JP2012171956A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an improved curable composition compounded with a surfactant and water in which the surfactant is hard to deposit on exposure to the air before use, and the effect of reducing unpolymerized amount on the surface maintains stably for a long period.SOLUTION: The curable composition comprises (A) 100 pts.mass of radically polymerizable monomer, (B) 0.1-10 pts.mass of water, (C) 0.001-5 pts.mass of an anionic surfactant in which the Li ion is a counter ion, and (D) an effective amount of a radical polymerization initiator.

Description

  The present invention provides a curable composition with a reduced surface unpolymerized amount that can be suitably used for dental use that is difficult to polymerize under oxygen interruption because of little polymerization inhibition by oxygen.

  The curable material is basically a material composed of a polymerizable monomer and a polymerization initiator. When the polymerization initiator is radically polymerizable, when the polymerization step is performed in air, an unpolymerized layer is formed on the exposed surface of the cured composition. This is because oxygen in the air combines with the curable material to form peroxide radicals on the surface of the curable material exposed to air, and the polymerization proceeds. This phenomenon is particularly noticeable when the radical polymerization initiator is of a chemical polymerization type in which a plurality of components are reacted to generate radicals, because the reaction time is long and greatly influenced by oxygen in the air.

  Conventionally, in order to provide a curable material having no unpolymerized layer on the surface, the contact with air is cut off by curing in a nitrogen atmosphere or in water, or providing an oxygen barrier layer using an oxygen barrier material. A method of radical polymerization of a curable material 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). Material), composite resin, resin material surface lubricity imparting material, denture base lining material, tooth nail polish and the like. 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 treatment using such materials is often used by directly curing in the oral cavity, and it is a method of reducing unpolymerization by curing in water or in a nitrogen atmosphere. It is necessary to take it out from the mouth once, and the shape formed in the mouth 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.

  Under these circumstances, a method for reducing surface unpolymerization by a curable material containing a surfactant and water has been developed (see Patent Documents 3 to 6). According to this method, water is dispersed in a matrix composed of radically polymerizable monomers, and curing by radical polymerization is performed in a state where such water is dispersed to form a cured product. That is, since radical polymerization is performed in a state where water is dispersed together with the surfactant, an appropriate water layer (containing a surfactant) is formed on the surface of the cured body formed as the polymerization proceeds. The layer is greatly improved in surface polymerizability by presuming that the layer prevents the direct contact between the cured material and air and suppresses the direct contact between the radical polymerizable monomer and the oral mucosa. And the amount of surface unpolymerization can be significantly reduced.

  In this document, examples of the surfactant to be blended include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, and among them, anionic interfaces having ester bonds It is described that a high effect is obtained when an activator such as sodium lauryl sulfate or sodium decyl sulfate is blended.

  In addition, it is also described that by blending a surfactant into a curable composition, an effect of exhibiting high adhesive force against living hard tissues such as teeth and reducing irritation and invasion can be obtained ( (See Patent Document 7).

JP 2000-128723 A JP 2004-284969 A JP 2006-291168 A JP 2007-008972 A JP 2007-063332 A JP 2008-285645 A JP 7-316391 A

  However, in the curable composition, as the surfactant to be mixed with the radical polymerizable monomer together with water, a counter ion such as sodium lauryl sulfate or sodium decyl sulfate, which is an anionic surfactant having an ester bond, is Na. When an anionic surfactant that is an ion is used, if the material is exposed to air before use, the surfactant will precipitate at the air contact interface, and the effect of reducing the amount of surface unpolymerization will not be fully exhibited. It was happening. That is, there is no problem when the liquid of the curable composition is sealed in a container, but the surfactant is deposited in a short time if it is taken out into the cup or the container lid is forgotten to be closed. There was a problem that the effect of reducing the amount of unpolymerized surface was weakened.

  For this reason, in a curable composition containing a surfactant and water, the surfactant does not easily precipitate even when exposed to air before use, and the effect of reducing the amount of unpolymerized surface can be stably maintained for a long period of time. There was a need to improve.

  The present inventors have intensively studied to achieve the above object. As a result, the curable composition obtained by using an anionic surfactant blended with the radical polymerizable monomer and water with a counter ion of Li ion can be obtained under air exposure before use. The present inventors have found that the surfactant is hardly precipitated and can stably maintain the effect of reducing the amount of unpolymerized surface for a long period of time, and have completed the present invention.

