JP2007063332A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which little forms unpolymerized layers on a surface in an oxygen-existing environment without an oxygen-blocking material, and can stably be stored even in a refrigerator. <P>SOLUTION: This curable composition comprises (A) 100 parts by mass of a radically polymerizable monomer, preferably a (meth)acrylic radically polymerizable monomer having a water absorbing capacity of not larger than 20% by weight, (B) 0.5 to 10 parts by mass of water, (C) 0.1 to 20 parts by mass of an anionic surfactant, preferably an alkyl sulfate, an alkyl benzene sulfonate, or an alkylsulfonate, (D) 0.1 to 10 parts by mass of a nonionic surfactant, and an effective amount of a polymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition. More specifically, the present invention relates to a novel curable composition in which the influence of oxygen during curing is reduced without providing an oxygen barrier layer.

  The curable composition is a material that basically includes a polymerizable monomer and a polymerization initiator. When the curable composition is radically polymerizable, when the polymerization step is performed in air, an unpolymerized layer is formed on the surface of the cured composition exposed to air. This is because oxygen in the air is combined with the curable composition to form peroxide radicals on the surface of the curable composition exposed to the air, and the progress of the polymerization is stopped.

  Conventionally, in order to provide a curable composition having no unpolymerized layer on the surface, it is cured in a nitrogen atmosphere or in water, and an oxygen barrier layer is provided by using an oxygen barrier material. A method of radically polymerizing a curable composition has been performed (see, for example, Patent Documents 1 and 2).

  The method of curing (meth) acrylate polymerizable monomers by radical polymerization is widely used in the field of dentistry. Examples of using such a method include dental cement, dental adhesive (bonding). Materials), composite resins, materials for imparting lubricity on the surface of resin dental materials, and manicures for teeth. If these dental restorations have an unpolymerized layer on the surface of the cured product, the surface hardness and colorability are lowered. Further, if there is an unpolymerized layer on the surface, the unpolymerized layer is entangled with the polishing bar when the cured body is polished and ground, so that the polishing property is lowered.

  Dental treatments using such materials are often cured directly in the oral cavity and cured in water or under a nitrogen atmosphere to reduce unpolymerization. It is necessary to take out from the oral cavity, and the shape formed in the oral cavity is deformed. There are many cases where it is difficult to form an oxygen barrier layer, and an oxygen barrier material cannot be used for a material having a low viscosity such as a bonding material.

  For this reason, the technique which reduces the influence of the oxygen at the time of hardening, without providing an oxygen interruption | blocking layer was calculated | required.

  On the other hand, it has been reported that by adding a surfactant to a radical polymerizable monomer, a curable composition with less irritation and invasion can be obtained when used as an adhesive for hard tissues such as teeth ( (See Patent Document 3). The curable composition may further contain water as a diluent solvent. In this case, first, water is applied to the teeth and dried, and then a component containing a radical polymerizable monomer and a surfactant is applied. It is used to cure. Therefore, the portion of the curable composition that is exposed to the atmosphere when cured is not a composition containing water. The document also discloses that an aqueous solution containing a surfactant is used as a primer composition, and further describes that a radical polymerizable monomer can be added thereto. However, it does not describe at all what effect can be obtained when the radically polymerizable monomer is further contained, and does not describe any experimental results corresponding to this embodiment.

  Further, in this document, examples of the surfactant used include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant in parallel. Then, only the combined system of the individual or a cationic surfactant and a nonionic surfactant has been tried. Thus, with the use of these specifically initiated surfactants, the resulting curable composition is still difficult to reduce to a high degree the effects of oxygen described above during curing, and the unpolymerized layer on the surface. The formation of can not be suppressed to a level that can be satisfied one step now. In addition, according to the additional test by the present inventors, when an anionic surfactant or the like is used as the surfactant, the curable composition is stored at refrigeration, specifically at 0 to 10 ° C. Occasionally, a phenomenon occurs in which the surfactant is precipitated, and it is difficult to stably store the surfactant for a long time.

JP 2000-128723 A JP 2004-284969 A JP 7-316391 A

  An object of the present invention is to provide a curable composition that hardly causes an unpolymerized surface on the surface even in the presence of oxygen, without using an oxygen blocking material, and that can be stably stored even in refrigeration. To do.

