JP2009144054A - Polymerizable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition which has the storage stability better than that of a conventional composition using a combination of a copper compound, cumene hydroperoxide and N-acetylthiourea, and has a suitable curing time. <P>SOLUTION: The polymerizable composition includes tert-butylhydroperoxide as an peroxdie, a thiourea derivative as a reducing substance, and a vanadium compound as an accelerator. Preferably, the thiourea derivative is of one or more kinds selected from ethylene thiourea, diethylthiourea, tetramethylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea, and the vanadium compound is of one or more kinds selected from vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate and vanadium benzoyl acetonate. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention particularly relates to a polymerizable composition used for tooth treatment.

  The present invention relates to a polymerizable composition in which two or more liquids or pastes are mixed and polymerized. More specifically, the present invention relates to a polymerizable composition that does not gel when the paste before polymerization is stored for a long time without refrigeration, and that the curing time is not delayed or accelerated by storage. The polymerizable composition can be used as various industrial adhesives and molding resins, and one particularly suitable application is dental use.

  As a means for polymerizing a polymerizable composition containing monomers, oligomers and prepolymers such as methacrylates and acrylates having radical polymerizability at room temperature, an organic peroxide-aromatic tertiary amine is combined as a chemical polymerization catalyst. The means used has been used for a long time. In this means, the amount of the organic peroxide and the aromatic tertiary amine to be blended in the paste-like composition is adjusted and the polymerization curing time is adjusted by using a polymerization inhibitor in combination, or the composition before polymerization is adjusted. Increases storage stability. However, there is a problem that the cured product after polymerization is discolored with time due to the aromatic tertiary amine. Furthermore, organic peroxide is an unstable substance. If a large amount of organic peroxide is added to the paste composition, the paste composition itself is likely to gel before polymerization when stored for a long time. In order to ensure storage stability for a long period of time, if a large amount of a polymerization inhibitor is added to the paste composition, there has been a problem that the polymerization curing time becomes remarkably long. For this reason, it has been necessary to take measures such as refrigerated storage of the conventional polymerizable composition to delay the reaction of the organic oxide.

Some compositions use a combination of an organic aromatic compound containing at least one —SO ₂ — group, a peroxide, and an aromatic tertiary amine, but use an organic peroxide-aromatic tertiary amine. Therefore, the problem of discoloration of the cured product and low storage stability cannot be solved.

  A polymerization means using oxidation of trialkylborane is also known, but since trialkylborane is more easily oxidized than aromatic tertiary amines, it is polymerizable containing radically polymerizable (meth) acrylate. The disadvantage is that it cannot be pre-mixed in the composition. For this reason, the trialkylborane must be stored in a container different from (meth) acrylate and added to the polymerizable composition at the time of use, and the operation is complicated.

  The present applicant has developed a polymerizable composition containing a ternary catalyst of pyrimidinetrione derivative-organohalogen compound-organometallic compound, and applied for the composition (see Patent Document 1). Since this composition does not contain an amine, the cured product is not colored and can be used even under acidic conditions. However, this system has a problem in the storage stability of pyrimidinetrione derivatives.

  In addition, a combination of cumene hydroperoxide and a thiourea derivative is also disclosed (for example, see Patent Document 2). This system is characterized by high thermal stability compared to conventional systems. However, the composition using this system has a problem that the curing reaction of cumene hydroperoxide and the thiourea derivative is slow, and even if their blending concentration is sufficient, it is not particularly suitable for use as an adhesive.

  As an improvement, there is a combination of cumene hydroperoxide and N-acetylthiourea as a redox reaction in the presence of a copper compound (see, for example, Patent Document 3). This system has a relatively high heat stability and does not contain an aromatic tertiary amine, so that there is no color change over time after curing. And it is the characteristics that it is not received by the acid of the (meth) acrylate which has the acid group currently mix | blended in order to provide adhesiveness to a composition, and the storage stability of a composition is good. However, especially in the case of dental materials, when a dental prosthesis is bonded to a tooth, it is required that the characteristics and the curing time to be properly cured in the time desired by the operator are constant depending on the product. It still cannot meet the required curing time stability.

