JP5230232B2 - Dental curable material kit - Google Patents

Description

  The present invention relates to a kit of a dental curable material useful as a room temperature polymerization resin or the like.

  In the field of dental treatment, various curable materials are used as denture base materials, dental filling restorative materials, dental adhesives and the like. For example, a room temperature polymerization resin is a material that can be used widely in dental treatment, for repairing a denture base and creating a temporary crown.

  The room-temperature polymerization resin is a liquid material composed of a powder and a constituent material of a part of a filler and a chemical polymerization radical polymerization initiator, and a constituent compound of the remainder of the radical polymerizable monomer and the chemical polymerization radical polymerization initiator. Is a material that starts and cures by radical polymerization. As a method of use, a kneading method in which a powder material and a liquid material are mixed using a stick in a container such as a rubber cup, or a liquid material is included in a brush, and the brush is attached to the powder material and attached to the brush tip. After mixing the powder material and the liquid material with a brushing method that blends the powder material and the liquid material that exudes from the brush, and makes a rough shape with the resulting mochi-shaped resin mud, after curing with a bar etc. It is generally used after shaping.

  Such a room temperature polymerization resin is widely used in the field of dentistry, and dental cement and the like are also used as a curable material having the same composition and packaging form. The chemical polymerization type radical polymerization initiator is a type of polymerization initiator that generates radicals when two or more kinds of compounds come into contact with each other.

  Since dental materials using the above-mentioned chemical polymerization type radical polymerization initiator are generally hardened in the oral cavity of a patient, it is required that heat generation during hardening is small. It is also important to control the time until the composition is cured (curing time) according to the clinical type. In order to control the exothermic temperature and the curing time, a technique for delaying the curing time by adding a polymerization inhibitor has been proposed (see Patent Document 1). When the curing time is controlled by this method, the polymerization inhibitor is used. Since the polymerization reaction proceeds at once after it is used up due to the delay of the curing time and disappears, there is no effect in reducing the heat generation during the curing.

  As a new solution to achieve both reduction in curing time and exotherm, the addition of a radical chain transfer agent as an additive reduces the heat generation temperature and adjusts the curing time without impairing its curability and physical properties. Can be achieved (see Patent Document 2). However, even if a radical chain transfer agent is added, a new problem has occurred. In other words, room temperature polymerization resin is a material that is used at various powder / liquid ratios. For example, when a cured body is obtained by pouring room temperature polymerization resin into a mold made of an impression material or plaster by an operator, an ordinary powder liquid is used. Resin mud mixed in a ratio is not suitable for casting because of its high viscosity, and it is used in a state of being easy to pour at low viscosity as a resin-rich resin mud. Thus, when a liquid containing a radical chain transfer agent is used under conditions (generally liquid-excess conditions) that deviate from the standard powder / liquid ratio, radical chain transfer is performed relative to the amount of polymerization initiator contained in the powder. The amount of the agent was excessive, and there was a drawback that the curing time was delayed beyond the assumption of the surgeon. In this case, the operator needs to wait for a long time until the resin mud is sufficiently cured, or to heat the mass of resin mud to increase the curing speed, and to cure the resin mud, Neither of them was troublesome for the surgeon.

JP-A-9-67222 JP-A-11-71220

  The present invention relates to a powder liquid type dental curable material comprising a radical polymerizable monomer, a resin powder, and a chemical polymerization type radical polymerization initiator as components. The objective is to control well without being affected by the difference in the powder-liquid ratio.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have conventionally known that a radical chain transfer agent is a liquid material containing a radical polymerizable monomer and a part of a constituent compound of a chemical polymerization type radical polymerization initiator. If the liquid material is divided into a liquid containing a radical chain transfer agent and a liquid not containing it, even if they are mixed at a liquid-to-liquid ratio, the cure is as desired by the surgeon. The inventors have conceived that it is possible to control the property and curing time. Further, when the liquid material is divided in this way, it has also been found that the storage stability of the liquid can be greatly improved depending on the type of constituent compound of the chemical polymerization type radical polymerization initiator to be coexisted, thereby completing the present invention. It came.

