JP5731178B2 - Method for producing dental filler - Google Patents

Description

  The present invention relates to a method for producing a dental filler. More specifically, the present invention relates to a method for producing a dental filler that maintains good consistency of a blended dental composition, and a dental composition containing a filler obtained by the method.

  A dental composition is a material that contains a polymerizable monomer, a polymerization initiator, and a filler, and is a material for filling and restoring a tooth defect and a decayed tooth.

  In order to improve scientific and engineering properties and reduce volume shrinkage during polymerization, composite materials in which polymerizable vinyl monomers and inorganic or organic fillers, organic-inorganic composite fillers are mixed are widely used in the dental field. . Among these, organic fillers and organic-inorganic composite fillers are fillers that are advantageous in improving easy polishing, reducing stickiness of paste, and reducing polymerization shrinkage.

  For example, a composite material using an organic-inorganic composite filler obtained by filling a polymerizable monomer with ultrafine particles, cured, and pulverized is proposed, and described in Patent Document 1 as having advantages such as operability and abrasiveness. Yes. Patent Document 2 discloses a composition containing an organic composite filler from the viewpoint of surface smoothness, thermal expansion coefficient, and polymerization shrinkage. Recently, fine particles such as silica and metal oxides are agglomerated to prepare agglomerated particles (aggregated filler) with a size of micron or more, and apparently used as substitutes for organic-inorganic composite fillers as large particles. As a result, it has been reported that the mechanical strength is improved as the paste properties are improved (see Patent Document 3).

  However, one of the purposes of blending organic fillers and organic-inorganic composite fillers is to reduce stickiness of the paste and to obtain good operability, but these fillers absorb monomers over time, There is a problem in the stability of the paste property that the paste containing the filler becomes harder with time.

  On the other hand, Patent Document 4 describes a production method in which a spherical inorganic filler and an ultrafine inorganic filler are simultaneously surface-treated from the viewpoint of improving the stability of paste properties.

Japanese Patent Publication No. 7-91170 Japanese Patent Laid-Open No. 5-194135 JP 2001-302429 A JP-A-4-210609

  An object of the present invention is a filler obtained by using an organic filler or an organic-inorganic composite filler, a method for producing a filler capable of maintaining good paste properties, and a dental containing a filler obtained by the method It is to provide a composition.

  As a result of intensive studies to solve the above problems, the present inventors have treated the surface of the organic-inorganic composite filler or organic filler used in the dental composition with an ultrafine inorganic filler and a silane coupling agent. The present inventors have found that the above technical problem can be solved by using the obtained surface coat filler, and have completed the present invention.

That is, the present invention
[1] The surface of the organic / inorganic composite filler or the organic filler is coated with the surface of the organic / inorganic composite filler or the organic filler, characterized in that the surface of the organic / inorganic composite filler or the organic filler is coated with an ultrafine inorganic filler composed of inorganic ultrafine particles and a silane coupling agent. The manufacturing method of a surface coat filler, and [2] It is related with the dental composition containing the surface coat filler obtained by the manufacturing method of said [1] description.

  Since the surface-coated filler obtained by the production method of the present invention prevents the absorption of the monomer, the dental composition containing the filler does not harden the paste with time and can maintain the paste properties well. There is an excellent effect.

FIG. 1 is a view showing a micrograph of the surface state of the surface coat filler B (Example 2) obtained by the production method of the present invention. The left figure is a photograph of x1000 magnification, and the right figure is an enlarged photograph (x5000 magnification) of a circled portion in the x1000 magnification photograph. FIG. 2 is a view showing a micrograph of the surface state of the organic-inorganic composite filler (a) that has not been surface-coated. The left figure is a photograph of x1000 magnification, and the right figure is an enlarged photograph (x5000 magnification) of a circled portion in the x1000 magnification photograph.

