JPS62175411A - 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 and giving high adhesive strength to dental enamel, dentine, metal and porcelain. 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) 0.01-20pts. of an organic sulfinamide (preferably aromatic sulfinamide), (B2) 0.01-10pts. of an organic peroxide (e.g. benzoyl peroxide) and (B3) 0.01-30pts. of an organic acid, acid anhydride or phosphoric acid ester such as 4-acryloxyethyl trimellitic acid (anhydride), bis(2- methacryloxyethyl)phosphoric acid, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a dental restorative composition having adhesive properties. More specifically, the present invention is a dental adhesive that exhibits excellent esthetics due to its hardening agent properties, and that firmly adheres to natural tooth enamel and dentin as well as various metal materials and ceramics. Restorative material compositions such as resins for use in cosmetics, composite resins, cement, and resins for front and near applications.

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, and products with excellent properties have been provided. has been done. For example, U.S. Patent No. 30661
Specification No. 12, Specification No. 3629187, Japanese Unexamined Patent Publication No. 4
8-1115 (Publication No. 3 and Special Publication No. 48-10364
Publication No. 8, etc. describes resins that are cured by redox polymerization, ultraviolet polymerization, or visible light polymerization using polymerization initiators and accelerators, and which mainly contain aromatic polyfunctional acrylates or methacrylates or urethane modified products thereof. Dental composite resins, adhesives,
A Kodaka fissure 1 dorsal sealing material and the like are disclosed.

Recently, in the field of dentistry, the above-mentioned binder resins, especially methacrylic monomers as the main component, abbreviated as BIS-GMA resin, have been used instead of the conventional instant polymerization resins mainly composed of methacrylate. A viscous composite material containing tapeworm inorganic filler is provided as a composite resin.

However, this type of dental composite renon generally has insufficient adhesion to the tooth structure, which may cause the restoration to fall 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 these clinical problems, methods have been developed to improve the adhesion between Componotrenone and tooth structure.

For example, the so-called acid edge blow method, in which enamel is treated with acid, has been known for a long time.
al Research), Volume 34 (6), No. 84
9 to 853 (1955)]. The bonding achieved by this method is not due to chemical bonding between the tooth substance and the bonding resin, but is mainly due to a mechanical fit in which the resin that has entered the microscopic grooves formed by demineralization of the enamel trabeculae hardens and becomes anchored. It has been found that the margin leakage test does not provide sufficient margin sealing properties due to the

In addition, proposals have been made to increase the adhesion between resin and tooth substance using methacrylic monomers containing phosphate ester residues or acid anhydride residues, but this type of Single turtles are 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 and ceramic 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.

Benzoyl peroxide and aromatic tertiary monomers are radically polymerizable monomers that have long been known as dental restorative compositions.
Compositions containing amine as a curing agent tend to discolor over time due to UV rays, heat, etc. due to products formed from intermediate products resulting from the reaction of two components of the curing agent, and have insufficient mechanical strength. Not only that, but the adhesion to tooth and metal is also low (approximately 0.5 to 0.0 for dentin that is not treated with acid).
6Kgf/C).

In addition to the above-mentioned curing agent system containing benzoyl peroxide and aromatic tertiary amine, 4-methacryloxyethyl trimellitic anhydride (JP-A-54-11149;
-1 '2338 Publication, '55-110171 Publication)), a charge transfer complex is rapidly formed between the aromatic tertiary amine and the acid anhydride residue immediately after mixing. Therefore, redox conversion is significantly delayed, the cured product becomes yellowish brown, and its adhesiveness is low.

The above curing agent system containing benzoyl peroxide and an aromatic tertiary amine is further supplemented with CI (,=CII-PO(OH)
z or Cl-1,=CH-C,H4-CH2PO(O
tl), etc. (Journal of Dental Research, Vol. 53, pp. 878-888, and Vol. 56, pp. 543-95)
In the case of a composition containing a compound (see page 2), the polymerization is significantly delayed or does not cure, and the expected adhesiveness cannot be obtained.

A composition containing peroxide and aromatic sulfinic acid as a curing agent solves the problem of discoloration, but not only does it not cure sufficiently due to the influence of moisture and oxygen, but the cured product also Due to the hygroscopic nature of the residual sulfinic acid, water absorption becomes high in the oral cavity, which tends to cause vitiligo and deterioration.

