JP2013193962A - Adhesive composition for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To further improve adhesiveness to tooth in a dental adhesive composition compounded with a polymerizable monomer containing a polymerizable monomer having an acidic group, and an inorganic filler.SOLUTION: There is provided an adhesive composition for dental use containing a polymerizable monomer component (A) including a polymerizable monomer (a1) having an acidic group, and an inorganic filler component (B) including an inorganic particle (b1) having an acidic group, preferably at least one kind of acidic group selected from phosphoric group, phosphonic group, sulfonic group and carboxylic group on a surface, and preferably further containing water (C) and a polymerization initiator (D).

Description

  The present invention relates to a dental adhesive composition, and more particularly to a dental adhesive composition useful as a dental primer, a dental bonding material, an adhesive composite resin, a dental resin cement, and the like.

  In the field of dental materials, a composite resin in which a filler made of inorganic particles is highly blended with a polymerizable monomer is used to restore a tooth having a defect caused by caries or the like. However, since the composite resin has almost no adhesion to the teeth, the restoration tooth surface is subjected to etching treatment and priming treatment prior to its use, and then a dental bonding material is applied thereon. -It is necessary to cure.

  In recent years, as a polymerizable monomer, those containing an acidic group have demineralized the tooth and dissolved the smear layer on the cutting surface, and also have a high affinity with the tooth, so water and It has been found that if a hydrophilic solvent and a small amount of an inorganic filler are blended as required and used as a dental primer, the etching treatment and the priming treatment can be performed simultaneously (self-etching primer). Further, by developing this knowledge and adding an acidic group-containing polymerizable monomer to the polymerizable monomer component of the bonding material, it is possible to treat teeth without requiring any of these complicated pretreatments. It has also been confirmed that high adhesiveness can be obtained (self-etching type bonding material; see Patent Documents 1 and 2).

  Furthermore, the so-called adhesive composite resin, in which the acidic group-containing polymerizable monomer is contained in the composite resin and directly adheres to the teeth without using a bonding material, has also been proposed. (See Patent Document 3).

  In addition, when cementing prostheses such as inlays and crowns to the cavity of a tooth, there is also a resin cement made of a curable composition containing a high content of inorganic filler containing an acidic group-containing polymerizable monomer. It is used.

  In the curable composition used for the purpose of adhering to these teeth, that is, the dental adhesive composition, first, the adhesive composite resin or resin cement is highly blended with inorganic particles as a filler as described above. Has been. In addition, inorganic particles are appropriately added to dental primers and dental bonding materials for the purpose of improving the mechanical strength of the cured product. However, even if these inorganic particles are blended as they are or are subjected to a surface treatment, they are only known to be treated with a silane coupling agent for the purpose of improving affinity for polymerizable monomers and forming chemical bonds. Not.

  In addition, it is known that the dental curable composition contains inorganic particles having a sulfonic acid group on the surface as a catalyst component that accelerates the polymerization and curing reaction (see Patent Document 4). However, the use of this dental curable composition is specifically a denture base lining material ([0014]), and is not a use requiring adhesion to the above-mentioned teeth. Even so, those containing an acidic group effective to enhance the adhesion to the teeth are not necessary to be blended, and since it causes irritation and sourness, it is rather undesirable to contain them. ([0030]).

JP2008-189579 JP 2005-263630 A JP2008-189579 JP 2005-263630 A

  As described above, in a dental adhesive composition in which a polymerizable monomer and an inorganic filler are blended, an acidic group-containing polymerizable monomer is contained as at least a part of the polymerizable monomer component. Adhesiveness to teeth is greatly improved, which is preferable. However, the adhesive strength is still not sufficient and further improvement has been desired. In particular, in order to increase the mechanical strength of the cured body itself, when the inorganic filler is highly blended, the content of the acidic group-containing polymerizable monomer is relatively reduced by that amount, so that the adhesive strength is increased. The decline was a big problem.