(式中、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子又は炭素数１〜３のアルキル基である)

That is, the present invention includes a) a radical polymerizable monomer, b) resin powder, c) a chemical polymerization radical polymerization initiator composed of a peroxide and an amine compound , and d) the following general formula (1) a kit of the dental curable material comprising a radical chain transfer agent represented in, (I) b) a resin powder and powder material comprising said peroxide, (II) a) a radical polymerizable monomer and the liquid material containing an amine compound, and (III) a) radical polymerizable monomer and d) kit dental curable material, characterized by comprising divided into the radical polymerization delay solution containing a radical chain transfer agent It is.
Further, a) a radical polymerizable monomer, b) a resin powder, c) a chemical polymerization radical polymerization initiator composed of a pyrimidinetrione derivative, an organometallic compound, and an organic halide, and d) the following general formula ( 1) a dental curable material kit comprising the radical chain transfer agent represented by 1), wherein (I) b) a powder containing resin powder, the pyrimidinetrione derivative and an organometallic compound; and (II) a) radical polymerization. A liquid material containing a polymerizable monomer and the organic halide, and (III) a radical polymerization retarding liquid containing a) a radical polymerizable monomer and d) a radical chain transfer agent. A kit of dental curable material.

(Wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

  The dental curable material kit of the present invention can control a low exothermic temperature and curing time to a desired length, and can reduce the influence of the powder / liquid ratio on the curing reaction compared to conventional kits. It is. In addition, since the operation time can be greatly shortened, there is no need to bother heating to cure the resin mud. Furthermore, these specific radical polymerization initiators can be used even when a combination of peroxide / amine or a combination of pyrimidinetrione derivative / organometallic compound / organic halide is used as a chemical polymerization type radical polymerization initiator. (II) The problem that the storage stability of the liquid material decreases, which becomes prominent when using, can be improved satisfactorily.

  Therefore, according to the present invention, there is provided an excellent kit of dental curable material that has high storage stability, can arbitrarily control the curing time, and does not delay the curing time even when the amount of liquid is excessive. Is done. This property is advantageous in a powder liquid type dental curable material that can be used by an operator by arbitrarily adjusting a powder liquid ratio, specifically, a hard lining material, a dental cement, and the like. In particular, it can be most advantageously applied to a room temperature polymerization resin.

  In the dental curable material kit of the present invention, b) resin powder is used as (I) powder material. Known resin powders can be used without limitation. Those that are familiar with the radical polymerizable monomer used as the liquid material are preferred. Specifically, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, ethylene-vinyl acetate copolymer, styrene- There are a butadiene copolymer, an acrylonitrile-styrene copolymer, an acrylonitrile-styrene-butadiene copolymer, and the like, and these can be used as one kind or a mixture of two or more kinds.

  The weight average molecular weight is not particularly limited, but generally it is preferably 5,000 to 1,000,000. Further, when the resin powder is made of a copolymer, the copolymerization ratio of each monomer unit is not particularly limited.

  The shape of the resin powder is not particularly limited, and may be irregular particles such as those obtained by ordinary pulverization, or may be spherical or substantially spherical particles. The average particle size of the resin powder is not particularly limited, but generally 0.005 to 200 microns is preferable.

  In the dental curable material kit of the present invention, a) radical polymerizable monomer is divided into (II) liquid material and (III) d) radical polymerization retarding liquid containing a radical chain transfer agent described later. Is blended. As the radical polymerizable monomer, a known (meth) acrylate polymerizable monomer is used without particular limitation. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2 -(Meth) acryloxyethyl propionate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate, 2,2-bis ((meth) acryloxy) Phenyl) propane, 2,2-bis [4- (2-hydroxy-3- (meth) acryloxyphenyl)] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2 -Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate , Trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized products, etc. Mixed seeds or two or more It may be used Te. In the (II) liquid material and (III) retardation liquid, the radical polymerizable monomers contained in each member may be the same or different.

  The radical polymerization initiator used in the present invention is of a chemical polymerization type comprising a combination of two or more compounds and generating radicals by contacting them. In the dental curable material kit of the present invention, each component compound of the chemical polymerization type radical polymerization initiator is an embodiment in which radicals are not generated during storage, and the (I) powder material, (II) liquid material, and (III) ) It is contained separately for any radical polymerization retarding solution.