Japanese Patent Publication No. 56-33363 discloses a technology that improves the curing speed of resin and its adhesion to tooth structure by blending diacyl peroxide, aromatic tertiary amine, and metal salt of aromatic sulfinic acid as curing agents. is disclosed. However, in this case, due to the poor solubility of the aromatic sulfinate in the radically polymerizable monomer, the mechanical strength of the cured product is affected by the presence of salts precipitated during polymerization of the system and insoluble residual curing agent components. and decreased water resistance and adhesion in the oral cavity.

Special Publication No. 42-14318 and No. 45-2919
Publication No. 5 discloses a technique for improving adhesion to tooth tissue, especially dentin, by using trialkylborane as a hardening agent, but trialkylborane,
For example, tri-n-butylborane can only be used in combination with very limited radically polymerizable monomers such as methacrylate, and its flammability poses clinical safety problems during storage. At the same time, 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, is highly safe in clinical operation, has no discoloration, has excellent aesthetics, and can be used only with the enamel and dentin of natural teeth. In order to provide a novel dental restorative material composition that exhibits durable and high adhesiveness to various metal materials, ceramic materials, etc., in combination with a radically polymerizable monomer and a hardening agent. It's Otsu's.

Means for Solving the Problems The dental restorative composition of the present invention is composed of a radically polymerizable monomer and a hardening agent, and is particularly characterized by the hardening agent. That is, if a combination of (a) organic sulfinic acid amide, (b) organic peroxide, and (c) organic acid, acid anhydride, or phosphoric acid ester is used as a curing agent, the cured product will change color and have an aesthetic effect. It was discovered that the adhesive has excellent properties and strongly adheres to tooth enamel and dentin, as well as metals and porcelain, leading to the creation of the present invention.

The feature of the present invention lies in the composition of the curing agent, which is different from the curing agent used in conventional dental renons by combining benzoyl peroxide and tertiary amine, or by combining organic peroxide and tertiary amine. In contrast to those in which metal salts of aromatic sulfinic acids were used in combination or alkyl boron derivatives, compounds consisting of the following combinations U'' were used: (a) organic sulfinic acid amide (b) organic peroxide (ha) ) It consists in using a combination of organic acids, acid anhydrides or phosphoric esters.

The composition of the present invention containing a radically polymerizable monomer and the above curing agent systems (a), (b), and (c) does not discolor, is aesthetically pleasing, and is strong against tooth tissue, metals, and even porcelain. Because of its adhesive properties, it is very effective as a dental restorative composition.

The present invention will be explained in more detail below. In this specification, "floor resin" refers to floor resin, repair resin, floor lining material, floor resin that can be bonded to metal floors, etc. , "Dental composite resin" means a dental composite resin containing an inorganic filler or an organic composite filler in its composition, abutment construction, etc., and "dental adhesive material" means a dental composite resin containing an inorganic filler or organic composite filler. t4'4 grade orthodontic welt material,
Pit fissure ii'+ff sealing material for prevention of caries, bonding material for 1゛41 family that can be used in conjunction with composite resin ill restoration, brimer for surface treatment, used with resin for eruption crowns made by photopolymerization or heat polymerization method "Dental cement" refers to metal-adhesive resins and porcelain-capturing adhesives that can be used, and "dental cement" refers to backing lining cements and resin cements that can be applied to crowns, inlays, inlays, bridges, and fixed teeth. "Resin for dental crowns" means hard resin baked by heat polymerization, hard resin photopolymerized, and the like.

