JPS6136204A - Curable resin composition for tooth - Google Patents

Abstract

PURPOSE:To produce a curable resin composition for tooth, composed of poly[(meth)acryloyloxyalkyl](iso)cyanurate, a vinyl compound and a polymerization initiator, having excellent curing characteristics, and giving a cured product having excellent characteristics. CONSTITUTION:The objective curable resin composition for tooth, having excellent curing characteristics such as the rate of cure, and giving a cured product having balanced and excellent properties such as strength, hardness, abrasion resistance, water resistance, adhesivity to tooth, etc., and suitable as a dental composite resin, hard resin, resin cement and dental adhesive, is produced by mixing (A) 100pts.wt. of the compound of formula I or formula II (at least two of X<1>-X<3> are acryloyl or methacryloyl, and the other one is H or alkyl; R<1>- R<3> are oxyalkylene or polyoxyalkylene), (B) usually 5-1,000pts.wt., preferably 20-600pts.wt. of a vinyl compound and (C) usually 0.01-20pts.wt., preferably 0.05-10pts.wt. of a polymerization initiator.

Description

[Detailed description of the invention] [Industrial application field] 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, the present invention relates to a curable composition that can exhibit excellent performance as a curable composition for teeth, such as a composite resin for teeth, a hard resin for teeth, and an adhesive for teeth.

[Conventional technology]

Conventionally, curable compositions for teeth such as composite resins, hard resins, and tooth adhesives have been made of curable compositions consisting of radically polymerizable monomers such as (meth)acrylate vinyl monomers and polymerization initiators. Many compositions have been proposed.

In addition to a high curing speed in the room temperature range, the properties required of tooth adhesives include excellent adhesive strength and water-resistant adhesive strength of the cured product to teeth.

In addition, for composite resins for teeth and hard resins for teeth, in addition to the excellent curing performance of the composition in the low temperature range near room temperature and the adhesive performance of the cured product to teeth as described above, the bending strength of the cured product , compressive strength,
It is required to have excellent mechanical properties such as hardness and abrasion resistance, and color tone. With the recent remarkable progress in tooth restorative treatment technology, the requirements for improving the above-mentioned performance of these hardening compositions for teeth have become extremely strict.

Among conventional tooth curable compositions comprising (meth)acrylic ester derivatives, various types of compounds have been proposed as (meth)acrylic ester compounds. For example, poly(meth)acrylate of alkane polyol, poly(meth)acrylate of polyoxyalkylene glycol,
Curable compositions with various types of compounds such as meth)acrylate, poly(meth)acrylate of aromatic (phenolic) polyhydroxyl compounds, poly(meth)acrylate of polyepoxy compounds, and poly(meth)acrylate of urethane polyols. It is proposed to be used as a component of objects. These polyfunctional (meta)
Curable compositions made solely of acrylic acid ester derivatives may have poor curing properties such as curing speed, or poor properties such as bending strength, compressive strength, hardness, abrasion resistance, adhesion to teeth, and color tone. Many of the physical properties are often inferior, and the above-mentioned required performance could not be fully satisfied. In addition, attempts have been made to improve these drawbacks by using a combination of two or more types of compounds among these components, but in either case, although the drawbacks can be improved to some extent, they are not sufficient. It was hard to say.

[Problem that the invention seeks to solve]

The present inventors recognized that the conventional curable compositions for teeth have the above-mentioned drawbacks, and created a curable composition for teeth that has excellent curing properties during curing and excellent properties of the obtained cured product. As a result of intensive studies, we found that a curable composition consisting of poly[(meth)acryloyloxyalkyl](iso)cyanurate fat, vinyl compound fb) and a polymerization initiator (C) was found to be a curable composition for teeth that satisfies the above objectives. The present invention was achieved by discovering that the present invention can be used as a composition.

[Summary of the invention]

To summarize the present invention, the present invention has the following formula: 181 General formula [Ia (Ia) (Hb) [wherein X', At least two of them are (meth)acryloyl groups, and R' % R2 and R3 represent an oxyalkylene group or a polyoxyalkylene group.] Poly[(meth)acryloyloxyalkyl] (
The gist of the invention is a curable resin composition for teeth comprising: iso)cyanurate, (bl vinyl compound, and (C1 polymerization initiator).

〔Effect of the invention〕

According to the present invention, the curable composition for teeth of the present invention has excellent curing properties such as curing speed, and the resulting cured product has good strength, hardness, abrasion resistance, water resistance, and adhesion to teeth. It is characterized by its overall excellent characteristics,
Suitable as composite resin for teeth, hard resin, resin cement, and adhesive for teeth.