  Examples of such a chemical polymerization type radical polymerization initiator include a combination of a peroxide and an amine compound that is a curing accelerator. Specific examples of the peroxide include dibenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and dilauroyl peroxide. As the amine compound, a secondary or tertiary amine in which an amine is bonded to an aryl group is preferably used. Examples thereof include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, p-tolyldiethanolamine and the like. The mixing ratio of the peroxide and the curing accelerator in the curable material is preferably in the range of 0.1 to 5 parts by mass of the amine compound with respect to 1 part by mass of the peroxide. As a combination of peroxide and amine compound, when (II) liquid material contains peroxide, (II) liquid material is easily gelated and cured by thermal decomposition of the peroxide, resulting in storage stability. It is preferable that the peroxide is contained in the powder material (I), and the amine compound is contained in the liquid material (II) because it becomes lacking.

  Another example of the chemical polymerization type radical initiator includes a combination of a borate compound and an acid. As the borate compound, those having at least one boron-aryl bond in one molecule are preferable from the viewpoint of storage stability.

  Specific examples of suitably used aryl borate compounds include borate compounds having one aryl group in one molecule (hereinafter also referred to as monoaryl borate): trialkylphenyl boron, trialkyl (p -Chlorophenyl) boron, trialkyl (p-fluorophenyl) boron, trialkyl (m-butylphenyl) boron, sodium salt, potassium salt, tetrabutylammonium salt of ethyl, trialkyl (m-butyloxyphenyl) boron, ethyl A pyridinium salt etc. can be mentioned. Here, specific examples of the alkyl group include an n-butyl group, an n-octyl group, and an n-dodecyl group.

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenyl boron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (m-butylphenyl) boron, and dialkyldi ( m-butyloxyphenyl) boron sodium salt, potassium salt, tetrabutylammonium salt, ethylpyridinium salt and the like. In addition, as an alkyl group in these compounds, the thing similar to the alkyl group in a monoaryl borate is illustrated.

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltri (p -Butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, sodium salt, potassium salt, tetrabutylammonium salt, ethylpyridinium salt of monoalkyltri (m-butyloxyphenyl) boron and the like. In addition, as an alkyl group in these compounds, the thing similar to the alkyl group in a monoaryl borate is illustrated.

  Examples of borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-butyl). Phenyl) boron, tetrakis (m-octyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (m-butyloxyphenyl) triphenylboron, (m-octyloxy) Examples thereof include sodium salt, potassium salt, tetrabutylammonium salt, and ethylpyridinium salt of phenyl) triphenylboron.

  These borate compounds can be used alone or in combination.

  The acid is not particularly limited, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid, maleic acid, citric acid, malonic acid, oxalic acid, propanesulfonic acid, benzenesulfonic acid and toluenesulfonic acid Can be used.

  The blending ratio of the borate compound and the acid in the curable material is preferably in the range of 0.5 to 100 parts by mass with respect to 1 part by mass of the borate compound. The combination of the borate compound and the acid has a poor storage stability when the borate compound as the starting radical source coexists with the radical polymerizable monomer. Therefore, the borate compound is contained in (I) the powder material, Is preferably contained in the liquid material (II).

  Furthermore, as a particularly preferable example of the chemical polymerization type radical initiator, a combination of a pyrimidinetrione derivative, an organometallic compound and an organic halide can be exemplified. This chemical polymerization type radical initiator is difficult to discolor after curing, and is particularly preferable as a chemical polymerization type radical initiator when the curable composition of the present invention is used for the purpose of a dental restorative material.

