JPS60112807A - Curable composition - Google Patents

Abstract

PURPOSE:The titled composition useful for the teeth, having improved curing characteristics, adhesiveness, strength, etc., obtained by blending a radically polymerizable monomer consisting of a specific aromatic polycarboxylic acid and a vinly compound with a curing agent having a specified composition. CONSTITUTION:100pts.wt. radically polymerizable monomer consisting of (A) a (meta)acryloyloxyl group-containing polycarboxylic acid anhydride having a structure wherein a (polyoxy)alkanepolyol has plural OH groups, at least one OH group and (meth)acrlyic acid form an ester, at least one OH group of the compound and one COOH group of aromatic polycarboxylic acid having >=3 COOH groups form an ester and (B) a radically polymerizable monomer of a vinyl compound is blended with a curing agent consisting of (C) 0.1-3pts.wt. diacyloxide, (D) 0.3-5pts.wt. aromatic amine, and (E) 0.1-0.9pt.wt. aromatic sulfinic acid, to give the desired composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has excellent curability in a low temperature region around room temperature,
The present invention relates to a curable composition that exhibits excellent adhesive performance such as water-resistant adhesive strength, hardness, strength, and color tone of the cured product. More specifically, it can exhibit excellent performance as a tooth curable composition such as tooth adhesive, tooth composite resin, tJi tooth hard resin, etc., and is particularly suitable for room-temperature hardening floor resins and their adhesives. The present invention relates to a curable composition that is excellent as an agent.

Conventionally, curable compositions for teeth such as adhesives for teeth, composite resins, and hard resins include (curable compositions consisting of radically polymerizable monomers such as methacrylic acid ester vinyl monomers and curing agents). Many have been proposed.

The performance required of tooth adhesives is that in addition to a high curing speed in the low temperature range around room temperature, the cured product must have excellent adhesive strength to teeth and metals and water-resistant adhesive strength. In addition, for composite resins for teeth and hard resins for teeth, in addition to the above-mentioned excellent curing performance of the composition in the low temperature region around room temperature and the adhesive performance of the cured product to teeth and metals, the cured product It is required that the mechanical properties such as strength, compressive strength, hardness, abrasion resistance, and color are excellent.With the recent remarkable progress in dental restorative treatment technology,
The requirements for improving the above-mentioned performance of these curable tooth compositions have become extremely severe.

Among conventional dental curable compositions consisting of radically polymerizable monomers such as vinyl (meth)acrylate monomers and hardening agents, those that attempt to achieve the above-mentioned performance improvement by improving the hardening agent. Some have also been proposed. For example, Japanese Patent Publication No. 56-53565 describes (meth)methacrylate, ethylene glycol dimethacrylate, bisphenol A diglycidyl methacrylate, triethylene glycol dimethacrylate, etc.
A specific composition consisting of diacyl peroxide, aromatic amine, and aromatic sulfinate as a curing agent for acrylic acid ester-based vinyl sulfinate has been used to improve performance such as curing speed, adhesion of the cured product to teeth, and degree of coloration. However, it is difficult to say that these curable compositions fully satisfy the above-mentioned performance.

The present applicant has discovered that when a composition consisting of a radically polymerizable monomer consisting of 4-methacryloyloxyethoxycarbonylphthalic acid or its acid anhydride and a vinyl compound and a free radical generator is used as a tooth adhesive, adhesiveness is achieved. Strength,
It was discovered that it has excellent adhesive performance such as water-resistant adhesive strength, and was published in Japanese Patent Application No. 52-121858 and Japanese Patent Publication No. 58-17.
I have already proposed this in Publication No. 515. Although this curable composition for teeth has excellent adhesive performance, mechanical properties, and color tone, there remains room for improvement in terms of curing speed.

In view of the above-mentioned state of the art of conventional curable tooth curable compositions and the performance requirements for these compositions, the present inventors have determined the curable performance of the composition, the adhesion performance of the cured product, the mechanical properties, As a result of intensive research into curable compositions with excellent water absorption resistance, boiling water resistance, and color tone, we found that a specific (meta)
A curable composition consisting of a radically polymerizable monomer consisting of an acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride and a vinyl compound, and a curing agent, in which diacyl peroxide, aromatic amine, and aromatic sulfinic acid are used as the curing agent. It has been discovered that the above object can be achieved by combining curing agents with specific compositions, and the present invention has been achieved.