  That is, the present invention comprises (A) 100 parts by mass of a radically polymerizable monomer, (B) 0.1 to 10 parts by mass of water, and (C) 0.1 to an anionic surfactant whose counter ion is Li ion. It is a curable composition comprising 10 parts by mass.

  Further, the present invention is mainly composed of (A) a radical polymerizable monomer, (B) water, (C) a liquid material comprising an anionic surfactant whose counter ion is Li ion, and a resin powder. A kit of a curable composition comprising a powder material is also provided.

  The curable composition of the present invention is cured in an environment where oxygen is present, in a state in which a surface unpolymerized layer is hardly generated without using a special means such as using an oxygen blocking material. The curable composition is less likely to precipitate a surfactant contained even under exposure to air, and can stably maintain the effect of reducing the amount of unpolymerized surface even after long-term storage.

  The curable composition of the present invention contains a radically polymerizable monomer, water, and an anionic surfactant whose counter ion is Li ion as essential components. The reason why the surfactant does not easily precipitate even under exposure to air and the effect of maintaining the effect of reducing the amount of unpolymerized surface over a long period of time is not necessarily clear, but the present inventors are as follows. Is estimated.

  That is, as the anionic surfactant, the sulfate ester salt that has been most commonly used in the past and also used in the prior art relating to a curable composition in which a surfactant and water are blended has a counter ion of Na ion. Is usually used. However, the Li ion (513.3 kJ / mol) has a higher first ionization energy than the Na ion (495.8 kJ / mol), so that the counter ion of the anionic surfactant is Li ion rather than Na ion. It is considered that the anionic surfactant can be brought into a stable ionic state in the curable composition when it is an ion. As a result, in a curable composition containing an anionic surfactant whose counter ion is Li ion, it is presumed that precipitation of the component is greatly suppressed even under air exposure.

  In the curable composition of the present invention, a certain amount of these anionic surfactants whose water or counter ion is Li ion is necessary to sufficiently exhibit the effect of reducing surface unpolymerization, but is too much. Even if it is too much, the strength of the cured product is lowered, or in some cases, it is not cured at all. From such a viewpoint, 0.1 to 10 parts by mass of water and 100 to 10 parts by mass of the radically polymerizable monomer contain an anionic surfactant having a counter ion of Li ion in the range of 0.1 to 10 parts by mass. It is necessary to make it. Hereinafter, each of these components will be described in detail.

  As the radical polymerizable monomer blended in the dental curable composition of the present invention, any radical polymerizable monomer that can be used for dental use can be used without any particular limitation. As such a radical polymerizable monomer, a (meth) acrylic polymerizable monomer is generally used.

  Examples of typical (meth) acrylic polymerizable monomers include those shown in the following (I) to (IV).

(I) Monofunctional monomers: Methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, acetoacetoxyethyl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid , Methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid, and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid 10-methacryloyloxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10- Taku Leroy oxy decamethylene dihydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonium acidic group-containing polymerizable monomers such as sulfonates.

(II) Bifunctional monomer (i) Aromatic compound-based 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-methacryloyloxydipropoxyphenyl) propane, 2 ( 4-Methacryloyloxydiethoxyphenyl) -2 (4-methacryl Royloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytri) Ethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate; -OH such as methacrylates such as 2-hydroxypropyl methacrylate and 3-chloro-2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates A vinyl monomer having a diisocyanate methyl benzene, diadduct and the like obtained from the addition of the diisocyanate compound having an aromatic group such as 4,4'-diphenylmethane diisocyanate.
(Ii) Aliphatic compound-based monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having an average molecular weight of 400, polyethylene glycol dimethacrylate having an average molecular weight of 600, butylene glycol dimethacrylate, neo Pentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, nonamethylenediol methacrylate, and acrylates corresponding to these methacrylates 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxy Vinyl monomers having —OH groups such as methacrylates such as 2-hydroxypropyl methacrylate or acrylates corresponding to these methacrylates, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis (4 Diadducts obtained from addition with diisocyanate compounds such as -cyclohexyl isocyanate); acrylic anhydride, methacrylic anhydride, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) ) Acidic group-containing polymerizable monomers such as phosphates.

(III) methacrylates such as trifunctional monomers trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.