  Pyrimidinetrione derivatives include 5-methylpyrimidinetrione, 5-ethylpyrimidinetrione, 5-propylpyrimidinetrione, 5-butylpyrimidinetrione, 5-isobutylpyrimidinetrione, 1,5-dimethylpyrimidinetrione, 1,5-diethylpyrimidine Trione, 1-methyl-5-ethylpyrimidinetrione, 1-ethyl-5-methylpyrimidinetrione, 1-methyl-5-butylpyrimidinetrione, 1-ethyl-5-butylpyrimidinetrione, 1-methyl-5-isobutylpyrimidine Trione, 1-ethyl-5-isobutylpyrimidinetrione, 1-methyl-5-cyclohexylpyrimidinetrione, 1-ethyl-5-cyclohexylpyrimidinetrione, 1-benzyl-5-phenylpyrimidinetrione 1,3,5-trimethylpyrimidinetrione, 1,3-dimethyl-5-ethylpyrimidinetrione, 1,3-dimethyl-5-butylpyrimidinetrione, 1,3-dimethyl-5-isobutylpyrimidinetrione, 1,3 5-triethylpyrimidinetrione, 1,3-diethyl-5-methylpyrimidinetrione, 1,3-diethyl-5-butylpyrimidinetrione, 1,3-diethyl-5-isobutylpyrimidinetrione, 1.3-dimethyl-5 Phenylpyrimidinetrione, 1.3-diethyl-5-phenylpyrimidinetrione, 1-ethyl-3-methyl-5-butylpyrimidinetrione, 1-ethyl-3-methyl-5-isobutylpyrimidinetrione, 1-methyl-3- Propyl-5-ethylpyrimidinetrione, 1-ethyl-3- Propyl-5-methylpyrimidinetrione, 1-cyclohexyl-5-methylpyrimidinetrione, 1-cyclohexyl-5-ethylpyrimidinetrione, 5-butyl-1-cyclohexylpyrimidinetrione, 5-sec-butyl-1-cyclohexylpyrimidinetrione, Examples include 1-cyclohexyl-5-hexylpyrimidinetrione, 1-cyclohexyl-5-octylpyrimidinetrione, 1,5-dicyclohexylpyrimidinetrione, and the like. Among these, a pyrimidinetrione derivative in which hydrogen bonded to a nitrogen atom is substituted with an alkyl group or a cycloalkyl group is particularly preferable from the viewpoint of solubility in a radical polymerizable monomer and radical polymerization activity.

  Specific examples of organometallic compounds include copper acetylacetone, copper 4-cyclohexylbutyrate, cupric acetate, copper oleate, manganese acetylacetone, manganese naphthenate, manganese octylate, acetylacetone cobalt, cobalt naphthenate, lithium acetylacetone, and lithium acetate. Zinc acetylacetone, zinc naphthenate, nickel acetylacetone, nickel acetate, acetylacetone aluminum, acetylacetone calcium, acetylacetone chromium, acetylacetone iron, sodium naphthenate, rare earth octoate and the like. These organometallic compounds can be used alone or in admixture of two or more.

  The organic halide is not particularly limited as long as it is a compound that forms halide ions in a solution, and a known compound can be used. Suitable halogen ion forming compounds include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, diisobutylamine hydrochloride, tetra-n-butylammonium chloride, triethylamine hydrochloride, trimethylamine hydrochloride, dimethylamine hydrochloride. Chloride, diethylamine hydrochloride, methylamine hydrochloride, ethylamine hydrochloride, isobutylamine hydrochloride, triethanolamine hydrochloride, β-phenylethylamine hydrochloride, acetylcholine chloride, 2-chlorotrimethylamine hydrochloride, (2-chloroethyl Triethylammonium chloride, tetra-decyldimethylbenzylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, trioctylmethylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, dilauryldimethylammonium bromide, tetrabutylammonium bromide, Examples thereof include benzyltriethylammonium bromide, and these may be used alone or in combination.

  When using the pyrimidinetrione derivative, organometallic compound, and organic halide as the chemical polymerization type radical initiator, the compounding ratio of each component in the curable material is the organometallic compound and organic with respect to 1 mol of the pyrimidinetrione derivative. Expressed in terms of the number of moles of halide, ranges of 0.00001 to 0.002 mole and 0.001 to 0.2 mole, respectively, are preferred.