  The present inventors have intensively studied to achieve the above object. As a result, when a small amount of water, an anionic surfactant and a nonionic surfactant are contained in the radical polymerizable monomer, a high polymerization inhibition reduction effect is exhibited, and further, storage stability in refrigeration is improved. As a result of finding the improvement and further studying it, the present invention has been completed.

  That is, the present invention comprises (A) 100 parts by mass of a radical polymerizable monomer, (B) 0.5 to 10 parts by mass of water, (C) 0.1 to 10 parts by mass of an anionic surfactant, (D) nonion. It is a curable composition comprising 0.1 to 10 parts by mass of a surfactant and an effective amount of a polymerization initiator.

  Here, as the component (A), a radical polymerizable monomer having a water absorption of 20 wt% or less is preferable, and as the component (C), an alkyl sulfate, an alkyl benzene sulfonate, or an alkyl sulfonate is preferable. As the component D), a general nonionic surfactant can be used.

  The curable composition of the present invention highly suppresses the formation of a surface unpolymerized layer without using special means such as using an oxygen-blocking material in an environment where oxygen is present, and thus the surface of the cured body. Improves mechanical strength and durability.

  The curable composition of the present invention comprises a radical polymerizable monomer, water, an anionic surfactant, a nonionic surfactant and a polymerization initiator as essential components.

  The radical polymerizable monomer is polymerized by the action of the polymerization initiator to give a cured product. By adding both water and a surfactant to the composition, an anion is obtained when the radical polymerizable monomer is cured. It is presumed that a layer composed of a surfactant, a nonionic surfactant and water is formed on the surface, and the layer composed of the surfactant and water inhibits the entry of oxygen into the interior and reduces surface unpolymerization. In addition, by combining an anionic surfactant and a nonionic surfactant, the effect of reducing surface unpolymerization is exerted synergistically higher than when each is used alone.

  Furthermore, when an anionic surfactant was used alone, there was a problem that the anionic surfactant was precipitated by refrigerated storage as described above, but the anionic surfactant and the nonionic surfactant By combining with an agent, precipitation of the anionic surfactant during refrigeration can be suppressed well.

  The curable composition of the present invention comprises a radical polymerizable monomer, water, an anionic surfactant, a nonionic surfactant and a polymerization initiator as essential components.

  The radically polymerizable monomer is polymerized by the action of the polymerization initiator to give a cured product. By adding both water and a surfactant to this composition, the interface becomes effective when the radically polymerizable monomer is cured. It is presumed that a layer of an activator and water is formed on the surface, and the layer composed of the surfactant and water inhibits the intrusion of oxygen into the interior and reduces surface unpolymerization. However, when the amount of water and surfactant is extremely large, the strength of the cured product is reduced, or in some cases, it is not cured at all. It is necessary to set it as the range of 5-10 mass parts, 0.1-10 mass parts of anionic surfactant, and 0.1-10 mass parts of nonionic surfactant. Hereinafter, each of these components will be described in detail.

  A well-known thing can be especially used for a radically polymerizable monomer mix | blended with the curable composition of this invention without a restriction | limiting. In particular, (meth) acrylic polymerizable monomers are common in that they are excellent in polymerizability and can be easily cured even near room temperature. Further, among these radical polymerizable monomers, those having a water absorption of 20 wt% or less are preferably used.

  Such a radical polymerizable monomer that does not correspond to a radical polymerizable monomer having a water absorption of 20 wt% or less, in other words, a radical polymerizable monomer having a water absorption of more than 20 wt%, Acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethacrylate of polyethylene glycol having an average molecular weight of 400, 2-methacryloyloxyethyl dihydrogen phosphate, bis (2-methacryloyloxyethyl) hydrogen phosphate, etc. In the present invention, these radically polymerizable monomers can also be used alone.

  In the present invention, it is preferable to use a radical polymerizable monomer having a water absorption of 20 wt% or less as described above. That is, when a radically polymerizable monomer having such water absorption is used, the effect of forming a surface active agent and water layer on the surface at the time of curing is further enhanced, and the effect of reducing surface unpolymerization is further increased. improves. From the viewpoint of more prominently exhibiting the above effects, it is more preferable to use a radically polymerizable monomer having a water absorption of 15 wt% or less.