  As a result of intensive studies to solve the above problems, the present inventors have used the above-described inorganic particles to be blended as inorganic fillers by using those having acidic groups on the surface. The present inventors have found that the problem can be solved and have completed the present invention.

That is, the present invention relates to a polymerizable monomer component (A) comprising an acidic group-containing polymerizable monomer a1) and an inorganic filler component comprising inorganic particles b1) having acidic groups on the surface ( B)
It is a dental adhesive composition characterized by containing.

  According to the present invention, in a dental adhesive composition containing a polymerizable monomer component containing an acidic group-containing polymerizable monomer and an inorganic filler component, at least one of the inorganic filler components Since some of them have an acidic group on the surface, the adhesive force to the teeth can be greatly increased. The reason why the adhesion force to the tooth is improved by using the inorganic particles having an acidic group on the surface in this way is that the amount of the acidic group may increase at the contact interface with the tooth. It is expected that the trapping ability of calcium ions generated by quality demineralization and dissolution of the smear layer is greatly enhanced.

  That is, the decalcification of the tooth due to acidic groups and the dissolution of the smear layer are such that the calcium ions generated by the action are not diffused and removed through the acidic groups present in the dental adhesive composition layer. The effect does not increase. Thus, if inorganic particles as fillers are dispersed in the dental adhesive composition layer, the trapping ability of the calcium ions is hindered in the presence of the particles, and the calcium ions are in contact with the tooth surface. It remains at the contact interface, and the decalcification and smear layer dissolving action does not appear uniformly. On the other hand, in the present invention, since an acidic group is also present on the surface of the inorganic particles, this obstruction is improved, and the trapping ability of calcium ions is homogenized in the layer, so that the demineralization of the tooth is performed. It is thought that the solubility of the smear layer is greatly improved.

  Thus, the dental adhesive composition of the present invention having a high adhesive force to teeth is extremely useful as a dental primer, a dental bonding material, an adhesive composite resin, a dental resin cement, and the like.

  Hereinafter, each component of the dental adhesive composition of the present invention will be described.

[(A) polymerizable monomer component]
In the dental adhesive composition of the present invention, as the polymerizable monomer, known polymerizable compounds such as radical polymerizable monomers and cationic polymerizable monomers can be used without any particular limitation. From the viewpoint of the polymerization rate, it is preferable to use a radical polymerizable monomer from the viewpoint of dental use. Preferred radical polymerizable groups include (meth) acryloyl groups, (meth) acryloyloxy groups, (meth) acryloylamino groups, (meth) acryloyl group derivative groups such as (meth) acryloylthio groups, vinyl groups, or And a styryl group. Of these, a (meth) acryloyl group, a (meth) acryloyloxy group, or a (meth) acryloylamino group is preferable from the viewpoint of polymerizability, and a (meth) acryloyloxy group is more preferable.

a1) Acidic group-containing polymerizable monomer The dental adhesive composition of the present invention contains an acidic group-containing polymerizable monomer as at least a part of the polymerizable monomer component. The acidic group-containing polymerizable monomer can be used without limitation as long as it is a polymerizable monomer having at least one acidic group in one molecule. Here, the acidic group is a functional group having a pKa of less than 5 and capable of dissociating active protons, and specifically includes a phosphoric acid group (phosphoric monoester group or phosphoric diester group), carboxyl group, sulfone. An acid group, a phosphone group, etc. can be mentioned. Among these, carboxyl groups and phosphate groups are more preferable as acidic groups having high adhesiveness to teeth, and phosphate groups are most preferable.