(IV) Tetrafunctional monomers pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), 4, Diaducts obtained from the addition of diisocyanate compounds such as 4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  These radically polymerizable monomers may be used alone or in combination of two or more. In addition, in the dental curable composition of the present invention, in addition to the (meth) acrylic polymerizable monomer, the above-mentioned is often used for ease of polymerization, adjustment of viscosity, or adjustment of other physical properties. It is also possible to mix and polymerize other polymerizable monomers other than the (meth) acrylic polymerizable monomer. 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 be used alone or in combination of two or more.

  As the water (B) that can be used in the curable composition of the present invention, conventionally known water can be used without any limitation, but it is preferable to use water that does not substantially contain impurities. More preferably, distilled water or ion-exchanged water is used.

The blending amount of (B) water in the present invention is 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) radical polymerizable monomer. More preferably, it is 0.3-8 mass parts with respect to 100 mass parts of (A) radically polymerizable monomer, More preferably, it is 0.5-5 mass parts. (B) When the blending amount of water is less than 0.1 parts by mass with respect to 100 parts by mass of the (A) radical polymerizable monomer, the effect of reducing surface unpolymerization cannot be obtained sufficiently. When exposed to air, the surfactant is deposited in a short time. On the other hand, when the blending amount of water exceeds 10 parts by mass, mechanical properties such as bending strength of the cured body are significantly lowered.

  In the curable composition of the present invention, specific examples of the anionic surfactant (C) whose counter ion is Li ion include higher fatty acid lithium, lithium alkyl sulfate, lithium alkyl sulfonate, and lithium alkyl aryl sulfonate. It can illustrate as a suitable thing.

  Examples of the higher fatty acid lithium include lithium salts of fatty acids having 8 to 20 carbon atoms such as lithium caproate, lithium caprylate, lithium caprate, lithium laurate, lithium myristate, lithium palmitate, lithium stearate, and lithium oleate. It can be illustrated.

  Examples of the lithium alkyl sulfate include lithium hexyl sulfate, lithium octyl sulfate, lithium decyl sulfate, lithium dodecyl sulfate, lithium tetradecyl sulfate, lithium hexadecyl sulfate, lithium alkyl octadecyl sulfate, and the like.

  Examples of the lithium alkyl sulfonate include lithium hexyl sulfonate, lithium octyl sulfonate, lithium decyl sulfonate, lithium dodecyl sulfonate, lithium tetradecyl sulfonate, lithium hexadecyl sulfonate, lithium octadecyl sulfonate, and the like. Examples thereof include lithium alkyl sulfonates.

  Lithium alkylarylsulfonates include lithium hexylbenzenesulfonate, lithium octylbenzenesulfonate, lithium decylbenzenesulfonate, lithium dodecylbenzenesulfonate, lithium tetradecylbenzenesulfonate, lithium hexadecylbenzenesulfonate, and octadecylbenzenesulfonate. Examples thereof include lithium alkylarylsulfonates having 6 to 18 carbon atoms excluding an aromatic ring such as lithium.

  Among these anionic surfactants, lithium alkyl sulfate having 6 to 18 carbon atoms is preferable because it is more difficult to precipitate under exposure to air before use. Compounds are preferred.

  The anionic surfactant (C) counter ion that can be used in the present invention is not limited to these, and can be used not only alone but also in combination of a plurality of types as necessary. . Further, a surfactant other than the anionic surfactant, that is, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like may be used in combination.

  In the present invention, the amount of (C) the anionic surfactant (the counter ion is Li ion) is 0.001 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer. It is 0.01 mass part-4 mass parts with respect to 100 mass parts of radically polymerizable monomers, More preferably, it is 0.05-3 mass parts.

  (C) When the amount of the anionic surfactant whose counter ion is Li ion is less than 0.001 part by mass with respect to 100 parts by mass of the radical polymerizable monomer, the effect of reducing surface unpolymerization Can not be obtained sufficiently, and when it exceeds 5 parts by mass, mechanical properties such as bending strength of the cured product are remarkably lowered.

  In order to polymerize the radical polymerizable monomer, the curable composition of the present invention usually contains a radical polymerization initiator. The radical 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. The radical polymerization initiator used in the dental field includes a chemical polymerization type (room temperature redox initiator), a photopolymerization type, a thermal polymerization type, and the like. In consideration of curing in the oral cavity, the chemical polymerization type and / or A photopolymerization type is preferred.