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

The radical polymerizable monomer used in the present invention is a radical polymerizable monomer that has been conventionally used in dental restorative materials such as floor resins, dental composite resins, dental adhesives, resin cements, and veneer resins. In addition to sexual 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)phenoquinpropyl methacrylate, neopentyl glycolone (meth)acrylate, Monoethylene glyco~luno(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(
meth)acrylate, tetraethylene glycolone (meth)acrylate, dodecaethylene glycol di(meth)acrylate, glycerin di(meth)acrylate,
Bisphenol A-di(meth)acrylate, 2.2'
-bis[(meth)acryloxyethoxyphenylcopropane, 2,2'-bis[(γ-(meth)acryloxy-β-hydroxypropoxy)phenylcopropane, trimedylolpropane tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, glycidyl (meth)acrylate, t-butylamino-ethyl methacrylate HF' salt, methyl-α-fluoroacrylate, 2,2.2-trifluoroethyl methacrylate, 2,2.2-trifluoroethyl -α-Fluoroacrylate and urethane bond-containing compounds are reaction products of diisocyanates and hydroxyl group-containing (meth)acrylates, and reaction products of diisocyanates and hydroxyl group-containing mono(meth)acrylates at a molar ratio of I:2. product, reaction product of diisocyanates and hydroxyl group-containing di(meth)acrylates in a molar ratio l:2, diisonoanates and hydroxyl group-containing mono(
Reaction product of meth)acrylate and di(meth)acrysades containing hydrogynyl groups in a molar ratio of 1:I:l, azuronurethane prepolymers having neuisocyanate groups at both ends, and mono(meth)acrysades containing hydroxyl groups. A reaction product with a molar ratio of 1:2 between the urethane prepolymers and the hydroquinol group-containing di(meth)acrylates, a reaction product between the urethane prepolymers and the hydroquinol group-containing di(meth)acrylates, and a hydroxyl group-containing monomer with the urethane prepolymers. Reaction products of (meth)acrylates and hydroxyl group-containing di(meth)acrylates in a molar ratio of 1:l:l, such as di((meth)acry[1xyethyl)xylene diurethane, di((
meth) acryloxyethyl) toluene diurethane, di(
(meth)acryloxyethyl)hexamethylene diurethane, di((meth)acryloxyethyl)trimedelhexamethylene diurethane, di((meth)acryloxyethyl)isophorone diurethane, bis[di((meth) Acryloxy) glycerol] hexamethylene diurethane,
Bis[di((meth)acryloxy)glycerol cotrimethylhexamethylene diurethane, bis[)((meth)
1.1゜Molar ratio of 3-trimethylhexamide diisonanate, 2-hydrogyneethyl (meth)acrylate and glycerin di(meth)acrylate, l:l
: Reaction product of 1, reaction product of isophorone diisonanate, 2-hydroxyethyl (meth)acrylate and glycerin di(meth)acrylate in a molar ratio of 1:I:1, (meth)acrylic acid and glycidyl meth Molar ratio with acrylate! :1 reaction product and I, I, 3
-1 trimethylhexamethylene diisocyanate and 2
-Hydroxyethyl methacrylate to glycidyl methacrylate molar ratio III to reaction product molar ratio 1:I :l reaction product, 2-hydroxyethyl methacrylate to glycidyl methacrylate molar ratio 1: The molar ratio of the reaction product of 1 to isophorone diisocyanate l · The molar ratio of the reaction product of l to (meth)acrylic acid and glycidyl methacrylate! Examples include a reaction product with a molar ratio of 1:1 and diphenylmethane diisocyanate.

The organic sulfinic acid amide used in the present invention has the following formula: % formula % (wherein R is an aliphatic or aromatic residue that may contain a substituent such as a halogen atom, an alkyl group, an alkoxy group, or an aryl group) and Ro and R'' may be the same or different and each independently represents a hydrogen atom, a lower alkyl group or an aryl group, or together with a nitrogen atom, represents a heterocyclic residue h. It will be done.

Aromatic sulfinic acid amide is a particularly suitable sulfinic acid amide because it not only has high solubility and activity for the above-mentioned radically polymerizable monomer, but also is easy to manufacture and has good storage stability. The following compounds are exemplified. Benzenesulfinamide, p-toluenesulfinamide, p-chlorobenzenesulfinamide, N, N
-dimethyl-benzenesulfinamide, N,N-dimethyl-p-toluenesulfinamide, N.

N-methyl-phenylbenzene sulfinamide, N
, N-dimethyl-p-chlorobenzenesulfinic acid amide, benzenesulfinic acid morpholide, p-toluenesulfinic acid morpholide, p-chlorobenzenesulfinic acid morpholide, benzenesulfinic acid piperidide, p-
Chlorbenzenesulfinic acid piperinide, N,N-dimethyl-β-naphthalene-sulfinamide, methanesulfinic acid anilide, methanesulfinic acid p-toluicide, and the like. Among these exemplified compounds, particularly preferred are p-toluenesulfinic acid morpholide, N,N-dimethyl-p-toluenesulfinic acid amide, benzenesulfinic acid moly71:lide, and N,N-dimethyl-benzenesulfinic acid amide. be.

Incidentally, if desired, an organic sulfinic acid amide of 2F1 or more may be used in combination.

The amount of organic sulfinic acid amide blended is approximately 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of the radically polymerizable monomer.

If the amount is less than 0.01 part by weight, the intended purpose of the present invention cannot be achieved, and if it is more than 20 parts by weight, the polymerization reaction will be excessively accelerated, causing deterioration of the cured product.