  The method for producing a surface-coated filler of the present invention is characterized in that the surface of an organic-inorganic composite filler or organic filler is surface-coated (also referred to as surface-coating treatment) using an ultrafine inorganic filler and a silane coupling agent. By performing such a treatment, a coating film (coat layer) in which the ultrafine inorganic filler is dispersed in the silane coupling agent layer is formed on the surface of the organic-inorganic composite filler or the organic filler. In this coating film, the silane coupling agent is considered to play the role of a monomer, and a monomer-containing layer-like layer obtained by impregnating the monomer with an organic-inorganic composite filler or organic filler is formed on the filler surface. It is inferred that Moreover, when the ultrafine inorganic filler is dispersed in such a layer, the strength of the coating film is improved and the thickness of the coating film is easily secured.

  Examples of the organic-inorganic composite filler and the organic filler used for the surface coating treatment include the following.

  The organic-inorganic composite filler is obtained by adding a polymerizable monomer to an inorganic filler in advance, forming a paste, polymerizing, and pulverizing. Examples of the polymerizable monomer include an aromatic polymerizable monomer (a) having a hydroxyl group, an aromatic polymerizable monomer (b) having no hydroxyl group, and / or an aliphatic polymerizable monomer (c). The polymerizable monomer containing is preferable.

  As the inorganic filler which is a raw material of the organic-inorganic composite filler, known ones used for dental compositions can be used without any limitation, and include inorganic ultrafine particles (inorganic nanoparticles) described later and various glasses. . In addition, the inorganic filler may be surface-treated with a known silane coupling agent from the viewpoint of easy compatibility with the monomer and bonding properties.

  Examples of various glasses (mainly composed of silica and optionally containing oxides such as heavy metals, boron, zirconium, titanium, and aluminum) include fused silica, quartz, soda lime silica glass, E glass, C Glass, glass powder of general composition such as borosilicate glass [Pyrex (registered trademark) glass], “Ray-SorbT3000” (manufactured by Kimble), “GM27884” (manufactured by Schott), “8235 series (8235 UF0. 7)) (manufactured by Schott), strontium boroaluminosilicate glass such as “Ray-SorbT2000” (manufactured by Kimble), lanthanum glass ceramics such as “GM31684” (manufactured by Schott), “GM35429” ” Kate glass, dental glass powders such as “G018-091” (manufactured by Schott), “G018-117” (manufactured by Schott), various ceramics, composite oxides, diatomaceous earth, kaolin, clay mineral (montmorillonite, etc.), Examples include activated clay, synthetic zeolite, mica, calcium fluoride, ytterbium fluoride, yttrium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, and hydroxyapatite.

  As the polymerizable monomer used in preparing the organic-inorganic composite filler, known polymerizable monomers used for dental compositions are used without any limitation. For example, aromatic polymerization having a hydroxyl group. The polymerizable monomer (a), the aromatic polymerizable monomer (b) having no hydroxyl group, and the aliphatic polymerizable monomer (c) are preferably used.

  In the present invention, the “polymerizable monomer” refers to a compound having at least one polymerizable group, and since a radical polymerization is generally performed in a dental composition, the polymerizable group is Usually, it is a radically polymerizable group. As the polymerizable group, a (meth) acryloyloxy group and a (meth) acryloylamino group are preferable, and a (meth) acryloyloxy group is more preferable from the viewpoint of easy availability of a polymerizable monomer, and safety to living bodies. From this viewpoint, a methacryloyloxy group is more preferable. In the present specification, (meth) acryloyl is a general term for acrylic and methacrylic.

  In the present invention, the “aromatic polymerizable monomer” refers to a polymerizable monomer having at least one aromatic ring. The aromatic ring may be any of a benzene ring, a condensed benzene ring (eg, naphthalene), a non-benzene aromatic ring, or a heteroaromatic ring (eg, pyridine ring, pyrrole ring), and preferably a benzene ring. .

  In the present invention, “aliphatic polymerizable monomer” refers to a polymerizable monomer having no aromatic ring.

  The aromatic polymerizable monomer (a) having a hydroxyl group is a polymerizable monomer having at least one hydroxyl group, at least one aromatic ring, and at least one polymerizable group. And the number of polymerizable groups is not particularly limited. From the viewpoint of availability and the mechanical strength of the cured product of the dental composition, the number of polymerizable groups is preferably 1 to 6, and more preferably 2 to 4. From the viewpoint of availability and hydrophilicity of the dental composition, the number of hydroxyl groups is preferably 1 to 3. From the viewpoint of availability and mechanical strength of the cured product of the dental composition, the number of aromatic rings is preferably 1 to 3, more preferably 2, and the polymerizable monomer (a) is a bisphenol A skeleton ( More preferably, it has a structure in which hydrogen is removed from two hydroxyl groups of bisphenol A.