  The water absorption shown here is calculated from the value obtained by the Karl Fischer method for the water content of the radically polymerizable monomer saturated and absorbed at 23 ° C., and is given by the following equation.

Water absorption = water content (g) / weight of radical polymerizable monomer (g) × 100
The water absorbency of the radical polymerizable monomer can be easily calculated by the above-described method, but for simplicity, 100 parts by mass of the polymerizable monomer and 20 parts by mass of water are mixed, and It can be judged whether it can be used as a polymerizable monomer used for the curable composition in this invention by becoming.

  In the curable composition of the present invention, the radical polymerizable monomer may be a mixture of two or more polymerizable monomers, and in this case, the water absorption is a value in the mixture ( In the present invention, the radical polymerizable monomer mixture is also simply referred to as a radical polymerizable monomer).

  Accordingly, a radically polymerizable monomer having a high water absorption by itself, such as the hydroxyethyl methacrylate exemplified above, is combined with a radical polymerizable monomer having a low water absorption to reduce the water absorption to 20 wt% or less as a whole. Can be used in the present invention.

  On the other hand, a radical polymerizable monomer having a water absorption of more than 20 wt% such as hydroxyethyl methacrylate may be used alone or in combination with a radical polymerizable monomer having a lower water absorption. When the water absorption is 20 wt% or more, it is presumed that a water layer is not formed on the surface, but the effect of reducing surface unpolymerization cannot be obtained.

  Among the radical polymerizable monomers having a water absorption of 20 wt% or less as described above, examples of the (meth) acrylic monomer include the following compounds.

  Methyl methacrylate, ethyl methacrylate, butyl methacrylate, isopropyl methacrylate, acetoacetoxyethyl methacrylate, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] Propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2 , 2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropo) Cyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyiso) Propoxyphenyl) propane, monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3- Tandiol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, nonamethylenediol methacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate And pentaerythritol tetramethacrylate.

  Among the above compounds, 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4- Methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2-bis (4-methacryloyloxytetra) Ethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 ( 4-Methacryloyloxydie Xylphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, nonamethylenediol methacrylate and the like have a water absorption rate of far less than 5 wt%.

  These radically polymerizable monomers can be used alone or in combination of two or more. In particular, when a monofunctional monomer and a bifunctional or trifunctional or higher monomer are used in combination, the amount of unpolymerized surface can be increased by blending a large amount of the bifunctional or trifunctional or higher monomer. Apart from this, it is preferable that the finally obtained cured product can have good mechanical properties such as strength and durability.

  In addition, acrylic acid, methacrylic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 400, 2-methacryloyloxyethyl dihydrogen phosphate, bis (2-methacryloyloxyethyl) hydrogen phosphate, etc. As described above, the water absorption by itself is far higher than 20 wt% or more, but such a polymerizable monomer is also a polymerizable monomer having a low water absorption, preferably such that the water absorption is less than 5 wt%. As described above, it can be used as the polymerizable monomer used in the curable composition of the present invention by using it together with the polymerizable monomer.

  Further, in the curable composition of the present invention, in addition to the (meth) acrylic polymerizable monomer, as exemplified above, for ease of polymerization, adjustment of viscosity, or adjustment of other physical properties. It is also possible to use a mixture of other radical polymerizable monomers other than the (meth) acrylic polymerizable monomer. Of course, in this case as well, the water absorption of the radical polymerizable monomer needs to be 20 wt% or less. Examples of these other polymerizable monomers include fumaric acid esters such as monomethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene, or α- Examples include methylstyrene derivatives; allyl compounds such as diallyl terephthalate, diallyl phthalate, and diallyl diglycol carbonate. These other polymerizable monomers can also be used alone or in combination of two or more.

  The compounding quantity of the water in this invention is 0.5-10 mass parts with respect to 100 mass parts of radically polymerizable monomers. The larger the blending amount, the more the formation of the surface unpolymerized layer can be reduced. On the other hand, the smaller the blending amount, the smaller the influence on mechanical properties such as bending strength. More preferably, it is 0.5-8 mass parts with respect to 100 mass parts of radically polymerizable monomers.