Examples of the organic peroxide used in the present invention include the following compounds: benzoyl peroxide, 4°4°-dichlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dilauryl peroxide, methyl ethyl ketone. peroxide, t-butyl peroxymaleic acid, succinic acid peroxide, etc. Among these peroxides, particularly suitable one has the following general formula (
However, premature esters of difunctional acids represented by R in the above formula (argyl group having 1 to 3 carbon atoms) are preferably used. A particularly preferred organic peroxide is t-
Butyl peroxymaleic acid, benzoyl peroxide, =1,4'-dichlorobenzoyl peroxide.

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

The amount of peroxide to be blended is approximately o, o+-to parts by weight, preferably 0.00 parts by weight, per 00 parts by weight of the radically polymerizable monomer.
It is 1 to 5 parts by weight. If the amount 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.

The curing agent in the present invention further includes an organic acid,
Acid anhydrides or phosphoric esters are used.

A combination of only an organic sulfinic acid amide and an organic peroxide has the problem that it does not cure or has a slow curing speed, resulting in a long curing time. Further, a similar problem occurs when a combination of only an organic sulfinic acid amide and an organic acidic component is used. On the other hand, in conventional curing agent systems using organic peroxides and tertiary amines, the curing rate is retarded by the addition of acidic components. However, in the present invention, the curing speed is accelerated by adding an acidic component such as an organic acid, acid anhydride, or phosphoric acid ester, and an appropriate curing time is provided.
It greatly contributes to improving adhesion.

The organic acids used in the present invention include general mono-, no-,
Although tri- and tetra-carboxylic acids and sulfonic acids can be used, suitable organic acids are radically polymerizable monomers having a carboxyl group in one molecule. For example, methacrylic acid, acrylic acid, 4-methacryloxyethyltrimethic acid, 4-acryloxyethyltrimethic acid, 6-methacryloxyethylnaphthalene 1,2.6-
1licarboxylic acid, N,0-dimethacryloxydyrosine,
Examples include 0-methacryloxydilonine, N-methacryloquine phenylalanine, and 1,4-dimethacryloxyethylpyromellisotate.

Next, as the acid anhydride, a rancal polymerizable monomer in which an acid anhydride group is bonded to an aryl group due to its structure is preferable. Suitable acid anhydrides include 4-methacryloxyethyltrimethic anhydride, 4-acryloxyethyltrimethic anhydride, 6-methacryloxyethylnaphthalene 1,2.6-
) Ricarboxylic anhydride, 6-Methacryloxyethylnaphthalene 2゜3.6-) Ricarboxylic anhydride, 4-Methacryloxyethoxylponylbrobionoyl 1.8-Naphthalic anhydride, 4-Methacryloxyethylnaphthalene Examples include 1,8,4-tricarboxylic anhydride.

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 C-T rapidly form in the composition. A complex formation reaction occurs, and the cured product takes on a yellow-brown color.
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 and organic sulfinic acid amides, the curing speed became stable, there was no yellowing, and the enamel and dentin of natural teeth were cured. It was discovered that it strongly adheres to metals, ceramics, etc.

Next, as the phosphoric acid ester, any radically polymerizable monomer having a phosphoric acid ester group in one molecule may be used. For example, (2-(meth)acryloxyethyl)
Examples include phosphoric acid, (2(meth)acryloxyethyl)phenylphospolybucic acid, and bis(2-(meth)acryloxyethyl)phosphoric acid.

Conventionally, these phosphoric acid esters have had the problem of significantly delayed polymerization or no 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 It has been found that this problem can be solved by the combined use of organic sulfinic acid amide and organic sulfinic acid amide, resulting in high adhesive strength.

The amount of the organic acid, acid anhydride or phosphoric ester used in the present invention is suitably 0.1 to 30 parts by weight or less based on 100 parts by weight of the radically polymerizable monomer. If it exceeds 30 parts by weight, it is not preferable because it causes a decrease in mechanical performance.

The organic acid, acid anhydride, or phosphoric ester may be added to a radically polymerizable monomold, and an organic sulfinic acid amide and an organic peroxide may be added thereto as a curing agent. It's a monkey.