  Examples of the polymerizable monomer (a) include 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane (hereinafter referred to as Bis-GMA). ), 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- [2,3-di (meth) acryloyloxypropoxy] phenyl] propane (hereinafter referred to as Bis3) 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- (meth) acryloyloxydiethoxyphenyl] propane, 2- [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- (meth) acryloyloxytriethoxyphenyl] propane, 2- [ - [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] -2- [4- (meth) acryloyloxy-di propoxy phenyl] propane.

  The aromatic polymerizable monomer (b) having no hydroxyl group is a polymerizable monomer having at least one aromatic ring and at least one polymerizable group and having no hydroxyl group. There is no particular limitation on the number of sex groups. From the viewpoint of availability and the mechanical strength of the cured product of the dental composition, the number of polymerizable groups is preferably 1 to 6, and more preferably 2 to 4. From the viewpoint of availability and the mechanical strength of the cured product of the dental composition, the number of aromatic rings is preferably 1 to 3, more preferably 2, and the polymerizable monomer (b) has a bisphenol A skeleton. More preferably, it has.

  Examples of the polymerizable monomer (b) include those represented by the formula (I):

Wherein R ¹ and R ² are each independently a hydrogen atom or a methyl group, m and n are 0 or a positive number indicating the average number of moles of ethoxy group added, and the sum of m and n Is preferably 1-6, more preferably 2-4)
For example, 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane in which m + n = 2.6 (hereinafter sometimes referred to as D2.6E), m + n = 6 2,2-bis [4- (meth) acryloyloxypolyethoxyphenyl] propane (e.g., 2,2-bis [4- (meth) acryloyloxytriethoxyphenyl] propane). These are collectively referred to as D6E. 2,2-bis [4- (meth) acryloyloxyphenyl] propane (m + n = 0), 2- [4- (meth) acryloyloxyethoxyphenyl] -2- [4- (meta ) Acryloyloxyphenyl] propane (m + n = 1), 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane (m + n = 2) ), 2- [4- (meth) acryloyloxydiethoxyphenyl] -2- [4- (meth) acryloyloxyethoxyphenyl] propane (m + n = 3), 2,2-bis [4- (meth) acryloyloxy Diethoxyphenyl] propane (m + n = 4), 2- [4- (meth) acryloyloxydiethoxyphenyl] -2- [4- (meth) acryloyloxytriethoxyphenyl] propane (m + n = 5), and the like. . The polymerizable monomer (b) includes 2,2-bis [4- (meth) acryloyloxydipropoxyphenyl] propane, 2- [4- (meth) acryloyloxydipropoxyphenyl] -2- [ 4- (meth) acryloyloxytriethoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxypropoxyphenyl] propane, 2,2-bis [4- (meth) acryloyloxyisopropoxyphenyl] propane, etc. Can also be used.

  The aliphatic polymerizable monomer (c) can be used without particular limitation as long as it is a polymerizable monomer having no aromatic ring. From the viewpoint of availability and the mechanical strength of the cured product of the dental composition, the number of polymerizable groups is preferably 1 to 6. The aliphatic polymerizable monomer (c) is an aliphatic polymerizable monomer (c-2) having a hydroxyl group even if the aliphatic polymerizable monomer (c-1) does not have a hydroxyl group. Also good.

  Examples of the polymerizable monomer (c-1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Lauryl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, (meth) acrylamide, ethylene glycol di (meth) acrylate (hereinafter sometimes referred to as 1G), triethylene glycol di (meth) acrylate (Hereinafter sometimes referred to as 3G), 1,2-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate (hereinafter sometimes referred to as NPG), propylene glycol di (meth) Acrylate, 1,3-butanedio Rudi (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate (hereinafter sometimes referred to as HD), 1,10-decanediol di (meth) ) Acrylate (hereinafter sometimes referred to as DD), 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) di (meth) acrylate (hereinafter sometimes referred to as UDMA), N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate (hereinafter referred to as U-4TH) ), Trimethylolethane tri (meth) acrylate, pentaerythritol tet (Meth) acrylate, 1,7-diaryl methacryloyloxy-2,2,6,6-tetramethyl-acryloyloxy-4- oxy heptane (hereinafter, may be described as DPE-6A) and the like.

