkyl, alkoxy, aryl, cyclohexyl, etc. 7. Dental restoration according to claim 1, wherein the barbituric acid derivative is 1-benzyl-5-phenylbarbituric acid, 5-butylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, etc. material composition. 8. A. B for 100 parts by weight of radically polymerizable monomer: (a) The following curing agent: (a) Organic peroxide: 0.01 to 10 parts by weight (b) Alkali metal salt of aromatic sulfinic acid, alkaline earth The dental restorative material composition according to claim 1, characterized in that it contains 0.01 to 20 parts by weight of a metal salt or amine salt and 0.01 to 20 parts by weight of (iii) a barbituric acid derivative. thing. 9. The dental restorative composition according to claim 1, further comprising filler or polymer particles. 10. The dental restorative material composition according to item 9, wherein the dental restorative material composition is an adhesive. 11. The dental restorative material composition according to item 9, wherein the dental restorative material composition is a floor resin. 12. The dental restorative material composition according to item 9, wherein the dental restorative material composition is cement. 13. The dental restorative material composition according to item 9, wherein the dental restorative material composition is a composite resin. 14. No. 9, wherein the dental restorative material composition is a resin for veneers
The dental restorative material composition described in . 15. Claim 1 further containing a volatile solvent
The dental restorative material composition described in . 16. The dental restorative material composition according to item 15, wherein the dental restorative material composition is an adhesive. 17. The dental restorative material composition according to claim 1, wherein the dental restorative material composition is an adhesive. 18. A, radically polymerizable monomer and B, the following curing agent (a) organic peroxide (b) alkali metal salt, alkaline earth metal salt or amine salt of aromatic sulfinic acid (c) barbituric acid derivative and (d) A dental restorative composition characterized by containing an organic acid or acid anhydride or a phosphoric acid ester compound. 19. Dental use according to claim 18, wherein the radically polymerizable monomer is a mono-, di-, tri-, or tetra-functional acrylate or methacrylate, and may contain a fluorine or urethane bond in the molecule. Restorative material composition. 20. The dental restoration according to claim 18, wherein the organic peroxide is t-butyl peroxymaleic acid, succinic acid peroxide, benzoyl peroxide, or 4,4'-dichlorobenzoyl peroxide. material composition. 21. The dental restorative composition according to claim 18, wherein the aromatic sulfinic acid salt is an alkali metal or alkaline earth metal salt of benzenesulfinic acid or para-toluenesulfinic acid. 22. The dental restorative composition according to claim 21, wherein the aromatic sulfinic acid salt is sodium benzenesulfinate or sodium para-toluenesulfinate. 23. The barbituric acid derivative has the following general formula: ▲ Formula,
There are chemical formulas, tables, etc.▼ (In the above formula, R_1, R_2, and R_3 are hydrogen atoms or aliphatic, aromatic, alicyclic, or heterocyclic residues, and these residues can also be halogen, alkyl, alkoxy , aryl, cyclohexyl, etc.) The dental restorative material composition according to claim 18. 24, barbituric acid derivatives include 1-benzyl-5-phenylbarbituric acid, 5-butylbarbituric acid, 1-
The dental restorative material composition according to claim 18, which is cyclohexyl-5-ethylbarbituric acid or the like. 25, organic acid or acid anhydride or organic phosphorus compound is 1
19. The dental restorative material composition according to claim 18, which has a structure containing at least one carboxyl group, sulfonic acid group, acid anhydride group, phosphoric acid group, or phosphonic acid group in the molecule. 26, organic acid or acid anhydride or organic phosphorus compound is 1
26. The dental restorative material composition according to claim 25, which has a structure having at least one radically polymerizable unsaturated group in the molecule. 27. The dental restorative material composition according to claims 25 and 26, wherein the organic acid is 4-acryloxyethyltrimethic acid or 4-methacryloxyethyltrimethic acid. 28. The dental restorative material composition according to claims 25 and 26, wherein the acid anhydride is 4-acryloxyethyltrimethic anhydride or 4-methacryloxyethyltrimethic anhydride. 29, the phosphoric acid ester compound is bis-[(2-hydroxyethyl)methacrylate]phosphoric acid, [(2-
The dental restorative material composition according to claims 25 and 26, which is methacryloxyethyl)phenyl]phosphoric acid. 30. A. B based on 100 parts by weight of radically polymerizable monomer: (a) The following curing agent: (a) Organic peroxide: 0.01 to 10 parts by weight (b) Alkali metal salt of aromatic sulfinic acid, alkaline earth Metal salt or amine salt: 0.01 to 20 parts by weight (c) Barbiturate derivative: 0.01 to 20 parts by weight and (d) Organic acid or acid anhydride or phosphoric acid ester compound: 0.1 to 30 parts by weight 19. The dental restorative material composition according to claim 18, comprising: 31. The dental restorative composition according to claim 18, further comprising filler or polymer particles. 32. The dental restorative material composition according to item 31, wherein the dental restorative material composition is an adhesive. 33. The dental restorative material composition according to item 31, wherein the dental restorative material composition is a floor resin. 34. The dental restorative material composition according to item 31, wherein the dental restorative material composition is cement. 35. The dental restorative material composition according to item 31, wherein the dental restorative material composition is a composite resin. 36. Third, the dental restorative material composition is a resin for veneers
The dental restorative material composition according to item 1. 37. Claim 1 further containing a volatile solvent
The dental restorative material composition according to item 8. 38. The dental restorative material composition according to item 37, wherein the dental restorative material composition is an adhesive. 39. The dental restorative material composition according to claim 18, wherein the dental restorative material composition is an adhesive.