  Pyrimidinetrione derivatives and organometallic compounds are often solid at room temperature. On the other hand, organic halides are generally liquid and paste-like at room temperature. Therefore, in order to keep the powder properties in the powder material (I), the organic halide is preferably contained in the liquid material (II). In addition, it is not preferable from the viewpoint of storage stability that two types selected from pyrimidinetrione derivatives, organometallic compounds, and organic halides are present in the liquid material (II) in any combination. From these, the chemical polymerization type radical initiator composed of a combination of the pyrimidinetrione derivative, the organometallic compound and the organic halide includes the pyrimidinetrione derivative and the organometallic compound in (I) the powder material, while the organic halide. (II) is most preferably contained in the liquid material.

  The above-mentioned chemical polymerization type radical initiator is prepared by mixing (I) powder material, (II) liquid material, and (III) radical polymerization retarding liquid into a dental curable material. The total amount of each constituent compound of the chemical polymerization radical polymerization initiator is in the range of 0.05 to 15 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained. Are preferably used. For this reason, each constituent compound has a suitable content in each of the components (I) to (III) in consideration of the mixing ratio of these members and the above curable material. It may be blended at an appropriate concentration.

  In the dental curable material kit of the present invention, d) the radical chain transfer agent is added to the a) radical polymerizable monomer as described above, and (III) is added to the kit structure as a radical polymerization retarding solution. Thereby, when (I) powder material and (II) liquid material are mixed, this (III) radical polymerization retarding liquid is also mixed in various amounts to obtain a polymerization initiator in the resulting curable material. On the other hand, the radical chain transfer agent can be allowed to act at an optimum concentration at which a desired exothermic temperature and curing time can be obtained.

  As the radical chain transfer agent, a known radical chain transfer agent is used without particular limitation. Specific examples include mercaptans, halogenated hydrocarbons, and phenyl-containing monoolefins. Mercaptans may be compounds having one mercapto group. As mercaptans, octyl mercaptan, lauryl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, m-thiocresol, thiophenol, thioglycol (2-mercaptoethanol), 2-ethylhexyl thioglycolate , Β-naphthalenethiol and the like. A halogenated hydrocarbon is a hydrocarbon substituted with at least one halogen atom (eg, chlorine, bromine, iodine). Examples of the halogenated hydrocarbon include carbon tetrachloride and ethylene bromide.

  Among them, a phenyl group-containing monoolefin is preferable, and 2-phenyl-1-propene (α-methylstyrene), 2-phenyl-1-butene, 2,4-diphenyl-4-methyl-1-pentene (α-methylstyrene). Dimer), 3,5-diphenyl-5-methyl-2-heptene, 2,4,6-triphenyl-4,6-dimethyl-1-heptene, 3,5,7-triphenyl-5-ethyl -7-methyl-2-nonene, 1,3-diphenyl-1-butene, 2,4-diphenyl-4-methyl-2-pentene, 3,5-diphenyl-5-methyl-3-heptene, 1, 1-diphenylethylene, 2,4-diphenyl-4-methyl-1-pentene, 2-phenyl-1-propene, 1,3-diphenyl-1-butene and the like. It can be used as a mixture of two or more.

Among the above radical chain transfer agents, the following general formula (1):
(Wherein R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)
Is particularly preferred. In the said General formula (1), the said C1-C3 alkyl group is a methyl group, an ethyl group, n-propyl group, or i-propyl group. The styrene derivative used in the present invention is not particularly limited as long as it is represented by the above general formula (1). However, in terms of availability, 2,4-diphenyl in which R ¹ and R ² are both methyl groups. It is preferably -4-methyl-1-pentene. Further, if necessary, a plurality of styrene derivatives having different R ¹ and R ² can be used in combination.

  In the present invention, when the radical chain transfer agent is a dental curable material by mixing (I) powder material, (II) liquid material, and (III) radical polymerization retarding liquid, It is preferable to use it in the range of 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable monomer contained. Although it cannot be determined unconditionally because it varies depending on the type and blending amount of each component constituting the curable material, the blending amount of the radical chain transfer agent with respect to 100 parts by mass of the radically polymerizable monomer contained in the curable material is the above. By setting the content within the range, the curing time of the obtained curable material is delayed by 4 to 300%, more surely 10 to 150%, compared to the case where the radical chain transfer agent is not blended at all. Similarly, it is possible to reduce the heat generation temperature in the range of 2 to 50%, more surely in the range of 5 to 35%.