  Examples of the polymerizable monomer (c-2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (HEMA), 3-hydroxypropyl (meth) acrylate, and 1,3-dihydroxy. Propyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylamide, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, diethylene glycol (meth) acrylate, Examples include pentaerythritol di (meth) acrylate and tetramethylolmethane tri (meth) acrylate. In addition, in this specification, (meth) acrylate is a general term for acrylic acid ester and methacrylic acid ester.

  These polymerizable monomers can be used alone or in combination of two or more. For example, the polymerizable monomer (a) alone or in combination of two or more, the polymerizable monomer (b) alone or in combination of two or more, or the polymerizable monomer (c) May be used alone or in combination of two or more. Also, a combination of the polymerizable monomer (a) and the polymerizable monomer (b), a combination of the polymerizable monomer (a) and the polymerizable monomer (c), or a polymerizable monomer The body (b) and the polymerizable monomer (c) may be used in combination, and the polymerizable monomer (a), the polymerizable monomer (b), and the polymerizable monomer (c) are all combined. May be used.

  The shape of the organic-inorganic composite filler is not particularly limited. The average particle size of the filler is preferably 100 μm or less, and more preferably 0.001 to 50 μm, from the viewpoints of handleability and mechanical strength of the resulting composition. In the present specification, the average particle diameter of the filler can be measured by any method known to those skilled in the art. For example, measurement with a laser diffraction type particle size distribution measuring apparatus described in the following examples, or SEM microscope, etc. It can easily be measured by direct observation used.

  Next, the organic filler will be described. As an organic filler, what polymerized the well-known polymerizable monomer used for a dental composition is used without a restriction | limiting, For example, the above-mentioned aromatic polymerizable monomer (a ), A polymerized polymerizable monomer containing an aromatic polymerizable monomer (b) having no hydroxyl group and / or an aliphatic polymerizable monomer (c) is preferably used. The shape of the organic filler is not particularly limited. The average particle size is preferably 100 μm or less.

  As the ultrafine inorganic filler used for the surface coating treatment, known inorganic ultrafine particles used for dental compositions can be used without any limitation.

Examples of the inorganic ultrafine particles include inorganic oxide particles such as silica, alumina, titania and zirconia, or composite oxide particles made of these, calcium phosphate, hydroxyapatite, yttrium fluoride, ytterbium fluoride and the like. Preferably, particles such as silica, alumina, titania and the like produced by a flame pyrolysis method, for example, manufactured by Nippon Aerosil Co., Ltd., trade names: “AEROSIL (registered trademark) 130”, “AEROSIL (registered trademark) OX50”, “AEROXIDE (registered trademark) AluC”, “AEROXIDE (registered trademark) TiO ₂ P25”, “AEROXIDE (registered trademark) TiO ₂ P25S”, “VP Zirconium Oxide 3-YSZ”, “VP Zirconium Oxide PH” are preferably used. It is done. These inorganic ultrafine particles may be subjected to a surface treatment according to a known method, but are preferably used in an untreated state.

  As the silane coupling agent used for the surface coating treatment, any known silane coupling agent used for a dental composition can be used without any limitation.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, 11-methacryloyloxyundecyltrimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like are used.

  The surface coating method is not particularly limited as long as the organic-inorganic composite filler or organic filler, the ultrafine inorganic filler, and the silane coupling agent can be mixed at the same time, and a known method can be used. it can. For example, a method of spraying and mixing an organic-inorganic composite filler or an organic filler and an untreated ultrafine inorganic filler with a silane coupling agent while stirring vigorously, a silane coupling agent and an organic-inorganic composite in an appropriate solvent After dispersing or dissolving the filler or organic filler and the surface-untreated ultrafine inorganic filler, stirring and mixing, removing the solvent, adding a silane coupling agent to an appropriate acid solvent, hydrolyzing, and then organic There is a method of adding an inorganic composite filler or an organic filler and a surface-untreated ultrafine inorganic filler, dispersing or dissolving the mixture, stirring and mixing, and then removing the solvent. By heating the mixture in the range, surface coating treatment, i.e., the surface of the organic-inorganic composite filler or organic filler Coat layer of the particles the inorganic filler dispersed silane coupling agent is formed. Note that the order of adding the organic-inorganic composite filler or organic filler, the ultrafine inorganic filler, and the silane coupling agent is not particularly limited as long as they can be mixed simultaneously.