  The anionic surfactant in this invention is 0.1-10 mass parts with respect to 100 mass parts of radically polymerizable monomers. The larger the amount, the more the formation of the surface unpolymerized layer can be reduced. On the other hand, the smaller the amount, the smaller the effect on the physical properties. More preferably, it is 0.3-3 mass parts with respect to 100 mass parts of radically polymerizable monomers.

  As such anionic surfactants, known ones can be used without particular limitation, but the use of those having an HLB (Hydrophilic Lipophilic Balance) of 20 or more, preferably 30 or more is the effect of the present invention. From the viewpoint of satisfactorily exhibiting good results. The upper limit of the HLB of the anionic surfactant is not particularly limited, but is generally 50 or less. Specific examples of such anionic surfactants include alkyl sulfates such as sodium decyl sulfate and sodium lauryl sulfate, alkyl sulfonates such as sodium hexanesulfonate and sodium decylsulfonate, sodium decylbenzenesulfonate, and laurylbenzene. Alkylbenzene sulfonates such as sodium sulfonate, aliphatic carboxylates such as sodium laurate, sodium stearate and sodium oleate, and alkyl ethers such as sodium lauryl ether sulfate obtained by sulfating adducts of lauryl alcohol and ethylene oxide Examples include sulfates, sulfosuccinic acid diesters such as sodium sulfosuccinate, and phosphate ester salts of higher alcohol ethylene oxide adducts.

  Of these, alkyl sulfates, alkyl sulfonates, and alkyl benzene sulfonates are more preferable, and those having 6 to 16 carbon atoms in the alkyl group are more preferable.

  The nonionic surfactant in this invention is 0.1-10 mass parts with respect to 100 mass parts of radically polymerizable monomers. The larger the amount, the more the precipitation of the anionic surfactant can be suppressed. On the other hand, the smaller the amount, the smaller the effect on the physical properties. More preferably, it is 0.3-3 mass parts with respect to 100 mass parts of radically polymerizable monomers.

  As such nonionic surfactants, known ones can be used without particular limitation. However, the use of one having an HLB of 3 or more, preferably 6 to 18 can exhibit the effect of the present invention well. It is preferable from the viewpoint. Such nonionic surfactants preferably have a polyoxyethylene group as a hydrophilic group. Specific examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylenes such as polyoxyethylene lauryl phenyl ether. Examples thereof include fatty acid polyoxyethylene esters such as ethylene alkylphenyl ether and fatty acid polyoxyethylene lauryl ester, and polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan lauryl ester.

  By using these surfactants together with water, when the radical polymerizable monomer is polymerized by the action of the polymerization initiator, the effect of inhibiting the penetration of oxygen into the interior is exhibited, and the surface unpolymerized amount is reduced. Reduced. The effect of reducing the surface unpolymerization is exerted highly synergistically by using the surfactant in combination with an anionic surfactant and a nonionic surfactant. Furthermore, when the anionic surfactant is used alone, the problem of precipitation of the anionic surfactant during refrigerated storage, which is remarkably expressed, is also caused by the anionic surfactant and the nonionic surfactant. By using in combination, it is satisfactorily suppressed.

  In the curable composition of the present invention, a polymerization initiator for polymerizing the radical polymerizable monomer is blended. The polymerization initiator can be used without any limitation as long as it can polymerize and cure the radical polymerizable monomer to be used, and a known polymerization initiator can be used. As polymerization initiators used in the dental field, there are chemical polymerization initiators (room temperature redox initiators), photopolymerization initiators, thermal polymerization initiators, etc., but taking into account curing in the oral cavity, chemical polymerization initiators And / or a photoinitiator is preferable.

  The chemical polymerization initiator is a polymerization initiator that is composed of two or more components and generates polymerization active species near room temperature by mixing all the components immediately before use. Such chemical polymerization initiators are typically amine compound / organic peroxide type.

  Specific examples of the amine compound include aromatic amine compounds such as N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N, N-diethanol-p-toluidine.

  As typical organic peroxides, organic peroxides classified into known ketone peroxides, peroxyketals, hydroperoxides, diaryl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates are preferable. .