  A chemical polymerization type radical polymerization initiator (chemical polymerization initiator) is composed of two or more components, and is a polymerization initiator that generates a 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, 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 type radical polymerization initiators (photopolymerization initiators), 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, 4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6- Dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzo L) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2, 6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,5,6-trimethylbenzoyl) -2,4,4- Acylphosphine oxide derivatives such as trimethylpentylphosphine oxide, diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9 , 10-F Α-diketones such as nanthrenequinone and acenaphthenequinone; benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin propyl ether; 2,4-diethoxythioxanthone, 2-chlorothioxanthone, methylthioxanthone A benzophenone derivative such as benzophenone, p, p′-dimethylaminobenzophenone, p, p′-methoxybenzophenone or the like is 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.

  In the present invention, the blending amount of the radical polymerization initiator (D) 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 a polymerization initiator or a radically polymerizable monomer. Generally, a radical polymerization initiator is 0.01-10 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 radical polymerization initiator, such as the acidic group-containing radical polymerizable monomer, the amount of the component constituting the radical polymerization initiator other than the compound is adjusted. The above range is preferable.

  The curable composition of the present invention is blended with the above (A) radical polymerizable monomer, (B) water, (C) an anionic surfactant whose counter ion is Li ion, and if necessary ( D) Arbitrary components such as radical polymerization initiators and fillers are uniformly mixed during 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.

  The dental curable composition of the present invention is used as it is as a surface lubricant or adhesive used for the purpose of imparting lubricity on the surface of various resin-based dental materials, repairing tooth nail polish and discolored teeth, etc. However, it can be used for a wider range of applications by combining with a filler. For example, when combined with organic fillers, denture repair materials, lining materials, temporary sealing materials filled in the cavity and temporary storage for a few days after returning the patient during the course of treatment It is suitably used as a material for forming an intermediate crown and 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 diameters of these fillers are not particularly limited, and fillers having an average particle diameter of 0.01 μm to 100 μm that 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 radical polymerizable monomer. Most preferably, it is in the range of 100 to 500 parts by mass.

  The dental 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. Also good. Moreover, in order to improve storage stability, it is also preferable to mix | blend a polymerization inhibitor.

Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples. In addition, the abbreviations of the compounds used in Examples and Comparative Examples shown in Examples are as follows.
[Radically polymerizable monomer]
3G; triethylene glycol dimethacrylate 14G; dimethacrylate ND of polyethylene glycol having a molecular weight of 600; 1,9-nonanediol dimethacrylate AAEM; acetoacetoxyethyl methacrylate HPr; 2-methacryloyloxyethyl propionate [radical polymerization initiator]
(Organic peroxide)
BPO; benzoyl peroxide perocta H; 1,1,3,3-tetramethylbutyl hydroperoxide (amine compound)
DEPT; N, N-diethanol-p-toluidine DMBE; ethyl dimethylbenzoate (α-diketone)
CQ: camphorquinone (aryl borate compound)
PhBTEOA; tetraphenyl boron triethanolamine salt (vanadium compound)
VOAA; vanadium oxide (IV) acetylacetonate [resin powder]
PEMA: Polyethylmethacrylate average particle size: 35 μm, weight average molecular weight: 500,000 [surfactant precipitation test]
The time from when the liquid of the curable composition was collected in a rubber cup until the surfactant was deposited in an open state in the air was visually observed. The time for which the precipitate occupies 30% of the liquid surface was defined as the deposition time. When the curable composition was the two liquid components of the first liquid and the second liquid, the average precipitation time for both was defined as the precipitation time.
[Surface unpolymerized weight measurement method]
The curable composition used was 5 minutes after collecting the liquid in a rubber cup. By filling the curable composition prepared in each Example or Comparative Example into a polyacetal mold having holes with a diameter of 50 mm and a thickness of 1 mm, and leaving it in a constant temperature bath at 37 ° C. for 15 minutes. Curing was performed. However, in Example 23 and Comparative Example 8, curing was performed by performing light irradiation for 30 seconds with a visible light irradiator (manufactured by Tokuyama Corporation, Powerlight).

Thereafter, the surface of the obtained cured product was washed with ethanol to remove the unpolymerized layer. The weight obtained by subtracting the weight of the cured product from which the unpolymerized layer was removed from the weight of the cured material filled in the mold was determined as the unpolymerized amount, and the weight per surface area was obtained.
[Bending strength measurement method]
The curable composition used was 5 minutes after collecting the liquid in a rubber cup. The curable composition was filled in 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 three-point bending test was performed by 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 to determine the bending strength.
Example 1
Evaluation was performed using 3G as a radical polymerizable monomer. That is, 3 parts by mass of 3 G of 100 parts by mass of 3G of 3 parts by weight of water, 1.5 parts by weight of lithium laurate, and 1.5 parts by weight of DEPT were mixed. Part of water, 1.5 parts by weight of lithium laurate and 3 parts by weight of BPO were mixed. About the dental curable composition which consists of this 1st liquid and 2nd liquid, the precipitation test of surfactant was done.