  The amount of the ultrafine inorganic filler used in the surface coating treatment is preferably 5 to 50 parts by weight and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the organic-inorganic composite filler or organic filler used for the treatment.

  The amount of the silane coupling agent used for the surface coating treatment is preferably 0.05 to 100 parts by weight, and 0.10 to 50 parts by weight with respect to 100 parts by weight of the organic-inorganic composite filler or organic filler used for the treatment. Is more preferable.

  Thus, the filler of the present invention (also referred to as a surface coat filler) in which a coating layer of a silane coupling agent in which an ultrafine inorganic filler is dispersed on the surface of the organic / inorganic composite filler or the organic filler is obtained. The obtained filler has an average particle size before the surface coating treatment of the organic-inorganic composite filler or the organic filler because the average particle size does not vary greatly depending on the coating of the ultrafine inorganic filler and the silane coupling agent. .

  The present invention also provides a dental composition containing the surface coat filler of the present invention.

  The dental composition of the present invention is not particularly limited as long as it contains the surface coat filler of the present invention, and can contain a polymerizable monomer or additive known in the art in addition to the filler. . In addition, from the viewpoint of imparting X-ray contrast properties, improving material strength, and obtaining good paste properties, fillers other than the above-mentioned surface coat fillers, such as inorganic fillers, ultrafine inorganic fillers, organic fillers that are not surface-coated, Inorganic composite fillers, organic fillers, inorganic fillers and ultrafine inorganic fillers that have been subjected to a known surface treatment other than the surface coating treatment can also be contained.

  10-80 weight% is preferable in a dental composition, and, as for content of a surface coat filler, 30-70 weight% is more preferable.

  As the polymerizable monomer, known polymerizable monomers used for dental compositions can be used without any limitation. For example, the above-mentioned aromatic polymerizable monomer having a hydroxyl group (a), A polymerizable monomer containing an aromatic polymerizable monomer (b) having no hydroxyl group and an aliphatic polymerizable monomer (c) is preferably used.

  The content of the polymerizable monomer in the dental composition is preferably 1 to 99% by weight, and more preferably 10 to 60% by weight.

  Examples of additives include polymerization initiators, polymerization accelerators, polymerization inhibitors, and the like, and pH adjusters, ultraviolet absorbers, antioxidants, colorants, antibacterial agents, X-ray contrast agents, sensitizers are used depending on the purpose. It is also possible to further add a sticking agent, a fluorescent agent and the like.

  As a polymerization initiator, the polymerization initiator currently used in the general industry can be selected suitably, and the polymerization initiator used for the dental use is used preferably. Among these, the polymerization initiator for photopolymerization and the polymerization initiator for chemical polymerization are used singly or in appropriate combination of two or more.

  Photopolymerization initiators include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, benzoin alkyl ethers, α-amino ketones And the like.

  Among the (bis) acylphosphine oxides, the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2 , 4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) A phosphonate etc. are mentioned. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis- (2,6-dichloro). Benzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -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-trimethylpentyl phosphine oxide and the like. Moreover, salts of (bis) acylphosphine oxides such as sodium salts and lithium salts of the above compounds can also be used as photopolymerization initiators.