According to the present invention, the composition has a high curing speed in a low temperature region around room temperature, has excellent adhesive performance such as adhesive strength and water-resistant adhesive strength, and has excellent mechanical properties such as hardness, compressive strength, hardness, and abrasion resistance of the cured product. It has excellent properties, water absorption resistance, boiling water resistance, and color tone, and fully satisfies the performance required for dental curable compositions such as dental adhesives, composite resins, hard resins, and floor resins. Therefore, in addition to being suitable for these dental applications, especially room-temperature curing floor resins and their adhesives, it can also be used for precision machining adhesives other than dental applications, metal adhesives, and various composites. It can also be used for resin, etc. Furthermore, since the curable composition of the present invention has excellent adhesion to teeth or metals, particularly water resistance and durability, it is suitably used for teeth, metals, and as an undercoat for paints.

To summarize the present invention, the present invention provides that (a) at least one hydroxyl group of an alkane polyol or boronoxyalkane polyol having at least two hydroxyl groups in one molecule is (
A (meth)acryloyloxyl group-containing aromatic compound having a structure in which a gostyl group of metaphacrylic acid is formed, and at least one hydroxyl group forms an ester with one carboxyl group of an aromatic polycarboxylic acid having at least 6 carboxyl groups. A curable composition comprising a radically polymerizable monomer consisting of a group polycarboxylic acid or its acid anhydride, and a (bl vinyl compound), and a curing agent, wherein the curing agent is added to the radically polymerizable monomer 100 type assembly. (c) diacyl peroxide in the range of 0.1 to 3.0 parts by weight, (d) aromatic amine in the range of 0.3 to 5.(] parts by weight, and (θ) 0.1 to 0. 9 parts by weight of an aromatic sulfinic acid or a salt thereof;
This is the gist of the invention.

In the curable composition of the present invention, one constituent of the radically polymerizable monomer component unit (methaneacryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride tal)
is one carboxyl group of an aromatic polycarboxylic acid in which at least one hydroxyl group of an alkane polyol or polyoxyalkane polyol having at least two hydroxyl groups in one molecule has at least five carboxyl groups. It is a compound with a structure that forms an ester with

As the alkane polyol having at least two hydroxyl groups in one molecule constituting the (meth)acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride (al), ethylene glycol, 1,2-propylene glycol, Examples include 1.5-propylene glycol, butylene glycol, hexylene glycol, trimethylolpropane, glycerin, and pentaerythritol.
(Polyoxyalkane polyols having + and 'J hydroxyl groups include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, diethylene glycol, ditrimethylolpropane, diglycerin, triglycerin, dipentaerythritol, etc.) For example,

Further, the (meth)acrylic acid component constituting the (meth)acryloyloxyl group-containing aromatic polycarboxylic acid is acrylic acid or methacrylic acid, and furthermore, the aromatic polycarboxylic acid component having at least 5 or more carboxyl groups. It is preferable that the acid is an aromatic polycarboxylic acid in which at least two carboxyl groups are bonded to adjacent carbon atoms on the aromatic nucleus, and specifically, hemimeric acid) 5fF,) limellitic acid, brenidic acid, merophane Examples include acids, pyromellitic acid, and the like.

The (meth)acryloyl subxyl group-containing aromatic polycarboxylic acid or its acid anhydride includes 4-(meth)acryloyloxymethoxylponylphthalic acid or its acid anhydride, 4-(meth)acryloyloxyethoxycarbonylphthal Acid matter is its acid anhydride, 4-(2-hydroxy-5-(meth)acryloyloxypropoxycarbonylsiphthalic acid or its acid anhydride, 2,3-bis(5,4-dicarbogysybenzoyloxy)propyl) (
meth)acrylate or its acid anhydride, 2-(5,4
-dicarbogycibenzoyloxy)-1,3-dimethacryloyloxypropane or its acid anhydride, [in the formula,
R represents a hydrogen atom or a methyl group. ] or acid anhydrides thereof. Among these, 4-(meth)acryloyloxyethoxycarbonylphthalic acid or its acid anhydride is particularly preferred.
Acryloyloxyethoxycarbonyl phthalic anhydride is preferred.