  Next, the first liquid and the second liquid were weighed and mixed so as to have a mass ratio of 104.5: 107, and the surface unpolymerized weight measurement and bending strength measurement were performed.

As a result, the deposition time of the surfactant was 10.5 minutes, the surface unpolymerized amount was 15.6 μg / mm ² , and the bending strength was 80.2 MPa.
Examples 2 to 24, Comparative Examples 1 to 9
The dental curable composition prepared in the same manner as in Example 1 was evaluated. The composition (amount is parts by mass) and the results are shown in Table 1.

  Moreover, the comparative test of the dental composition (amount is a mass part) each prepared by the method similar to Example 1 as another comparison object was done. The composition and results are shown in Table 2.

  In Examples 2 to 24, each component was blended so as to satisfy the constitution shown in the present invention, but the surfactant deposition time, surface unpolymerized weight, and bending strength were all good values. was gotten.

  On the other hand, Comparative Examples 1 and 2 are cases where an anionic surfactant whose counter ion is Na ion is used as the surfactant, but in any case, the deposition time of the surfactant is accelerated, The amount of unpolymerized surface also increased.

  Further, Comparative Example 3 was a case where the blending amount of water was small, but the deposition time of the surfactant was quickened, and the surface unpolymerized amount was also increased.

  In Comparative Example 4, since the amount of water added was large, the strength of the cured body was low, and the bending strength was significantly reduced.

  Comparative Example 5 was a case where no surfactant was added. However, precipitation of the surfactant could not occur, but the amount of surface unpolymerization increased significantly.

  In Comparative Example 6, the surfactant was added excessively, but the deposition time of the surfactant was significantly increased, and the surface unpolymerized amount was also increased.

Comparative Examples 7 to 9 are cases where an anionic surfactant having a counter ion of Na ion was used as the surfactant. In all cases, the deposition time of the surfactant was accelerated, and the surface unpolymerized amount increased. .
Example 25
Evaluation was performed using ND and 14G as radical polymerizable monomers. That is, 70 parts by mass of ND, 30 parts by mass of 14G, 3 parts by mass of water, 1.5 parts by mass of lithium dodecylate, and 1 part by mass of DEPT, and resin powder as PMA 100 parts by mass Thus, a powder mixed with 1 part by mass of BPO was prepared. About the liquid of the dental curable composition which consists of this liquid and powder, the precipitation test of surfactant was done.

  Next, the liquid and the powder were weighed and mixed so as to have a mass ratio of 105.5: 202, and the surface unpolymerized weight measurement and bending strength measurement were performed.

As a result, the deposition time of the surfactant was 12.0 minutes, the surface unpolymerized amount was 6.7 μg / mm ² , and the bending strength was 135.1 MPa.
Example 26, Comparative Examples 10 and 11
The dental curable composition prepared in the same manner as in Example 25 was evaluated. The composition (amount is parts by mass) and the results are shown in Table 3.

  In Examples 25 and 26, each component was blended so as to satisfy the constitution shown in the present invention, but all of the precipitation of surfactant, surface unpolymerized weight, and bending strength had good values. Obtained.

  On the other hand, Comparative Examples 10 and 11 are cases where an anionic surfactant whose counter ion is Na ion is used as the surfactant. In either case, the deposition time of the surfactant is increased, The amount of unpolymerized surface also increased.

Claims (5)

  (A) 100 mass parts of radically polymerizable monomer, (B) 0.1-10 mass parts of water, (C) 0.001-5 mass parts of anionic surfactant whose counter ion is Li ion A curable composition.   The curable composition according to claim 1, further comprising (D) an effective amount of a radical polymerization initiator.   The curable composition according to claim 1 or 2, which is used for dentistry.   (A) a radical polymerizable monomer, (B) water, (C) a liquid material containing an anionic surfactant whose counter ion is Li ion, and a powder material mainly composed of resin powder Kit of curable composition.   The kit of curable composition of Claim 4 which is for dentistry.