JP 2003-105008 A JP 58-219281 A JP 2007-056020 A

  Therefore, the present invention has better storage stability than a composition using a combination of a conventional copper compound, cumene hydroperoxide, and N-acetylthiourea, and the polymerization curing time is delayed by the storage from the time of product design. It is an object of the present invention to provide a polymerizable composition that does not become premature.

  As a result of intensive studies to solve the above problems, the present inventors have obtained excellent curability when tert-butyl hydroperoxide as a peroxide, a thiourea derivative as a reducing substance, and a vanadium compound as an accelerator, and The present invention was completed by finding that a polymerizable composition having excellent storage stability was obtained.

  That is, the present invention provides a first component containing tert-butyl hydroperoxide as a peroxide substance in (meth) acrylate, a second component containing a thiourea derivative as a reducing substance and vanadium compound as a polymerization accelerator in (meth) acrylate. A polymerizable composition comprising

  The polymerizable composition of the present invention may contain a filler component in one or both of the first component and the second component, and part or all of the (meth) acrylate has an acid group (meta ) If it is an acrylate, the adhesive effect can also be imparted to teeth, ceramics such as zirconia and alumina, which are materials for dental restorations, or alloys containing noble metals.

  The polymerizable composition according to the present invention is an excellent polymerizable composition having better storage stability than a composition using a combination of a conventional copper compound, cumene hydroperoxide and N-acetylthiourea.

  (Meth) acrylate in the present invention means various monomers, oligomers and prepolymers of acrylate or methacrylate. Specific examples of the (meth) acrylate used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxypropyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxyethyl ( (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-1,3 Di (meth) acryloxypropane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1 , 3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meta) ) Acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polybutylene glycol di (meth) acrylate Over preparative, include bisphenol A diglycidyl (meth) acrylate, these monomers or oligomers or prepolymers can be suitably used. Moreover, as a (meth) acrylate having a urethane bond, di-2- (meth) acryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, 1,3,5-tris [1,3-bis {( (Meth) acryloyloxy} -2-propoxycarbonylaminohexane] -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione, 2,2-bis-4- (3- (meta ) Acrylicoxy-2-hydroxypropyl) -phenylpropane, etc., and consists of 2,2'-di (4-hydroxycyclohexyl) propane, 2-oxypanone, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate. Urethane oligomer (meth) acrylate, 1,3-butanediol and hexamethylene diisocyanate When 2-hydroxyethyl (meth) urethane oligomer consisting of acrylates (meth) acrylate. These can be used individually or in mixture of 2 or more types.

  In the present invention, a (meth) acrylate having an acid group can also be used. One of the characteristics of tert-butyl hydroperoxide is that it is stable to (meth) acrylates having no acid group and (meth) acrylates having an acid group. The (meth) acrylate having an acid group has an effect of imparting adhesiveness to a polymerizable composition, dental materials, ceramics such as zirconia and alumina, which are materials for dental restorations, and alloys containing noble metals. The (meth) acrylate having an acid group is preferably a (meth) acrylate having a phosphate group or a carboxyl group, and a (meth) acrylate having one or more phosphate groups or carboxyl groups in one molecule is used. it can. Since the phosphoric acid group has a stronger acidity than the carboxyl group, the effect of dissolving the smear layer on the tooth surface and the demineralization of the tooth is high, and in particular, the effect of improving the high adhesion to the enamel is exhibited. Examples of the (meth) acrylate having a phosphoric acid group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydro Gen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl phenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 1,3-di (meth) Acryloylpropane-2-dihydrogen phosphate, 1,3-di (meth) acryloylpropane-2-phenylhydrogen phosphate, bis [5- {2- (meth) acryloyloxyate Aryloxycarbonyl} heptyl] hydrogen phosphate, and the like. Among these, 10- (meth) acryloyloxydecyl dihydrogen phosphate is particularly preferable from the viewpoints of adhesiveness and stability of (meth) acrylate itself. These (meth) acrylates having a phosphoric acid group may be used alone or in admixture of two or more.