In the curable composition of the present invention, vinyl compounds (b) which are other constituents of the one pararadically polymerizable monomer component unit include (methacrylic acid) such as methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Argyl acrylate, acrylic acid, methacrylic acid, acrylic acid-2
-Hydroxyethyl, 2-hydroxyethyl methacrylate, ethylene glycol di(meth)acrylate, brobylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(methacrylate, butylene) Glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloyloxyphenyl)propane, 2,2-bis(
4-(meth)acryloyloxycyclohegycyl]propane, 2,2-bis[5-(meth)acryloyloxycyclohegycyl]propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra( Examples include meth)acrylate, dipentaerythritol, styrene, and vinyl acetate, and mixtures of two or more of these can also be used.

In the curable composition of the present invention, the diacyl peroxide (c) is specifically diacetyl peroxide, capril peroxide, dilauroyl peroxide, diacetyl peroxide, dibenzoyl peroxide, p
, p-dichlorodibenzoyl peroxide, pep-dimethoxydibenzoyl peroxide, 11111)'-
Examples include dimethyl dibenzoyl peroxide and pIp-dinitrocyhenzoyl peroxide. Among these diacyl peroxides, dibenzoyl peroxide is preferred.

In the curable composition of the present invention, the aromatic amine fcll used as a curing agent component has at least one aryl group bonded to the nitrogen atom, and is a primary amine,
Although either a secondary amine or a tertiary amine can be used, a tertiary amine is preferably used. in particular,
Aniline, toluidine, xylidine, phenylenediamine, N,N-diethylaniline, N,N-diethylaniline, N,N-di(β-hydroxyethyl)aniline,
N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dimethylanisidine, N,N-diethylanisidine, N,N-dimethyl-t-butylaniline,
N,N-diethyl-t-butylaniline, N,N-dimethyl-p-chloroaniline, diphenylamine, N,N
-bis(β-hydroxyethyl)-p-toluidine and the like can be exemplified. Among these, N, i
l-dimethyl-p-toluidine, N,N-dimethyl-p
-t-butylaniline, N,N-dimethylanisidine,
111. such as N,N-dimethyl-p-chloroaniline at least in the p-position of benzene coral. Tertiary amines having a child-donating substituent group are preferred, especially N,N-dimethyl-
p-Toluidine is preferred.

In the curable composition of the present invention, as the aromatic sulfinic acid or its salt tel, ordinary alkali metal salts, alkaline earth metal salts, amine salts, and ammonium salt compounds of aromatic sulfin a or aromatic sulfinic acid are used. However, it is preferable to use an aromatic sulfinate because the color tone of the cured product is excellent. Examples of alkali metal salts include lithium salts, sodium salts, and potassium salts; examples of alkali metal salts include magnesium salts, calcium salts, strontium salts, and barium salts. The amine salts include methylamine, ethylamine, propylamine, butylamine,
Salts of primary amines such as aniline, toluidine, phenylenediamine, xylylenediamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, N-methylaniline, N-ethylaniline,
diphenylamine, salts of secondary amines such as N-methyltoluidine, trimethylamine, triethylamine salts luridine, N,N-dimethylaniline, N,N-di(β-hydroxyethylaniline, N,N-diethylamine,
Examples include salts of tertiary amines such as N,N-dimethyltoluidine and N,N-bis(β-hydroxyethyl)toluidine. Examples of salts of ammonium compounds include ammonium salts, tetramethylammonium salts, and tetraethylammonium salts. salt, detrabropylammonium salt,
Examples include trimethylbenzylammonium salt.

The aromatic sulfinic acids include benzenesulfin 9, a-) luenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, tesilbenzenesulfin Na, l' deci/l/benzenesulfinic acid, chlorobenzenesulfinic acid. Examples include naphthalene sulfinic acid and naphthalene sulfinic acid.