[Means and effects for solving the problems] Bis[(meth)acryloyloxyalkyl](iso)cyanurate (al) used in the curable resin composition for teeth of the present invention
is the general formula (I) [1a) (I
I b) (where x', x2 and x3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these are (meth)acryloyl groups, and R1, R2 and R3 are Indicates an oxyalkylene group or a polyoxyalkylene group.] Poly [(meth)acryloyloxyalkyl]
(iso)cyanurate, tris[(meth)acryloyloxyalkyl] (iso)cyanurate, bis[(meth)acryloyloxyalkyl] (iso)
Although it may be cyanurate or a mixture thereof, those containing bis[(meth)acryloyloxyalkyl](iso)cyanurate as a main component are preferred. XI
, X2 and X3 are usually C1-C4 alkyl groups. Also, R', II
2 and R3 are an oxyalkylene group having 1 to 12 carbon atoms, preferably 2 to 4 carbon atoms, or a multimer of the oxyalkylene group, usually a dimer to a dodecamer, preferably a dodecamer. It is a dimer or a tetramer. The poly [(meth)acryloyloxyalkyl]
Specifically, the isocyanurates include tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, tris(2
-Acryloyloxypropyl) isocyanurate, tris(2-methacryloyloxypropyl)isocyanurate, bis(acryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, bis(methacryloyloxyethyl)methoxyethyl Isocyanurate, bis(2-acryloyloxypropyl)-2
-Ethoxypropyl isocyanurate, bis(2-methacryloyloxypropyl-2-hydroxypropyl isocyanurate), tris[acryloyldi(oxyethylene)]isocyanurate, tris[methacryloyldi(oxyethylene)]isocyanurate, etc. Further, as the poly [(meth)acryloyloxyalkyl] (iso)cyanurate, tris(acryloyloxyethyl) cyanurate, tris(methacryloyloxyethyl) cyanurate, tris(meth)acryloyloxyethyl oxyethyl) cyanurate, tris (2-acryloyloxypropyl) cyanurate, tris (2-methacryloyloxypropyl) cyanurate, bis (acryloyloxyethyl) hydroxyethyl cyanurate, bis (methacryloyloxyethyl) methoxyethyl cyanurate, bis (2 −
Acryloyloxypropyl-2-ethoxypropyl cyanurate, bis(2-methacryloyloxypropyl)-2=hydroxypropyl cyanurate, Tris[(
Examples include acryloyl di(oxyethylene)] cyanurate and tris(methacryloyl di(oxyethylene)) cyanurate, and mixtures of two or more of these may also be used.

The vinyl compound (bl is an ordinary radically polymerizable carbon/carbon unsaturated monomer, and more specifically, an unsaturated carboxylic acid monomer, an ester Examples include unsaturated monomers, nitrile unsaturated monomers, aromatic vinyl compounds, etc. Examples of the unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, and 4-(meth)acryloyloxy. Examples of such ester unsaturated monomers include (meth)acrylic acid ester monomers, and lower aliphatic carboxylic acid unsaturated esters such as vinyl acetate and allyl acetate. Examples of the nitrile unsaturated monomer include acrylonitrile, methacrylonitrile, etc.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, isoprobenitolene, and the like.

More specifically, the (meth)acrylic acid ester monomer is acrylic acid or methacrylic acid.
It is a (meth)acrylic acid ester compound formed from a hydroxyl compound or a polyhydric hydroxyl compound. More specifically, examples include alkyl (meth)acrylates such as methyl (meth)acrylate and ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4- (meth)acryloyloxyethoxycarbonyl phthalic anhydride, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate Acrylate, neopentyl glycol di(
meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acryle-1-12,2-bis[4-(meth)acryloyloxyphenyl]propane, 1,3-di(meth)acryloyloxy Ethoxybenzene, 2.2-bis[4-(meth)acryloyloxycyclohexyl]propane, 2.
Examples include 2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. I can do it.

In the curable composition for teeth of the present invention, the blending ratio of the vinyl compound is usually 5 to 1000 parts by weight, preferably 20 to 1000 parts by weight, per 100 parts by weight of poly[(meth)acryloyloxyalkyl](iso)cyanurate. 6
00 parts by weight.

The polymerization initiator (C1) blended into the curable resin composition for teeth of the present invention is a free radical generator or a photosensitizer. benzoyl peroxide, cumene hydroperoxide, t-butyl perbivalate, benzoyl peroxide
Examples include aromatic tertiary amines. Aromatic tertiary amines to be combined with benzoyl peroxide include N,N-dimethylanline, N,N-dimethyl-〇-toluidine,
N,N-dimethyl-p-toluidine, N,N-dimethyl-p-t-butylaniline, N,N-getanolaniline, N,N-getanol-p-)luidine, and the like. Examples of the photosensitizer include carbonyl compounds such as benzoin methyl ether, benzoin isopropyl ether, diacetyl, camphorquinone, and benzyl, and combination systems of the carbonyl compounds and aromatic tertiary amines. In addition to the aromatic tertiary amines shown in the free radical generator section, (CH3)2N
+COz”, (C11,)2N-G-C(hCJ, (C
113) 2N-@-CHN Natokaakerareru. The amount of the polymerization initiator fcl used is usually 0.01 to 20 parts by weight per 100 parts by weight of the above-mentioned poly[(meth)acryloyloxyalkyl](iso)cyanurate a) and vinyl compound (b). within the range, preferably 0
．． It is preferably in the range of 0.05 to 10 parts by weight.