In the present invention, a tertiary amine may be added as a curing agent component if desired. That is, the curing rate is accelerated by adding a tertiary amine to the composition of the present invention. In particular, when 1-butylbaroxymaleic acid is used as the organic peroxide, it can be used as a quaternary curing agent for organic sulfinic acid amides, organic acids, and tertiary amines without any discoloration and has excellent aesthetic properties. The present invention also provides a composition that has strong adhesion to teeth and metals. Further, even when diacyl peroxide is used as the organic peroxide, by appropriately selecting the amount of tertiary amine used, there is an effect of accelerating the curing rate without causing discoloration of the cured product. Examples of the tertiary amine include N,N-dimethyl-p-toluidine, jetanol-p-)luidine, N,N-dimethylaminoethyl methacrylate, and the like. The amount of the tertiary amine used is 0.01 to 5 parts by weight per 100 parts by weight of the monomer.

In the present invention, a photopolymerization initiator and a photopolymerization accelerator may be added if desired. As the photopolymerization initiator, penzoin methyl ether, penzoin ethyl ether, benzoin isopropyl ether, benzoin, benzophenone, 2-chlorodioxanthone, 9. Examples of so-called ultraviolet sensitizers include visible light sensitizers such as lO-anthraquinone, camphorquinone, benzyl, 4,4°-dichlorobenzyl, and diacetyl. As the photopolymerization accelerator, N,N-dimethyl-p-)luidine, toluethylamine, trihexylamine, 2-dimethylaminoethanol, N-methylgetanolamine, N,N-dimethylaminoethyl methacrylate, N,N -Noethylamino methacrylate and the like are exemplified.

A plurality of photopolymerization initiators and photopolymerization accelerators may be used, and each is used in an amount of 0.001 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomer. .

The dental restorative material composition of the present invention can be used for various purposes such as adhesives, cements, composites, floor resins, and anterior veneer resins, and may be combined with fillers and polymers depending on the purpose of use.

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.

In order to enhance the bonding with the binder resin, these inorganic fillers are preferably used after being subjected to surface treatment with a silane compound or the like. As this silane compound. γ
- A so-called silane coupling agent such as methacryloxypropyltrimethoxysilane or vinylchlorosilane is used to coat the inorganic filler in an amount of 0.1 to 20 parts by weight. Also useful are organic composite fillers prepared by kneading and polymerizing these inorganic fillers with monomers in advance and then pulverizing them.

Examples of the polymer include polymethyl methacrylate, polyethyl methacrylate-1, and various polymerizable polypolymers or copolymers.

A stabilizer may be added to the dental restorative material composition of the present invention, if necessary. Stabilizers include hydroquinone, hydroquinone momomethyl ether, hydroxymethoxybenzophenone, butylated hydroxytoluene, etc., and the amount used is preferably 0.01 to 3.0 parts by weight per 100 parts by weight of the monomer.

The three components of the curing agent used in the dental restorative composition of the present invention are (a) organic sulfinic acid amide, (b) organic peroxide, and (c) organic acid, acid anhydride, or phosphoric ester. Preferably, it is stored in 3 packages or in 2 packages (a) and (b) + (c), and it is preferable that (a) and (c) are stored together in the polymerizable monomer. do not have. When a tertiary amine is added as desired, it is stored together with (a).

The composition of the present invention exhibits its polymerization and curing ability when the compositions stored in three or two packages are mixed together before use. For example, (1)
A restorative material composition is obtained by mixing agent A in which component (a) is contained in a polymerizable monomer and agent B in which component (b) and (c) are contained in polymerizable monomers.

Alternatively, (2) a restorative material composition is obtained by kneading agent A and agent C, in which the filler contains (b) and (c) (T).

Or (3), D in which the filler contains the component (A)
The agent and agent B are kneaded together to obtain a restorative material composition.

Or (4) polymerizable monomers (a) and (b), respectively.
(c) A restorative material composition is obtained by simultaneously mixing the separately contained agents A, E, and F. Or (5) filler (
It is used by simultaneously kneading G agent, A agent, and F agent containing B) to obtain a restorative material composition.
There are no other restrictions on the combinations other than the restriction that and (iii) are not allowed to coexist in the polymerizable monomer. Furthermore, volatile solvents or monomer liquids (a) or (b) or (
A solution prepared by dissolving c) or (b) + (c) can also be used as a pretreatment agent.

Effects of the Invention As described above, the dental restorative material composition of the present invention has excellent aesthetic properties with no discoloration over time compared to the case where the conventional hardener system described above is used, and is moreover resistant to dentin, metal, and ceramics. It has the property of having strong adhesion to materials, making it a great contribution to this field.