  The water-soluble acyl phosphine oxides preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion or ammonium ion in the acyl phosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of water-soluble acylphosphine oxides include monomethylacetylphosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethylbenzoylphosphonate / sodium, monomethyl (1-oxobutyl) phosphonate / sodium, monomethyl (2-methyl) -1-oxopropyl) phosphonate sodium, acetylphosphonate sodium, monomethylacetylphosphonate sodium, acetylmethylphosphonate sodium, methyl-4- (hydroxymethoxyphosphinyl) -4-oxobutanoate sodium salt, methyl -4-oxophosphonobutanoate monosodium salt, acetylphenylphosphinate sodium salt, (1-oxopropyl) pliers Phosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphinate sodium, methyl (1,1-dimethyl) methylphosphine Sodium phosphate, sodium (1,1-diethoxyethyl) methylphosphinate, sodium (1,1-diethoxyethyl) methylphosphinate, methyl-4- (hydroxymethylphosphinyl) -4-oxobuta Noate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl ( 2-methyl-1,3-thia Lidin-2-yl) phosphinate sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphinate sodium salt, acetylphosphinate sodium salt, (1,1-diethoxyethyl) phosphinate Sodium salt, (1,1-diethoxyethyl) methyl phosphinateSodium salt, methyl (2-methyloxathiolan-2-yl) phosphinatesodium salt, methyl (2,4,5-trimethyl-1, 3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phosphinate sodium salt, (1-methoxyvinyl) methylphosphinate sodium salt, (1-ethylthiovinyl) methylphosphinate・ Sodium salt, methyl (2-methylpar Hydro-1,3-diazin-2-yl) phosphinate sodium salt, methyl (2-methylperhydro-1,3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3- Diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl Methyl phosphinate oxime / Natrium salt, acetyl methyl phosphinate-O-benzyl oxime / sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate / sodium salt, methyl (1-phenyliminoethyl) phosphinate / Sodium salt, methyl (1-phenylhydride Zonethyl) phosphinate sodium salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methyl phosphinate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) Methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl methyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate・ Sodium salt, (1,1-dimethoxypropyl) methylphosphinate, dodecylguanidine salt, (1,1-dimethoxypropyl) methylphosphinate, isopropylamine salt, acetylmethylphosphinate Semicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2,4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3 , 5-Dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide Examples include potassium salts and ammonium salts of 2,4,6-trimethylbenzoylphenylphosphine oxide. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferred.

  Examples of the quaternary ammonium salt of thioxanthones or thioxanthones include thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy-9H-thioxanthen-4-yloxy)- N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9- Oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium Id, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy-3- (1,3 , 4-Trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a suitable thioxanthone is 2-chlorothioxanthen-9-one, and a suitable quaternary ammonium salt of thioxanthones is 2-hydroxy- 3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of α-diketones include diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, acenaphthenequinone, and the like. Can be mentioned. Among these, camphorquinone is preferable from the viewpoint of having a maximum absorption wavelength in the visible light region.

  Examples of benzoin alkyl ethers include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, and α-diketones.

  As the chemical polymerization initiator, an organic peroxide is preferably used. The organic peroxide is not particularly limited, and those known in the art can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

  Examples of the ketone peroxide include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

  Examples of the hydroperoxide include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

  Examples of the diacyl peroxide include acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and the like. Can be mentioned.

  Dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3- Examples thereof include bis (t-butylperoxyisopropyl) benzene and 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne.

  Peroxyketals include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t- And butyl peroxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester.

  Peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate. Ate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, Examples thereof include t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxymaleic acid.

  As peroxydicarbonate, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, di-n -Propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, diallyl peroxydicarbonate and the like.

  Among these organic peroxides, diacyl peroxide is preferably used, and among these, benzoyl peroxide is more preferably used from the comprehensive balance of safety, storage stability, and radical generating ability.

  Examples of the polymerization accelerator include amines, sulfinic acid and salts thereof, aldehydes, and thiol compounds.

  Amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Amine, and the like. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the composition, and among them, N-methyldiethanolamine and triethanolamine are more preferably used.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N , N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4- Examples include butyl dimethylaminobenzoate. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of sulfinic acid and salts thereof include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, calcium p-toluenesulfinate, benzenesulfinic acid, and benzenesulfin. Sodium sulfate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, 2,4,6-trimethylbenzenesulfine Potassium acetate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate, 2,4,6-to Sodium ethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate, 2,4,6-triisopropylbenzene Sulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, lithium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropyl Examples thereof include calcium benzenesulfinate, and sodium benzenesulfinate, sodium p-toluenesulfinate, and sodium 2,4,6-triisopropylbenzenesulfinate are preferable.