  Examples of the (meth) acrylate having a carboxyl group include 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloxyethyl trimellitic anhydride, 4- (meth) acryloxydecyl trimellitic acid, 4 -(Meth) acryloxydecyl trimellitic anhydride, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 1,4-di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxy Examples thereof include ethyl maleic acid, 2- (meth) acryloyloxyethyl phthalic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid. Among these, 4- (meth) acryloxyethyl trimellitic acid and 4- (meth) acryloxyethyl trimellitic anhydride are particularly preferable from the viewpoint of adhesiveness.

  The polymerization reaction used in the polymerizable composition according to the present invention utilizes a redox reaction of tert-butyl hydroperoxide and a thiourea derivative. The first component of the present application contains tert-butyl hydroperoxide as a peroxide substance in (meth) acrylate. The second component contains a thiourea derivative as a reducing substance and a vanadium compound as a polymerization accelerator.

  The tert-butyl hydroperoxide is preferably added in an amount of 0.1 to 10% by weight in the first component, and if it is less than 0.1% by weight, the function as a redox polymerization initiator tends to be insufficient, and 10% by weight If blended in excess, the (meth) acrylate in the first component tends to be easily polymerized, and the storage stability of the composition is lowered.

  The thiourea derivative is a reducing substance for redox polymerization and is a stable substance in (meth) acrylate. The thiourea derivative is preferably contained in the second component in an amount of 0.1 to 10% by weight. If the amount is less than 0.1% by weight, the ability as a polymerization catalyst is insufficient. ) In many cases, it does not dissolve in acrylate. As thiourea derivatives, ethylene thiourea, diethyl thiourea, tetramethyl thiourea, N-acetyl thiourea, N-benzoyl thiourea, diphenyl thiourea, dicyclohexyl thiourea, etc. can be used, especially N-acetyl thiourea, N-benzoyl thiourea Is preferred.

  A vanadium compound is a polymerization accelerator for redox polymerization and is a stable substance in (meth) acrylate. The vanadium compound is preferably blended in the second component in an amount of 0.001 to 1% by weight. If it is less than 0.001% by weight, the effect as a polymerization accelerator tends to be insufficient, and if it exceeds 1% by weight, the second component appears to be colored dark green, or (meth) acrylate is stored during storage. Since there exists a possibility of making it superpose | polymerize, it is not preferable. Examples of the vanadium compound include vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, and vanadium acetylacetonate and vanadyl acetylacetonate are particularly preferable.

  The polymerizable composition according to the present invention may further contain a filler component in each component. The filler component increases the strength of the composition. For example, when used as a dental adhesive composition, there is an effect of improving the operability by making the components into a paste if necessary. Fillers include silicic anhydride, barium glass, alumina glass, potassium glass, fluoroaluminosilicate glass, synthetic zeolite, calcium phosphate, feldspar, fumed silica, aluminum silicate, calcium silicate, magnesium carbonate, hydrous silicic acid There are powders such as hydrous calcium silicate, hydrous aluminum silicate and quartz. These fillers can be combined with (meth) acrylates such as γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltri (methoxyethoxy) silane, etc. It may be surface-treated with a silane coupling agent. In addition, an organic-inorganic composite filler prepared by previously mixing the above filler with a monomer or oligomer and curing it, and then pulverizing it can also be used. These fillers can be used alone or in admixture of two or more. Among these, anhydrous silicic acid, hydrous silicic acid, hydrous calcium silicate, and hydrous aluminum silicate have an effect of preventing the polymerizable composition before polymerization from gelling even when stored for a long period of time. Needless to say, different fillers may be used for the first component and the second component used in the present invention.

  The mixing ratio of the first component and the second component of the polymerizable composition according to the present invention is preferably 10: 1 to 1:10 by weight. Outside this range, it is difficult to balance the polymerization catalysts, which may cause problems in polymerization. The polymerizable composition according to the present invention may be mixed manually by an operator using a spatula and kneaded paper, or an automixing system using a mixing tip may be used.