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

Implementation Example! ~4 and Comparative Examples 1 to 6 Powder A Silanized silica powder 75.0 parts by weight Silanized barium sulfate 25.0 parts by weight Liquid agent B Butylated hydroxytoluene 0.05 parts by weight The filler was treated with γ-methacryloxy The conventional acetic acid method was carried out on silica or barium sulfate using propyltrimethoxysilane.

That is, 100 parts by weight of a solution of γ-methacryloxopropyltrimethoxysilane dissolved in a 0.1% acetic acid aqueous solution to a concentration of 2.0% by weight was mixed with 100 parts by weight of the filler, and then a slurry was air-dried. Surface treatment was carried out by heat treatment at 80°C for 2 hours and further at 120°C for 30 minutes.

A curing agent was mixed into the powder and liquid B as shown in Table 1, and the powder-liquid ratio was 3.2:1.0 (weight).
Table 2 shows the results of the curing time, color tone of the cured product, adhesion to metal, and adhesion to semi-dental enamel when each powder solution was kneaded at a ratio of .

In the adhesion test, the kneaded paste composition described in Table 1 was applied to the body, and a stainless steel rod (SUS-3
04: 5 mmφ) were pressed together, and after curing the specimen, it was immersed in distilled water at 37° C. for 24 hours, and then the tensile adhesive strength was measured at a tensile speed of 1 mm/mm using a universal tensile tester (manufactured by Toyo Sokki Co., Ltd.).

Table 1 Note: 'npo: benzoyl peroxide' t-B
PM^: t-butilver oxymaleic acid 3 Organic acid: 4-acryloxyethyl trimellitic acid' P-TSNa: Sodium p-toluenesulfinate' P-TSMO: p-Toluenesulfinic acid morpholide 8 Tertiary amine : N,N-di(β-hydroxyethyl)
-1)-Toluidine As is clear from Tables 1 and 2, Comparative Example 3 using a conventional curing agent system consisting of benzoyl peroxide and tertiary amine was cured in 12 minutes, but the cured product was yellow. Changed metal
The metal and enamel-metal bond strengths were also extremely low. Comparative Example 4 in which an organic acid was added to the system of Comparative Example 3
The curing time was significantly delayed at 100 minutes, and the adhesive strength was also low. Therefore, in Comparative Example 5, the amount of curing agent was increased in order to obtain an appropriate curing time, but in this case, although the metal-to-metal adhesive strength was improved, the cured product was significantly yellowed and the enamel-to-metal bond was improved. The adhesive strength was insufficient. On the other hand, in Comparative Example 6 using a conventional curing agent system consisting of benzoyl peroxide, tertiary amine, and sodium aromatic sulfinate, the cured product did not discolor after 5 minutes of curing time, but the metal-to-metal, enamel -Metal adhesive strength was low.

On the other hand, when using the curing agent system of the present invention, that is, the curing agent system consisting of an organic sulfinic acid amide, an organic peroxide, and an organic acid, the cured product changes color as shown in Examples 1 to 4. However, the metal-to-metal and enamel-to-metal adhesive strengths showed excellent results. Example! As is clear from the fact that when the organic acid was removed from the curing agent system used in Comparative Example 1, the curing time was significantly delayed to 42 minutes. Organic acids have the effect of promoting polymerization, and when compared to the conventional benzoyl peroxide tertiary amine curing agent system combined with an organic acid, polymerization is significantly delayed, which has the exact opposite effect. . Furthermore, by using a radically polymerizable monomer having an acidic group in one molecule, which is effective in improving adhesive properties as an organic acid, the metal-to-metal and enamel-to-metal adhesive strengths were significantly improved.

In Comparative Example 2, in which the organic peroxide was removed from the curing agent system used in Example 1, no curing occurred.

From the above results, when using the curing agent system of the present invention, that is, the curing agent system consisting of polysulfinic acid amide, organic peroxide, and organic acid, compared to the case where the curing agent system of the prior art was used. It is clear that it has excellent aesthetics, adhesion to metals, and adhesion to tooth structure.

A comparison between Examples 1 and 2 shows that the use of a tertiary amine in the curing agent system of the present invention is effective in shortening the curing time.

Examples 5 to 7 and Comparative Example 7 Silane-treated silica powder 75.0 parts by weight M parts silane-treated barium sulfate 25.0 parts by weight Liquid agent D Butylated hydroxytoluene 0.05 parts by weight The silane treatment of the filler It was carried out according to the method described in Examples 1 to 4.