  On the other hand, when the blending amount of the radical chain transfer agent with respect to 100 parts by mass of the radically polymerizable monomer contained in the curable material is less than 0.01 parts by mass, the effect of reducing the curing heat generation is sufficient. Therefore, it is difficult to sufficiently develop the effect of controlling the curing time. Moreover, when a compounding quantity exceeds 10 mass parts, there exists a possibility that hardening time may be overdue and the physical property of a hardening body falls. From these, the radical chain transfer agent is preferably used when (III) the curable material is used in the radical polymerization retarding liquid in consideration of the mixing ratio of the respective members (I) to (III). What is necessary is just to mix | blend by the appropriate density | concentration with which a content is achieved. In general, it is preferable to add 0.05 to 10% by mass, more preferably 0.1 to 5% by mass in the (III) radical polymerization retarding solution.

  Other components can be added to the dental curable composition contained in the kit of the dental curable material of the present invention as necessary. To give specific examples, (I) the powder material is mixed with quartz powder, alumina powder, glass powder, calcium carbonate, titanium oxide, dry silica, wet silica, etc. as inorganic fillers in order to adjust operability and the like. It is also possible that these can be used as one or a mixture of two or more.

  In addition, (II) liquid material and (III) radical polymerization delay liquid include organic solvents such as ethanol, polymerization inhibitors such as butylhydroxytoluene and methoxyhydroquinone, 4-methoxy-2-hydroxybenzophenone, 2- (2 It is also possible to mix ultraviolet absorbers such as -benzotriazole) -p-cresol. In addition, various other additives such as dyes, pigments, and fragrances can be blended into appropriate components in the members (I) to (III) according to their properties.

  By the way, in a dental curable material kit containing a radical chain transfer agent, a chemical polymerization type radical polymerization initiator as a combination of the above-mentioned peroxide / amine compound, or pyrimidinetrione derivative / organometallic compound / organic When a combination of halides is used, the radical chain transfer agent as in the present invention (III) as a radical polymerization retarding liquid must be blended with the component (II) separately from the liquid material. The material is easily gelled during storage and storage stability is deteriorated. The cause of this is not necessarily clear, but as described above, when the chemical polymerization radical polymerization initiator of the above combination is used, (II) the liquid material preferably contains an amine compound or an organic halide. Become. When the radical chain transfer agent is further contained in the liquid material of this aspect, radicals (or ionic initiators) are likely to be generated during storage, and finally the liquid gels quickly. It will occur. On the other hand, as in the dental curable material kit of the present invention, the radical chain transfer agent (III) as a radical polymerization delay liquid, when (II) is separately added to the liquid material, The radical chain transfer agent does not coexist with an amine compound or an organic halide in the same solution, and as a result, the storage stability of the liquid material (II) is greatly improved.

  The dental curable material kit of the present invention having the above-mentioned configuration is prepared by mixing (I) powder material, (II) liquid material, and (III) radical polymerization retarding liquid simultaneously or in any order. And may be used as a curable material. The mixing ratio of the radically polymerizable monomer contained in the liquid material (II) and the liquid for delaying radical polymerization (III) and the resin powder contained in the powder material (I) is not particularly limited. Considering the properties and the strength of the cured product, the resin powder is preferably in the range of 25 to 400 parts by mass with respect to 100 parts by mass of the total of the former radical polymerizable monomer. As described above, the dental curable material kit of the present invention eliminates the problem that the amount of the radical chain transfer agent is excessive in the mode of use as a resin mud with excessive liquid. From the viewpoint of exhibiting, it is more preferable to mix so as to be in the range of 25 to 150 parts by mass with respect to 100 parts by mass in total of the radical polymerizable monomers. A suitable mixing ratio of such a radical polymerizable monomer and resin powder, and a suitable content of a chemical polymerization type radical polymerization initiator and a radical chain transfer agent contained in the curable material described above. Moreover, what is necessary is just to adjust content of each component in each member of (I)-(III).