Specifically, the aromatic sulfinate salts include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, barium benzenesulfinate, and benzenesulfinate. butylamine salt,
Benzenesulfinate aniline salt, benzenesulfinate toluidine salt, henzenesulfinate phenylenediamine salt, benzenesulfinate diethylamine salt, benzenesulfinate diphenylamine salt, benzenesulfinate triethylamine salt, benzenesulfine Cσ
Ammonium l'7 l\, tetramethylammonium benzenesulfinate, trimethylbenzylammonium benzenesulfinate, lithium 0-toluenesulfinate, thorium o-1-toluenesulfinate, calcium 0-toluenesulfinate, 0-toluenesulfinate Acid aniline salt, 0-) ammonium toluenesulfinate, tetraethylammonium 0-toluenesulfinate, p-) lithium toluenesulfinate, p-) sodium toluenesulfinate, p-) potassium toluenesulfinate, barium p-toluenesulfinate, p-)
/reninsulfinic acid ethylamine '8 Tetrabutylammonium, sodium β-naphthalenesulfinate, strontium β-naphthalenesulfinate, triethylamine β-naphthalenesulfinate, N-methyltoluidine β-naphthalenesulfinate, ammonium β-→-phthalenesulfinate, β-naphthalene Examples include trimethylbenzylammonium sulfinate. Among these, lithium salts, sodium salts, magnesium salts, calcium salts, and barium salts of penzelsulfinic acid and p-)luenesulfinic acid are preferred.

In the curable composition of the present invention, when an aromatic amine salt of an aromatic sulfinic acid is used as the aromatic sulfinate (θ), the aromatic amine salt of the aromatic sulfinic acid or the aromatic amine fd) and the aromatic sulfinic acid (θ), there is no need to add an aromatic amine in the curable composition of the present invention. Furthermore, in the curable composition of the present invention, the aromatic amine (d)
When mixed with the aromatic sulfinate (fe) in the presence of a radically polymerizable monomer, polymerization usually occurs within a few minutes. Therefore, from the viewpoint of storage stability, the aromatic amine (dl
and the aromatic sulfinate (e) are divided and blended into the curable composition of the present invention.

In the curable composition of the present invention, the (meth)acryloyloxyl group, (containing aromatic polycarboxylic acid or its acid anhydride (a) The ratio of each component is usually 0.1 to 50% of the (meth)acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride fa)
% by weight, preferably in the range of 1 to 10% by weight;
The vinyl compound (bl is usually 70 to 99.9% by weight)
, preferably in the range of 90 to 99% by weight.

In the curable composition of the present invention, the blending ratio of each component of diacyl peroxide (c), aromatic amine (d), and aromatic sulfinic acid or its salt (e) to the radically polymerizable monomer + 00 parts by weight is They are as follows. That is, diacyl peroxide (0) is 0.
The aromatic amine fd) is in the range of 0.5 to 5 parts by weight, and the aromatic sulfinic acid or salt thereof (θ) is in the range of 0.1 to 0.9 parts by weight. Furthermore, the diacyl peroxide (C) must be in the range of 0.1 to 5 parts, and the aromatic amine (d) must be in the range of 0.5 to 2.5 parts. , aromatic sulfinic acid or its salt (e) is preferably in the range of 0.2 to 0.8 parts by weight.

If the blending ratio of the diacyl peroxide (C) is less than 0.1 part by weight, it will take a long time to cure the curable composition at room temperature, and the water absorption resistance of the cured product will not be sufficient. If the amount exceeds 100%, the adhesive strength and color of the cured product will decrease. When the blending ratio of the aromatic amine (d) is less than 0.6 parts by weight,
It takes a long time to cure the curable composition at room temperature, and the adhesive strength of the cured product becomes insufficient, and if the amount exceeds 5 parts by weight, the hue of the cured product decreases.

When the blending ratio of the aromatic sulfinic acid or its salt (θ) is less than 0.1 part by weight, the hue of the cured product decreases, the adhesive strength of the cured product becomes insufficient, and
．． If the amount exceeds 9 parts by weight, the adhesive strength of the cured product will decrease, and the water absorption resistance and boiling water resistance will decrease.

The curable composition of the present invention may further contain other components as necessary, such as a powdered inorganic filler, an organic polymer, an inorganic filler, and an acrylic monomer containing a polyfunctional acrylic single nail member. Composite fillers obtained by polymerizing and in the presence of a radical polymerization initiator, tackifiers, polymerization accelerators, polymerization regulators, polymerization inhibitors, etc. can also be blended. Specific examples of the powdered inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica/alumina, alumina, titanium oxide, calcium phosphate, glass powder, and quartz powder. Examples of the organic polymer include wax, ethylene/vinyl acetate copolymer, polymethyl acrylate, polymethyl methacrylate, and copolymers thereof. The blending ratio of these components is appropriate.