A curing agent was added to the powder C and the liquid as shown in Table 3, and the powder/liquid ratio was 3.2 as in Examples 1 to 4.
An example of a composition in which each powder liquid was taken and mixed at a ratio of 1.0 (weight ratio)! Tests similar to those conducted in 4 to 4 were conducted. The results are shown in Table 3.

Cl2-BPO: 4,4'-dichlorobenzoyl peroxide 3 Organic acid: 4-methacryloxyethyl trimellitic acid 4-acid anhydride = 4-acryloxyethyl trimellitic anhydride 0 Metal Nistainless steel (SUS 304
) emery paper #1000 polishing surface 7 Metallic stainless steel (SO3304) emery paper #240 polishing surface 8 enamel; beef enamel emery paper #1000 polishing Example 8 and 9 E-agent silanized silica powder 75. 0 parts by weight Silanized barium sulfate 25.0 parts by weight Mitsuke dimethacrylate 35.0 parts by weight Methyl methacrylate 20.0 parts by weight Butylated hydroxytoluene 0.051 ff 1 part Danshu- Silanized silica powder 75.0 parts by weight Silanized sulfuric acid Barium 25.0 parts by weight trimellitic acid
3.0 parts by weight 4-acryloquine edyltrimethic anhydride 2.0 parts by weight Trimethylhexamethylene diurethane 55.0 parts by weight Triethylene glycol dimethacrylate 30.0 parts by weight 2 -Hydroxypropyl methacrylate! 5.0 parts by weight Butylated hydroxytoluene 0.05 parts by weight The silane treatment was carried out under the same conditions as the acetic acid method in Examples 1 to 4. A composition obtained by mixing the above E agent and F agent at a weight ratio of 3.5:1, and a composition in which agent G and agent (■) were mixed at a weight ratio of 3.5:1.
The adhesion test results of the compositions mixed at a weight ratio of 1 to various adherends are shown in Table 4 as Examples 8 and 9. The adhesion test was conducted in the same manner as in Examples 1-4.

Table 4 1 Metal: Shofu Sufroy Nickel (Ni-Cr alloy;
(manufactured by Shofusha Co., Ltd.) with alumina oxide 8 Enamel: Emery paper #600 polished surface of natural tooth enamel (no acid treatment) 3 Dentin: Emery paper #600 polished surface of natural tooth enamel ( (No acid treatment) 4 Porcelain material: Shofu Unibond (manufactured by Shofusha Co., Ltd. porcelain) enamel color Medium α: Indicates destruction of the porcelain adherend, as is clear from Table 4, which was observed on all test specimens. The inventive composition is 446 kgr/cn+'', 496 kgr/cn+'' on sandblasted metal.
kgf/cm” and has a strong bond of 45 kg not only to tooth enamel but also to dentin without any treatment.
gf/cm” and 46 kgf/cm’. Furthermore, it was found to have excellent adhesion properties of 1.5 gf/cm” and 46 kgf/cm’.
30 kgf/cm" and I 20 kgf/cm", indicating that it has high adhesive properties.

Example 10~! l 1 anal polymethyl methacrylate powder 85.0 polyethyl methacrylate powder! 5. O1-Butyl peroxymaleic 3.0 acid 4-acryloxyethyl trimellitic acid 5.0 J agent Part by weight Silanized silica powder 60.0 Polymethyl methacrylate powder 35.0 Polyethyl methacrylate powder 5.0 t-Butyl peroxy Maleic
3.0 Acid 4-acryloxyethyl trimellitic acid 5.0 Part by weight of anhydride Methyl methacrylate 75.0 Ethyl methacrylate) 20.0 p-Toluenesulfinic acid morpholide 2.0 Butylated hydroxytoluene 0.05! , agent
Part by weight Methyl methacrylate
95. Op-toluenesulfinic acid morpholide
2.0 Butylated hydroxytoluene 0.
05 Test the curing time, color tone of the cured product, and adhesion to various adherends of the composition prepared by mixing the above L agent, J agent, J agent, and L agent at the powder-liquid ratio shown in Table 5. did. The results are shown in Table 5.

In addition, the adhesion test method and the silane treatment method for silica stone are as described in Example 1~
It was carried out according to 4.