  More specifically, examples of ketone peroxides include methyl ethyl ketone peroxide, cyclohexanoperoxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide. Peroxyketals include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) 3,3,5-trimethylcyclohexanone, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclodecane, 2,2-bis (t-butyl Peroxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane and the like. Hydroperoxides include P-methane hydroperoxide, diisopropylbenzene peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydro A peroxide etc. are mentioned. Dialkyl peroxides include α, α-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, and t-butylcumi. Examples include ruperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane-3, and the like. Diacyl peroxides include isobutyryl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinic acid peroxide. Examples thereof include oxides, m-toluoyl benzoyl peroxide, and benzoyl peroxides. Peroxycarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di- Examples include 2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, and the like.

  Peroxyesters include α, α-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1- Cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl Peroxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , T-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3.5 , 5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylper Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-m-toluoylbenzoate , T-butylperoxybenzoate, bis ( - butylperoxy) isophthalate.

  Further, t-butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and the like can also be used as suitable organic peroxides.

  The organic peroxide to be used may be appropriately selected and used, and it may be used alone or in combination of two or more. Among them, hydroperoxides, ketone peroxides, peroxyesters and diacyl Peroxides are particularly preferred from the viewpoint of polymerization activity. Furthermore, among these, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 60 ° C. or higher from the viewpoint of storage stability when a curable composition is used.

  A system obtained by further adding a sulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid and its salt to an initiator system comprising the organic peroxide and the amine compound, and a barbituric acid system such as 5-butylbarbituric acid Even if an initiator is blended, it can be used without any problem.

  An aryl borate compound / acidic compound polymerization initiator that utilizes the fact that an aryl borate compound is decomposed by an acid to generate a radical can also be used.

  The aryl borate compound is not particularly limited as long as it is a compound having at least one boron-aryl bond in the molecule, and known compounds can be used, but among them, three in one molecule are considered in view of storage stability. Alternatively, an aryl borate compound having four boron-aryl bonds is preferably used, and an aryl borate compound having four boron-aryl bonds is more preferable from the viewpoint of easy handling, synthesis, and availability.

  As borate compounds having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyltris (3, 5-bistrifluoromethyl) phenylboron, monoalkyltris [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, monoalkyltris ( p-nitrophenyl) boron, monoalkyltris (m-nitrophenyl) boron, monoalkyltris (p-butylphenyl) boron, monoalkyltris (m-butylphenyl) boron, monoalkyltris (p-butyloxyphenyl) Boron, monoalkyltris (m-butyloxy Phenyl) boron, monoalkyltris (p-octyloxyphenyl) boron, monoalkyltris (m-octyloxyphenyl) boron (in any compound, alkyl is n-butyl, n-octyl or n-dodecyl) ), Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butyl A pyridinium salt, a methyl quinolinium salt, an ethyl quinolinium salt, a butyl quinolinium salt, etc. can be mentioned.

  Moreover, as a borate compound having four boron-aryl bonds in one molecule, tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) Phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m -Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyloxy) Phenyl) boron, tetrakis (m-o Tiloxyphenyl) boron (wherein alkyl represents any of n-butyl, n-octyl or n-dodecyl in any compound), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt Tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. Can be mentioned.

  Two or more of these aryl borate compounds may be used in combination.

As the acidic compound, an acidic group-containing radical polymerizable monomer can be preferably used, and at least one acidic group in one molecule, or an acid anhydride structure in which two of the acidic groups are condensed by dehydration, or an acidic group Any known compound may be used as long as it has an acid halide group in which the hydroxyl group is substituted with a halogen and at least one radically polymerizable unsaturated group. Here, the acidic group refers to a group in which an aqueous solution or aqueous suspension of a radical polymerizable monomer having the group exhibits acidity. Examples of the acidic group include a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphinico group {═P (═O) OH}, a phosphono group {—P (═O) (OH) ₂ }, and the like. In addition, examples in which these groups are acid anhydrides or acid halides are exemplified. Specific examples of such an acidic group-containing radical polymerizable monomer are as exemplified in the radical polymerizable monomer in the present invention.