  Examples of aldehydes include terephthalaldehyde and benzaldehyde derivatives. Examples of the benzaldehyde derivative include dimethylaminobenzaldehyde, p-methyloxybenzaldehyde, p-ethyloxybenzaldehyde, pn-octyloxybenzaldehyde and the like. Among these, pn-octyloxybenzaldehyde is preferably used from the viewpoint of curability.

  Examples of the thiol compound include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  Examples of the polymerization inhibitor include 2,6-di-butylhydroxytoluene, hydroquinone, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, 2,6-t-butylphenol, and the like. May be.

  The dental composition of the present invention is not particularly limited as long as it contains a surface coat filler, and can be easily produced by methods known to those skilled in the art.

  The dental composition of the present invention is applied to the adhesive surface with the curable composition alone and used as a so-called self-adhesive cement or the like, after applying another liquid such as a primer to the adhesive surface. The dental composition of the present invention can also be applied and used.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited at all by these Examples. The test methods, materials, etc. used in the examples are summarized below.

[Average particle size of filler]
The average particle size is measured by using a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, model “SALD-2100”) or by direct observation with an SEM microscope (manufactured by Hitachi, Ltd., S-4000).

Production Example 1 [nuclear filler (organic-inorganic composite filler (a))]
2,2, -bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA) 75 parts by weight, triethylene glycol dimethacrylate (3G) 25 parts by weight, benzoyl peroxide 0.5 50 g of polymerizable monomer mixture consisting of parts by weight is coated with 10 parts by weight of γ-methacryloxypropyltrimethoxysilane with respect to 100 parts by weight of AEROSIL (registered trademark) OX50 (manufactured by Nippon Aerosil Co., Ltd., average particle size 40 nm). A composition obtained by mixing and kneading 50 g of the treated filler and homogenizing it was heated and cured at 100 ° C. for 24 hours in a nitrogen atmosphere, and pulverized and classified to obtain a particle size range of 0.1 to 0.1%. An organic-inorganic composite filler (a) having an average particle size of 20 μm at 100 μm was obtained.

Production Example 2 [nuclear filler (organic filler (b))]
2,2, -bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA) 75 parts by weight, triethylene glycol dimethacrylate (3G) 25 parts by weight, benzoyl peroxide 0.5 By crushing and classifying a polymerizable monomer mixture consisting of parts by weight of a polymerizable monomer mixture heated at 100 ° C. for 24 hours under a nitrogen atmosphere, an average particle size of 20 μm with a particle size range of 0.1 to 100 μm. The organic filler (b) was obtained.

Production Example 3 [nuclear filler (inorganic filler (c))]
Surface treatment was performed with 4.2 parts by weight of γ-methacryloxypropyltrimethoxysilane per 100 parts by weight of barium glass (manufactured by Schott: 8235 UF0.7), and an inorganic filler (c )

Production Example 4 [nuclear filler (surface treated ultrafine inorganic filler (d))]
Surface treatment is performed with 25 parts by weight of γ-methacryloxypropyltrimethoxysilane to 100 parts by weight of AEROSIL (registered trademark) 130 (manufactured by Nippon Aerosil Co., Ltd., average particle diameter 16 nm), and surface treated ultrafine inorganic filler (d) Got.

Examples 1 to 4 (surface coat filler)
After hydrolyzing by adding a silane coupling agent (γ-methacryloxypropyltrimethoxysilane) to an acetic acid aqueous solution, 100 parts by weight of filler shown in the table is added and dispersed and stirred, and then AEROSIL (registered trademark) 130 [surface treatment In order to distinguish it from the ultrafine inorganic filler (d), the surface untreated ultrafine inorganic filler is also added in the amount shown in Table 1 and further dispersed and stirred to obtain a slurry. The obtained slurry was freeze-dried and then heat-treated at 90 ° C. for 3 hours to obtain a filler (hereinafter referred to as a surface coat filler).