Table 5 (Note) 1. Emery paper #1000 polished surface of metal/stainless steel plate (SUS 304) 2. Metal stainless steel rod (SUS 304; 5mmφ
) emery, Lee paper #240 polishing side 3, enamel: natural tooth enamel emery paper 4100
0 Polished surface 4, enamel: 30% phosphoric acid on raw tooth enamel
Second-treated surface 5, dentin: Emery paper #1000 polished surface of natural tooth dentin Example 12 Eruption treatment agent Heavy-duty methyl methacrylate 88t-butyl peroxymale acid 2 The above pretreatment agent was applied to the natural tooth dentin and The composition described in Example 8 was used to coat dentin and metal (Ni-Cr) in one layer on the metal surface.
An adhesion test was conducted on the alloy (manufactured by Shofusha Co., Ltd.) and the result was 7.
An adhesive strength of 0 kN/cm' was obtained.

Example 13 When carrying out a dye leakage test using Shofu Super Lux Daylight (manufactured by Shofu Co., Ltd.) according to its instruction manual, 40 parts by weight of di(methacryloxethyl) trimedelhexamethylene diurethane, bisphenol A monomer mixture of 10 parts by weight of diglycidyl methacrylate, 30 parts by weight of triethylene glycol dimethacrylate, 10 parts by weight of neopentyl glycol dimethacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, and 0.1 part by weight of butylated hydroxytoluene. divided into two parts, 3.0 parts by weight of t-butylperoxymalequacid and 1.5 parts by weight of 4-acryloxyethyl trimellitic acid on one side, and 20 parts by weight of N,N-dimethyl-benzenesulfinic acid amide on the other side. , 1 part by weight of benzyl, and 2.0 parts by weight of N-methyljetanolamine were prepared, and the above tests were conducted.

After forming a cavity with a diameter of 3xx and a width of 211R on a freshly extracted human tooth, it was treated with phosphoric acid edging, washed with water, dried, and then a mixture of equal amounts of the above two liquids was applied, air was blown, and Shofu Super Lux Daylight was applied. Makabe,
Almost no dye was observed to enter the cavity. On the other hand, the above 2
When a dye leakage test was conducted in the same manner as above using a liquid from which all curing agent components other than benzyl and N-methyljetanolamine were removed from a curing agent system with a liquid acid component, the dye penetrated through the true wall and into the dental pulp. Even the cavity was recognized.

Ta.

Claims (1)

[Claims] 1. A dental restorative composition containing a radically polymerizable monomer and a hardening agent, wherein the hardening agent is (a) an organic sulfinic acid amide, (b) an organic peroxide, and (c) an organic acid. A dental restorative material composition comprising an anhydride or a phosphate ester. 2. The dental restorative material composition according to claim 1, wherein the organic sulfinic acid amide is an aromatic sulfinic acid amide. 3. Aromatic sulfinic acid amide is benzenesulfinic acid morpholide, p-toluenesulfinic acid morpholide,
N,N-dimethyl-p-toluenesulfinamide,
The dental restorative material composition according to claim 2, which is N,N-dimethyl-benzenesulfinic acid amide or the like. 4. The dental restorative composition according to claim 1, wherein the organic peroxide is t-butyl peroxymaleic acid, benzoyl peroxide, and 4,4'-dichlorobenzoyl peroxide. 5. The organic acid, acid anhydride, or phosphoric ester has at least one carboxyl group, acid anhydride group, or phosphoric ester group in one molecule, and at least one radically polymerizable unsaturated group The dental restorative material composition according to claim 1, comprising a structure having: 6, the organic acid is 4-acryloxyethyl trimellitic acid,
The dental restorative material composition according to claim 1, which is 4-methacryloxyethyl trimellitic acid. 7. The dental restorative material composition according to claim 1, wherein the acid anhydride is 4-acryloxyethyl trimellitic anhydride or 4-methacryloxyethyl trimellitic anhydride. 8. The phosphoric acid esters are bis(2-methacryloxyethyl)phosphoric acid, [(2-methacryloxyethyl)
The dental restorative material composition according to claim 1, which is phenyl]phosphoric acid. 9. Based on 100 parts by weight of the radically polymerizable monomer, the curing agent is (a) 0.01 to 20 parts by weight of organic sulfinic acid amide (b) 0.01 to 10 parts by weight of organic peroxide (c) organic acid , acid anhydride or phosphoric ester 0.1~
The dental restorative composition according to claim 1, comprising 30 parts by weight. 10. The dental restorative composition according to claim 1, further comprising filler or polymer particles. 11. Claim 1 further containing a volatile solvent
The dental restorative material composition described in .