  In addition, it is also preferable to use a combination of an organic peroxide and / or a transition metal compound in addition to such an aryl borate compound / acidic compound polymerization initiator. The organic peroxide is as described above. The transition metal compound is preferably a + IV and / or + V vanadium compound. Specific examples of the + IV and / or + V vanadium compounds include divanadium tetraoxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis ( 1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V), etc. A vanadium compound is mentioned.

  As photopolymerization initiators, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphinate Ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenyl Phosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine Side, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2 Acyl such as 1,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide Phosphine oxide derivatives, diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9,10-phenanthrenequinone , Acenaphthene Α-diketone such as non; benzoin alkyl ether such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether; thioxanthone derivatives such as 2,4-diethoxythioxanthone, 2-chlorothioxanthone and methylthioxanthone; benzophenone , Benzophenone derivatives such as p, p′-dimethylaminobenzophenone and p, p′-methoxybenzophenone are preferably used.

  These photopolymerization initiators may be used alone or in combination of two or more. Among the above photopolymerization initiators, α-diketones are preferable from the viewpoints of good polymerization activity and low harm to the living body. When α-diketone is used, it is preferably used in combination with a tertiary amine compound. Tertiary amine compounds that can be used in combination with α-diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline. N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N- Dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl Ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p Toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β -Naphtylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N- Examples include dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol.

  Each of the above polymerization initiators can be used not only alone but also in combination of a plurality of types as required.

  In the present invention, the blending amount of the polymerization initiator is not particularly limited as long as it is an amount capable of polymerizing the radical polymerizable monomer and curing the curable composition of the present invention. What is necessary is just to select a well-known compounding quantity suitably according to the kind of polymerizable monomer. Generally, a polymerization initiator is 0.01-30 mass parts with respect to 100 mass parts of radically polymerizable monomers, Preferably it is 0.1-5 mass parts. However, when a radical polymerizable compound is used as one component of the polymerization initiator like the acidic group-containing radical polymerizable monomer, the amount of the component constituting the polymerization initiator other than the compound is within the above range. It is preferable that

  The curable composition of the present invention can be used as it is as a surface lubricant or an adhesive used for the purpose of imparting lubricity on the surface of various resin-based dental materials, repairing tooth nail polish and discolored teeth. However, it can be used for a wider range of applications by combining with a filler. For example, when combined with an organic filler, a denture repair material, a back layer material, a temporary sealing material filled in the cavity for several days after returning the patient once during the course of treatment, and It is preferably used as a temporary crown and a material for producing a bridge. When combined with an inorganic filler, it is suitably used as a dental restorative material such as a composite resin, hard resin, inlay, onlay, and crown.

  Specific examples of typical fillers that can be suitably used include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, and crosslinked poly as organic fillers. Examples include ethyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-styrene-butadiene copolymer, which are used as one kind or a mixture of two or more kinds. be able to.

  Specific examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Further, among the inorganic fillers, examples of the cation-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass. These may be used alone or in combination of two or more.

  In some cases, a granular organic-inorganic composite filler obtained by adding a polymerizable monomer to these inorganic fillers in advance to form a paste, polymerizing, and pulverizing is used.

  The particle size of these fillers is not particularly limited, and fillers having an average particle size of 0.01 μm to 100 μm, which are generally used as dental materials, can be appropriately used depending on the purpose. Moreover, the refractive index of a filler is not specifically limited, The thing of the range of 1.4-1.7 which a general dental filler has can be used without a restriction | limiting.

  Furthermore, when spherical inorganic fillers are used among the above-mentioned fillers, the surface smoothness of the obtained cured product is increased, and an excellent restoration material can be obtained.

  It is desirable to treat the above-mentioned inorganic filler with a surface treating agent typified by a silane coupling agent in order to improve the compatibility with the polymerizable monomer and improve the mechanical strength and water resistance. The surface treatment method may be performed by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, Vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used.

  The proportion of these fillers may be appropriately determined in consideration of the viscosity (operability) when mixed with the polymerizable monomer and the mechanical properties of the cured product, depending on the purpose of use. , 50 to 1500 parts by weight, preferably 70 to 1000 parts by weight, based on 100 parts by weight of the polymerizable monomer.