Examples 5-10 and Comparative Examples 1-2 (dental composition)
2,2, -bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA) 75 parts by weight, triethylene glycol dimethacrylate (3G) 25 parts by weight, α-as a polymerization initiator A polymerizable monomer mixture (A) was prepared by dissolving 0.5 part by weight of camphorquinone and 1.0 part by weight of ethyl N, N-dimethylaminobenzoate as a polymerization accelerator. The obtained polymerizable monomer mixture (A) was mixed and kneaded with the filler shown in Table 2 to make the mixture uniform and vacuum degassed, and then used for dental use in Examples 5-10 and Comparative Examples 1-2. A composition was obtained.

  The physical properties of the obtained dental composition were examined according to the following method. The results are shown in Table 2.

[Consistency]
Each paste (paste-like dental composition) is defoamed under vacuum and filled in a syringe, and then left in a thermostat (humidity 40%) at 25 ° C. for 1 day, and then a consistency test is performed. Specifically, 0.25 mL of the paste is weighed on a glass plate with a polyester film interposed therebetween, the polyester film is placed thereon, and a weight with a 1 kg glass plate is placed on the glass plate for 30 seconds to stretch the paste. The shortest and longest distances of the paste spread in a circle are measured, and the average is taken as the initial consistency (mm). On the other hand, the paste (paste-like dental composition) defoamed under vacuum and filled into a syringe was left in a 50 ° C. incubator (humidity 40%) for 7 days and then left at 25 ° C. for 2 hours. Consistency is measured by the above method for the paste, and the consistency (mm) is obtained after storage. In addition, since the composition which shows the initial stage consistency about 16-17 mm has moderate viscosity, it is used suitably.

The consistency stability is evaluated by the consistency maintenance rate (%) calculated by the following formula (1). A consistency maintenance rate of 85% or more is judged good.
Consistency maintenance rate (%) = Consistency after storage / Initial consistency × 100 Formula (1)

  From the above results, it can be seen that a composition having a stable paste consistency can be obtained by using the surface coat filler. More specifically, when Example 6 and Comparative Example 1 are compared, Comparative Example 1 that contains the same type of filler, but the organic-inorganic composite filler is not surface-coated, has a large consistency reduction rate. The initial consistency was also small. It can be seen that the familiarity between the filler and the monomer is poor. Further, even when Example 8 and Comparative Example 2 were compared, Comparative Example 2 containing a filler not subjected to surface coating treatment had a large decrease in consistency and a small initial consistency. In addition to the examples described above, Examples 5, 7, 9, and 10 containing a surface-coated filler also have a low consistency reduction rate and are excellent in paste consistency stability. 9 suggests that even if the content of the organic-inorganic composite filler that absorbs the monomer is increased, it is possible to maintain the paste consistency by surface coating in advance. Thus, the composition with which paste consistency was stabilized was able to be obtained by using the filler manufactured by the manufacturing method of this invention.

  Moreover, the surface state of the surface coat filler B (Example 2) manufactured by the manufacturing method of the present invention is shown in FIG. 1, and the organic inorganic composite filler (a) not subjected to surface coating, which is a core filler of the surface coat filler. The surface state is shown in FIG. It can be seen that the surface-coated filler is finely coated on the filler surface with fine particles.

  In dentistry, the operability of the paste is one of the important sensory elements, and it is not preferred that the paste properties change. Since the dental composition using the filler manufactured by the present invention has a stable paste consistency, it can maintain an appropriate paste property for a long period of time. In the field of dentistry, it is preferably used as a substitute for a part or the whole of a natural tooth.

Claims (4)

A surface-coated filler having a surface coated with an organic-inorganic composite filler or an organic filler, characterized in that the surface of the organic-inorganic composite filler or the organic filler is coated with an ultrafine inorganic filler composed of inorganic ultrafine particles and a silane coupling agent. Manufacturing method. The production method according to claim 1, wherein 5 to 50 parts by weight of an ultrafine inorganic filler composed of inorganic ultrafine particles is used with respect to 100 parts by weight of the organic-inorganic composite filler or the organic filler.   The production method according to claim 1 or 2, wherein the organic-inorganic composite filler or the organic filler has an average particle size of 100 µm or less.   A dental composition comprising a surface coat filler obtained by the production method according to claim 1.