The curable resin composition for teeth of the present invention may be a composition consisting only of the above-mentioned three essential components, but may further include a polymerization inhibitor, a filler, a pigment, an X-ray contrast agent, an ultraviolet absorber, (
Various additives can be blended, such as (reactive) oligomers and polymers such as polymethyl methacrylate.

The blending ratio of these additives is appropriate. Specifically, fillers include glass powder, mica, glass peas, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, alumina, silica alumina, calcium phosphate, calcium carbonate, silica stone, silica sand, quartz, kaolinite, Examples include montmorillonite, sericite, talc, chlorite, pottery stone, and feldspar. In addition, the surfaces of these fillers treated with alkyl carboxylates, silane couplers, titanium couplers, Cl2S1 (C113)z, alcohol, etc. can also be used.

The composition of the present invention does not require a solvent, but the poly[(meth)acryloyloxyalkyl](iso)cyanurate + al and vinyl compound (bl) of the present invention are mixed to form a homogeneous solution, and then a polymerization initiator ( It is preferable to manufacture by adding C1 and a filler as necessary to make a paste.Also, it can be manufactured by mixing the above components at the same time to make a paste.Also, if the polymerization initiator is benzoyl peroxide For systems where polymerization starts at room temperature, such as aromatic tertiary amines, divide the above paste into two, and
It is preferable to mix one paste with benzoyl peroxide and the other with an aromatic tertiary amine, divide the paste into two pastes, and mix them immediately before use.

The composition of the present invention thus obtained is cured by leaving it at room temperature or by irradiating it with visible light. In the case of photocuring, the material is irradiated with light using a high-pressure, medium-pressure, or low-pressure mercury lamp, halogen lamp, or the like.

The composition of the present invention has the advantage that it has excellent curability at room temperature, and that the cured product has good water absorption, hardness, compressive strength, bending strength, etc. Therefore, it is suitable for use as dental composite resins, hardened resins, resin cements, and dental adhesives.

〔Example〕

Next, the present invention will be specifically explained using examples.

In addition, in Examples and Comparative Examples, evaluation was performed by the following method.

(1) Brinell strength It was carried out according to JIS-T6509.

(2) Compressive strength test pieces were prepared by filling a Teflon mold with an inner diameter of 5 mm and a thickness of 3 mm with the composition, curing it, polishing the surface with #600 emery paper, and placing it in water at 37°C for 1 hour.
Soaked for a day. Thereafter, the moisture was wiped off, and measurement was performed using an Instron testing machine at 23° C. and a compression speed of 2 mm/min.

(3) Bending strength It was carried out according to IS O/D I 54049.

(4) Water absorption amount It was carried out according to JIS T6509.

The abbreviations used in the following Examples and Comparative Examples represent the following compounds, respectively.

THEIG --- Same as above R'=R2=>C
O□C112CI+□-3G-')-Co, (C■
2co2o) 30CO Aerosil RM-50 (manufactured by KK) was added to make a paste. Fill a Teflon mold for each test piece with the paste, place cellophane paper on the top, and irradiate it with visible light (a length 350-700 nm) for 30 seconds using a visible light irradiator (Translux, manufactured by Kultur). A test piece was prepared. The results are shown in Table 1.

Examples 2 to 5, Comparative Examples 1 to 2 In Example 1, poly(methacryloyloxyalkyl)isocyanurate ial and vinyl compound (b)
Example 1 was carried out in the same manner as in Example 1, except that the compounds listed in Table 1 were used in the amounts listed in Table 1.

The results are shown in Table 1.

Example 6 2.3 g of bis(methacryloyloxyethyl)hydroxyethyl isocyanurate, 2.3 g of triethylene glycol dimethacrylate, 0.0 g of benzoyl peroxide.
05g of benzoyl peroxide in paste [A] and paste CA) consisting of 5.5g of fine powder silica (manufactured by Nippon Aerosil KM, Aerosil RM-50).
．． Paste CB) was prepared using 0.02 g of Jetanol-p-)luidine instead of 0.05 g.

The pastes (A) and CB) were kneaded in equal weight and cured to prepare a test piece.

The results are shown in Table 2.

Example 7, Comparative Example 3 In Example 6, the same method as in Example 6 was conducted except that the monomers shown in Table 2 were used in the amounts shown in Table 2. The results are shown in Table 1.

Claims (1)

[Claims] (1) (a) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I a] or ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ [I b] [In the formula, X^1, X^2 and X^3 represent an acryloyl group, a methacryloyl group, a hydrogen atom or an alkyl group, and at least two of these is a (meth)acryloyl group, and R^1, R^2 and R^3 represent an oxyalkylene group or a polyoxyalkylene group. A curable resin composition for teeth comprising poly[(meth)acryloyloxyalkyl](iso)cyanurate represented by the following formula, (b) a vinyl compound, and (c) a polymerization initiator.