  The curable composition of the present invention may be further blended with coloring materials such as pigments and fluorescent pigments in order to match the color tone of teeth and gums, or an ultraviolet absorber may be added to prevent discoloration against ultraviolet rays. . Moreover, in order to improve storage stability, it is also preferable to mix | blend a polymerization inhibitor.

  The curable composition of the present invention comprises (A) a radical polymerizable monomer, (B) water, (C) an anionic surfactant, (D) a nonionic surfactant, (E) a radical polymerization initiator. , And optional components such as a filler to be blended as necessary are uniformly mixed at the time of use. Here, the term “uniform” refers not only to a state in which all components are dissolved alternately, but also to a state in which water is emulsified in a radical polymerizable monomer or a state in which an insoluble component such as a filler is dispersed, The uniformity may be such that phase separation or the like cannot be confirmed with the naked eye. In consideration of storage stability and the like, it may be divided into two or more until just before use.

  Such a curable composition may be produced according to a known method and is not particularly limited.

  Moreover, the curable composition of this invention can be utilized not only for a dental use but for general industry.

  EXAMPLES Hereinafter, although an Example is given and this invention is shown concretely, this invention is not restrict | limited at all by these Examples.

  The compounds used in Examples and Comparative Examples and their abbreviations are shown below.

[Anionic surfactant]
SLS; sodium lauryl sulfate HLB40
SDS; sodium decyl sulfate HLB41
SOS; sodium octane sulfonate LBS; sodium laurylbenzene sulfonate

[Cationic surfactant]
LTMACl; Lauryltrimethylammonium chloride HLB11

[Nonionic surfactant]
POEL4; polyoxyethylene (4) lauryl ether HLB10
POEL10; polyoxyethylene (10) lauryl ether HLB14
POEO2; polyoxyethylene (2) oleyl ether HLB8
POEO7; polyoxyethylene (7) oleyl ether HLB11
POEO15; polyoxyethylene (15) oleyl ether HLB16

[Radically polymerizable monomer]
AAEM; acetoacetoxyethyl methacrylate HD; 1,6-hexanediol dimethacrylate 3G; triethylene glycol dimethacrylate HEMA; hydroxyethyl methacrylate

[Polymerization initiator]
(Organic peroxide)
BPO: Benzoyl peroxide (amine compound)
DMPT; N, N-dimethyl-p-toluidine

(Water absorption measurement method)
The polymerizable monomer was mixed with water at 23 ° C., and the water content of the saturated polymerizable water-absorbing radical polymerizable monomer was measured by Karl Fischer (MODEL CA-02, manufactured by Mitsubishi Chemical Corporation).

[Method for measuring the amount of unpolymerized surface]
The curable composition was filled into a polyacetal mold having a hole with a diameter of 5 mm and a thickness of 1 mm, and allowed to cure in a constant temperature bath at 37 ° C. for 15 minutes. Thereafter, the unpolymerized layer was removed with ethanol. The weight obtained by subtracting the weight of the cured product after removing the unpolymerized portion with ethanol from the initially filled weight was determined as the unpolymerized amount, and the weight per surface area was obtained.

[Bending strength measurement method]
The curable composition was filled into a polyacetal mold having a rectangular hole having a width of 4 mm, a thickness of 2 mm, and a length of 40 mm, and allowed to cure in a constant temperature bath at 37 ° C. for 15 minutes. A bending strength was obtained by performing a three-point bending test with a strength tester (manufactured by Shimadzu Corporation, Autograph) under the conditions of a crosshead speed of 1 mm / min and a span distance of 15 mm.

[Storage stability test]
The sample was stored in a refrigerator at 4 ° C. for 1 week, and the precipitation of the surfactant from the sample was examined and evaluated in the following two stages.
Surfactant is not deposited ○
Surfactant is deposited ×
Example 1
Evaluation was performed using 3G having a water absorption of 1.7 wt% as the radical polymerizable monomer. That is, 100 parts by weight of 3G, 3 parts by weight of water, 1.5 parts by weight of SLS, 1.5 parts by weight of POEL4, and 3 parts by weight of BPO were mixed with 100 parts by weight of 3G. A second liquid prepared by mixing 3 parts by mass of water, 1.5 parts by mass of SLS, 1.5 parts by mass of POEL4 and 1.5 parts by mass of DMPT was prepared. The first liquid and the second liquid were weighed and mixed so as to have a mass ratio of 109: 107.5 and evaluated. As a result, the surface unpolymerized amount was 3 μg / mm ² , and the bending strength of the cured body was 80 MPa. In addition, precipitation of the surfactant was not observed in the storage stability test.