  Of course, a photopolymerization catalyst, an antibacterial agent, a pigment and the like that are usually used can be appropriately blended in the polymerizable composition according to the present invention as needed. In addition, water can be added to increase the reactivity of acid-reactive fillers such as fluoroaluminosilicate glass and (meth) acrylate having an acid group, and further to the properties of (meth) acrylate having an acid group. .

  The first component and the second component were prepared according to the formulation (% by weight) shown in Tables 2 to 5, and a storage stability test was performed.

Abbreviations in Tables 2 to 5 are as follows.
Bis-GMA: 2,2-bis-4- (3-methacryloxy-2-hydroxypropyl) -phenylpropane
TEGDMA: Triethylene glycol dimethacrylate
UDMA: Di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate
GDMA: 2-hydroxy-1,3-dimethacryloxypropane

MDP: 10-methacryloyloxydecyl dihydrogen phosphate
4META: 4-Methacryloxyethyl trimellitic anhydride

t-BHP: tert-butyl hydroperoxide
CHP: Cumene hydroperoxide

NATU: N-acetylthiourea
NBTU: N-benzoylthiourea

V (acac) 2: vanadyl acetylacetonate
V (acac) 3: Vanadium acetylacetonate

Cu (acac) 2: Copper acetylacetonate

SiO2: Silicon dioxide Aerosil: Fumed silica (trade name R812, manufactured by Nippon Aerosil Co., Ltd.)

  Table 1 shows the composition of the glass powder I.

<Table 1>

TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide
IA: 6-tert-butyl-2,4-xylenol
DW: Water

"Confirmation test for storage stability"
In each Example and Comparative Example, the polymerizable composition was stored at 23 ° C. and 50 ° C., and the curing time was measured after 0 (prepared), 4, 8, and 12 weeks, respectively. In a constant temperature room of 23 ± 1 ° C., 0.2 g of the first component and 0.2 g of the second component are measured on a kneaded paper and mixed uniformly by performing a kneading operation for 15 seconds using a spatula. The exothermic curve of the polymerizable composition was measured according to ISO 4029: 2000 7.6. Moreover, the reading method of hardening time was based on ISO4029: 20007.8. The results are shown in Tables 2-5.

  As is apparent from Tables 2 to 5, tert-butyl hydroperoxide-thiourea derivatives regardless of the presence or absence of (meth) acrylates having different compositions or acid groups of (meth) acrylates commonly used in dental materials -Vanadium compound initiator-based polymerization compositions have a relatively low degree of cure delay. Specifically, the curing reaction is quicker in the state (0 weeks) at the time of preparation before the start of storage than the cumene hydroperoxide-thiourea derivative-copper compound initiator system, especially as seen in Examples 4 and 5. In addition, a sufficiently short cure time occurs even with a relatively small amount of tert-butyl hydroperoxide. On the other hand, in the cumene hydroperoxide-thiourea derivative-copper compound initiator system, there is a case where the curing reaction does not occur, the curing delay is large at 50 ° C. storage, and it is also delayed at 23 ° C. storage.

<Table 2>

<Table 3>

<Table 4>

<Table 5>

Claims (4)

A first component comprising tert-butyl hydroperoxide as a peroxide in (meth) acrylate,
A polymerizable composition comprising (meth) acrylate and a second component containing a thiourea derivative as a reducing substance and a vanadium compound as a polymerization accelerator. The polymerizable composition according to claim 1, comprising a filler component in one or both of the first component and the second component. The thiourea derivative is one or more selected from ethylenethiourea, diethylthiourea, tetramethylthiourea, N-acetylthiourea, N-benzoylthiourea, diphenylthiourea and dicyclohexylthiourea. The polymerizable composition as described. The vanadium compound is one or more selected from vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, and vanadium benzoylacetonate, according to any one of claims 1 to 3. Polymerizable composition.