  In general, from the viewpoint of good operability, the ratio of the total capacity of (II) liquid material and (III) radical polymerization retarding liquid to 1 g of (I) powder material is more preferably 0.2 to 5 g, more preferably It is preferable to mix each member of (I)-(III) so that it may become 0.4g-5g, Most preferably, it is 0.475g. In addition, since the mixing operation of the powder material and the liquid material is easy, (I) the powder material, (II) the liquid material, and (III) the radical polymerization retarding liquid are first described in (II) the liquid material, It is effective to mix the (III) radical polymerization retarding liquid and to mix the resulting mixed liquid and (I) the powder material. In this case, each of the compounds constituting the chemical polymerization type radical polymerization initiator is an embodiment in which no radical is generated when the (II) liquid material and (III) radical polymerization retarding liquid that are previously performed are mixed. It is preferable to divide into each member of I) to (III).

  The mixing of (I) the powder material, (II) liquid material, (III) radical polymerization retarding liquid, and these mixed liquids may be carried out by a brushing method or a method using a spatula. In addition, it is efficient to store the liquid material (II) and the liquid (III) for delaying radical polymerization in an eye drop container, and to provide each for mixing with the powder material (I).

  Examples and comparative examples relating to the present invention are shown below, but the present invention is not limited to these examples. The evaluation was performed by the following method.

(1) Measurement of curing heat generation and curing time The maximum temperature and the curing time were evaluated by a heat generation method using a thermistor thermometer. First, the liquid material and the delay liquid were mixed at a ratio of x: 10-X, 1.0 ± 0.01 g of the powder material and 0.48 g of the obtained mixed liquid were mixed, and kneaded for 20 seconds. Next, after pouring into a polyacetal mold having a hole of 6 mmφ at the center of 2 cm × 2 cm × 1 cm, a thermistor thermometer was inserted, and the maximum temperature was measured with a recorder. Further, the time from the start of kneading until the maximum temperature was recorded was measured at the same time, and this time was taken as the curing time. The measurement was performed in a constant temperature room at 23 ° C.

  Moreover, the hardening time measurement on liquid excess conditions was measured with the following method. The excess liquid condition is that the liquid material and the delay liquid are first mixed at a ratio of x: 10-X, and 0.75 ± 0.01 g of the powder material and 0.71 g of the obtained mixed liquid are mixed. The mixing ratio of the powder liquid was (powder liquid ratio 1 g / 0.95 g). Moreover, the mixing ratio when the powder material 0.5 ± 0.01 g and the mixed liquid 0.95 g were mixed (powder liquid ratio 1 g / 1.9 g), the powder material 0.4 ± 0.01 g and the mixed liquid 1 The mixing ratio when .14 g was mixed was (powder-liquid ratio 1 g / 2.85 g), and the powder and liquid were kneaded for 20 seconds at these powder-liquid ratios. Next, after pouring into a polyacetal mold having a hole of 6 mmφ at the center of 2 cm × 2 cm × 1 cm, a thermistor thermometer was inserted, and the maximum temperature was measured with a recorder. Further, the time from the start of kneading until the maximum temperature was recorded was measured at the same time, and this time was taken as the curing time. The measurement was performed in a constant temperature room at 23 ° C.

(2) Storage stability test The storage stability test was conducted by the following method. First, 5 ml of each of the prepared liquid material and delay liquid was placed in a 6 ml brown bottle, sealed, and subjected to an acceleration test at 60 ° C., and the state of the liquid after 6 months was visually evaluated according to the evaluation criteria shown in Table 1.

  Table 2 shows abbreviations of the compounds used in Examples and Comparative Examples of the present invention.

  Table 3 shows the composition of (I) powder material used in the examples and comparative examples conducted this time, Table 4 shows the composition of (II) liquid material, and (III) shows the composition of liquid for retarding radical polymerization. This is shown in FIG.

Examples 1-7, Comparative Examples 1-4
Each combination shown in Table 3, Table 4, and Table 5 is obtained by mixing (I) powder material, (II) liquid material, and (III) radical polymerization retarding liquid at the mixing ratio of each member. Regarding the curable material to be obtained, (1) measurement of curing heat generation and curing time was performed. The results are shown in Tables 6 to 8 together with the composition of the curable material.