Next, the present invention will be specifically illustrated by examples.

The following abbreviations used in Table 1 below represent the following compounds, respectively.

MMA...Methyl methacrylate HDM...1,6-hexylene glycol dimethacrylate TMPT...Trimethylolpropane trimethacrylate DMPT...N,N-dimethyl-p- ) Louisin D
MBA...N,N-dimethyl-pt-butylaniline FTSL...p-) Sodium luenesulfinate PTSS...p-) Sodium luenesulfinate PT S kA... p-) Magnesium toluenesulfinate FTSB...p~Barium toluenesulfinate BPO...Dibenzoyl peroxide (1) Preparation of adhesive test piece Cobalt-chromium alloy (trade name: Cincolylum, manufactured by Seikan Kogyo) ) or a metal piece of nickel-chromium alloy (trade name: SB Bondroy, manufactured by Seikan Kogyo Co., Ltd.) with a flat surface of approximately 1 CIll, after polishing the flat surface well with A1 emery paper.
5071 alumina oxide (manufactured by Beld Sunflare OL)
B-602 Regular] was used for sandblasting. After that, it was washed with water and air-dried, and then a cellophane tape with a circular hole of 5.4 mm in diameter (approximately 10 mm x I Dm
m), apply the curable composition described in Examples or Comparative Examples to the circular hole, adhere an acrylic rod with a diameter of 5 mm by the butt method, and cure for 1 hour at room temperature to prepare an adhesive test piece. did.

(If) Method for evaluating physical properties (1) Adhesive strength After soaking the adhesive test piece in water at 37°C for 24 hours,
Alternately soak in cold water at 4°C and hot water at 60°C for 1 minute each.
It was immersed 00 times for a total of 10 hours. After that, it was left in the air at a temperature of 25°C for 10 minutes, and then the adhesive strength between the alloy and the acrylic pellet was measured at a humidity of 25°C and a tensile speed of 2 mm/'+nin.

(2) Water absorption rate of cured product The water absorption rate was determined in accordance with the standards for room-temperature polymerization resins for denture base repair specified by the Japan Dental Materials Industry Cooperative Association.

Example 1 95 parts by weight of methyl methacrylate, 4-methacryloyloxyethoxycarbonylphthalic anhydride (4-Meta
) 5 parts by weight, dimethyl-p-)luidine (DMPT
70 parts by weight of a composition liquid consisting of 1 part by weight of 70 parts by weight of dibenzoylper, 0.5 parts by weight of BPO, 0.5 parts by weight of sodium p-toluenesulfinate (pTss) and 0.5 parts by weight of polymethyl methacrylate powder. The curing time, color tone, adhesive strength, and water absorption of a curable composition prepared by mixing 100 parts by weight of dispersed polymer powder with 100 parts by weight of the dispersed polymer powder were examined. The results are shown in Table 1.

Examples 2 to 11, Comparative Examples 1 to 7 In Example 1, the compounds listed in Table 1 as the radically polymerizable monomer, diacyl peroxide, aromatic amine, and aromatic sulfinate were used in the amounts listed in Table 1. The curing time, color tone of the cured product,
Adhesive strength and water absorption were examined. The results are shown in Table 1.

/ / /

Claims (1)

[Claims] (1) (aJ i At least one hydroxyl group of the alkane polyofur or polyoxyalkane polyol having at least two hydroxyl groups in the molecule forms an ester of (meth)acrylic acid, and at least one has a structure in which a hydroxyl group forms an ester with one carboxyl group of an aromatic polycarboxylic acid having at least 6 carboxyl groups (meth)
A curable composition comprising a radically polymerizable monomer consisting of an acryloyloxyl group-containing aromatic polycarboxylic acid or its acid anhydride, and (1) a vinyl compound, and a curing agent, wherein the curing agent is (Q) diacyl peroxide in the range of 0.1 to 5 parts by weight, (at[1,5 to 5 parts by weight of aromatic amine, and (θ) 0.1 to 5 parts by weight, based on 100 parts by weight of the polymer. 1. A curable composition comprising, as a curing agent, an aromatic sulfinic acid or a salt thereof in an amount of 0.9 parts by weight.