Examples 2-8
A sample was prepared in the same manner as in Example 1 except that the type of surfactant used was changed as described in Table 1, and the surface unpolymerized amount and storage stability were evaluated. The results are also shown in Table 1.

Comparative Example 1
The radical polymerizable monomer 3G was cured using a polymerization initiator composed of BPO and DMPT without blending any of water and surfactant. As a result, the surface unpolymerized amount was 730 μg / mm ² . The bending strength of the cured body was 83 MPa.

Comparative Examples 2-11
A cured product was prepared and evaluated in the same manner as in Example 1 so as to have the composition shown in Table 1. Table 1 shows the unpolymerized amount of the surface and the evaluation results of the storage stability test.

Example 9
Evaluation was performed in the same manner as in Example 1 except that HD having a water absorption of 0.1 wt% was used as the radical polymerizable monomer. As a result, the amount of unpolymerized surface was 5 μg / mm ² .

Comparative Example 12
The radical polymerizable monomer HD was cured using a polymerization initiator composed of BPO and DMPT without blending any of water and surfactant. As a result, the surface unpolymerized amount was 512 μg / mm ² .

Comparative Examples 13 and 14
A cured product was prepared and evaluated in the same manner as in Example 9 so as to have the composition shown in Table 2. Table 2 shows the unpolymerized amount of the surface and the evaluation results of the storage stability test.

Example 10
As the radical polymerizable monomer, a mixture of 70 parts by mass of AAEM and 30 parts by mass of HEMA was prepared. The water absorption of this polymerizable monomer mixture was measured and found to be 10.3 wt%. When a cured product was prepared and evaluated in the same manner as in Example 1 except that this was used in place of 3G, the surface unpolymerized amount was 8 μg / mm ² . In addition, precipitation of the surfactant was not observed in the storage stability test.

Examples 11-13, Comparative Examples 15-17
A cured product was prepared and evaluated in the same manner as in Example 1 using a polymerizable monomer mixture of AAEM and HEMA so as to have the composition shown in Table 2. Table 2 shows the water absorption of the polymerizable monomer mixture, and the evaluation results of the surface unpolymerized amount and storage stability.

Examples 14 and 15, Comparative Examples 18 and 19
A cured product was prepared and evaluated in the same manner as in Example 1 except that the blending amount of water was changed so that the composition shown in Table 3 was obtained. The evaluation results of the surface unpolymerized amount, bending strength, and storage stability are shown in Table 3 together with the results of Example 1.

Examples 16 and 17, Comparative Examples 20 and 21
A cured product was prepared and evaluated in the same manner as in Example 1 except that the amount of the anionic surfactant was changed so as to obtain the composition shown in Table 4. The evaluation results of the surface unpolymerized amount, bending strength, and storage stability are shown in Table 4 together with the results of Example 1.

Examples 18 and 19, Comparative Examples 22 and 23
A cured product was prepared and evaluated in the same manner as in Example 1 except that the amount of the nonionic surfactant was changed so as to obtain the composition shown in Table 5. The evaluation results of the surface unpolymerized amount, bending strength, and storage stability are shown in Table 5 together with the results of Example 1.

Claims (5)

  (A) radically polymerizable monomer 100 parts by mass, (B) water 0.5-10 parts by mass, (C) anionic surfactant 0.1-10 parts by mass, (D) nonionic surfactant 0 A curable composition comprising 1 to 10 parts by mass and an effective amount of a polymerization initiator.   The curable composition according to claim 1, wherein the radically polymerizable monomer (A) has a water absorption of 20 wt% or less.   (C) The curable composition according to claim 1 or 2, wherein the anionic surfactant is an alkyl sulfate, an alkyl benzene sulfonate, or an alkyl sulfonate.   The curable composition according to any one of claims 1 to 3, which is cured in a state where at least a part of the surface is opened to an atmosphere containing oxygen.   The curable composition according to claim 1, 2, or 3, which is used for dentistry.