Examples 8-18, Comparative Examples 5-7
(2) A storage stability test was conducted on the liquid material (II) having the composition shown in Table 4 and the liquid composition for delaying radical polymerization (III) having the composition shown in Table 5. The results are shown in Tables 9 and 10.

In Examples 1 to 6, the liquid material and the delay liquid are mixed at a ratio of 5: 5. Comparative Examples 1 to 3 are obtained by adding a chemical polymerization type radical polymerization initiator and a radical chain transfer agent to one liquid, and Comparative Example 4 does not contain a radical chain transfer agent.

  As shown in Example 1, mixing is performed at a normal powder / liquid ratio [powder / liquid ratio: 2 g / 0.95 g (powder: liquid: liquid ratio for delay is 0.68: 0.16: 0.16)]. In this case, the maximum temperature is 40 ° C. and the curing time is 370 seconds, but the liquid (mixed liquid of the liquid material and the liquid for delay) is excessive (powder / liquid ratio 1 g / 1.9 g). By adjusting the blending amount of the liquid (powder material: liquid material: retarding liquid ratio is 0.34: 0.59: 0.07), it was possible to obtain substantially the same maximum temperature and curing time. In addition, the storage stability of the liquid material and the delay liquid used in this example was good with a score of 1 (Examples 8 and 14). On the other hand, as shown in Comparative Example 1, in the case where both the polymerization initiator and the chain transfer agent are added to the liquid material, the mixture of the normal powder material and the liquid material has the same composition. The maximum temperature and curing time were the same as in Example 1, but when the liquid was excessive, the amount of chain transfer agent was excessive and the maximum temperature was almost the same, but the curing time was delayed by 70 seconds. The storage stability of the liquid was score 2 (Comparative Example 5), and gelation of the liquid was observed in the storage stability test for 6 months at 60 ° C. Similarly, in Examples 2 to 6, even when the amount of liquid was excessive, both the maximum temperature and the curing time were able to maintain values almost equal to those in the case of a normal powder / liquid ratio.

  In addition, as shown in Examples 9 to 18, the storage stability of the polymerization initiator and the chain transfer agent divided into the liquid material and the delay liquid was good with a score of 1, but the polymerization initiator and Gelation was observed in the liquid materials used in Comparative Examples 5 to 7 in which the chain transfer agent coexists in the liquid.

  In Examples 4 to 7, the compositions of the powder material, the liquid material, and the radical retarding liquid were changed, indicating that the curing time could be controlled.

  In Example 7, the composition of the powder material, the liquid material, and the radical polymerization delay liquid is the same, the ratio of the liquid material: retard liquid is 9: 1 to 3: 7, and the powder / liquid ratio is 2/0. The mixture is changed to 95 to 1 / 2.85. It was possible to control the curing time by changing the ratio of the liquid material and the retarding liquid at any powder / liquid ratio.

  Comparative Example 4 shows a system that does not contain a chain transfer agent. When the curing time is delayed in this system, the curing time can only be adjusted by adjusting the powder / liquid ratio. The control time of the curing time was not good as compared with the case of containing.

Claims (2)

a) radical polymerizable monomer, b) resin powder, c) chemical polymerization radical polymerization initiator composed of peroxide and amine compound , and d) radical chain transfer represented by the following general formula (1) A dental curable material kit containing an agent, wherein (I) b) a powder material containing a resin powder and the peroxide , (II) a) a liquid material containing a radical polymerizable monomer and the amine compound , and (III) a) radical polymerizable monomer and d) kit dental curable material, characterized by comprising divided into the radical polymerization delay solution containing a radical chain transfer agent.

(Wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) a) a radical polymerizable monomer, b) a resin powder, c) a chemical polymerization radical polymerization initiator composed of a pyrimidinetrione derivative, an organometallic compound, and an organic halide, and d) the following general formula (1) A dental curable material kit containing a radical chain transfer agent represented by the formula: (I) b) a resin powder, a powder material containing the pyrimidinetrione derivative and an organometallic compound, and (II) a) a radical polymerizable monomer. A dental material characterized by being divided into a liquid material containing a monomer and the organic halide, and (III) a) a radical polymerizable monomer and d) a radical polymerization retarding solution containing a radical chain transfer agent Kit of curable material.

(Wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)