  Specific examples of such acidic group-containing radical polymerizable monomers include 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, (meth) acryloyloxyethyl dihydrogen phosphate, bis ((meth) acryloyloxy). Phosphoric acids such as ethyl) hydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, bis ((meth) acryloyloxyhexyl) hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate Group-containing radical polymerizable monomers; phosphonic acid group-containing radical polymerizable monomers such as vinylphosphonic acid; 2- (meth) acryloyloxyethyl hydrogen maleate, 2- (meth) acryloyloxye Hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxyethyl-1,1-undecanedicarboxylic acid, 2- (meth) acryloyloxyethyl-3′- Methacryloyloxy-2 ′-(3,4-dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, N- (meth) acryloylglycine, N -Carboxylic acid group-containing radical polymerizable monomers such as (meth) acryloyl aspartic acid; styrene sulfonic acid, 3-sulfopropane (meth) acrylate, 2- (meth) acrylamide-2-methylpropanesulfonic acid, etc. And sulfonic acid group-containing radical polymerizable monomers. Moreover, these acidic group-containing radically polymerizable monomers may be used in combination of two or more if necessary.

  These acidic group-containing polymerizable monomers a1) are not limited in their blending amounts, and the entire polymerizable monomer component may be only the acidic group-containing polymerizable monomer. From the viewpoint of adjusting the permeability to the tooth in the primer and the bonding material, and improving the mechanical strength of the cured product, it is preferable to use it together with the acidic group-free polymerizable monomer a2).

a2) Non-acidic group-containing polymerizable monomer Specific examples of non-acidic group-containing polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyethyl propionate, or 2- Water-insoluble (meth) acrylate monomers having one polymerizable unsaturated group such as methacryloxyethyl acetoacetate; 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (Meth) acrylate, polyethylene Water-soluble (meth) acrylate monomers having one polymerizable unsaturated group such as ethylene glycol mono (meth) acrylate or ethoxylated undecenol (meth) acrylate; nonaethylene glycol di (meth) acrylate, deca Water-soluble (meta) having a plurality of polymerizable unsaturated groups such as ethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, or pentaerythritol di (meth) acrylate ) Acrylate monomers, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol (Meth) acrylate, dipropylene 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, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol methane Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa Aliphatic water-insoluble (meth) acrylate monomers having a plurality of polymerizable unsaturated groups such as meth) acrylate or urethane dimethacrylate; or 2,2-bis ((meth) acryloxyphenyl) propane 2,2-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis Aromatic non-water-soluble compounds having a plurality of polymerizable unsaturated groups such as (4- (meth) acryloxypolyethoxyphenyl) propane or 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane ( And (meth) acrylate monomers.

  Among these non-acidic group-containing polymerizable monomers, polyfunctional ones having two or more polymerizable unsaturated groups are preferably used. These polymerizable monomers having no acidic group may be used alone or in combination of two or more.

[(B) Inorganic filler component]
b1) Inorganic particles having an acidic group on the surface In the inorganic particles having an acidic group on the surface, known inorganic particles can be applied without particular limitation as the core particles, and periodic groups I, II, III, IV, It can be selected from transition metals or their oxides or halides, sulfates, mixtures or composite salts thereof. Specifically, a single oxide or a complex oxide of a metal such as silicon, titanium, aluminum, zirconium, tin, or a semimetal, can be given. As the composite oxide, those containing alkali metal or alkaline earth metal such as sodium, potassium, magnesium and calcium are also suitable. Among these, silicon is a single oxide or a composite oxide containing silicon as a constituent element (hereinafter referred to as silicon-based oxidation) because of its excellent chemical stability and easy surface treatment with a silane coupling agent or the like. Are preferred. In addition, the refractive index of the inorganic particles is not particularly limited, but when a dental adhesive composition is used as an adhesive composite resin, from the viewpoint of color compatibility between the obtained cured product and a tooth, a general dental use The thing of the range of 1.4-1.7 which the inorganic filler of has is preferable.

  More specific examples of silicon-based oxides include silicas such as quartz, precipitated silica, fumed silica, sol-gel silica; silica-titania, silica-zirconia, silica-barium oxide, silica-lanthania, silica-alumina, silica -Calcia, silica-strontium oxide, silica-magnesia, silica-titania-sodium oxide, silica-titania-potassium oxide, silica-zirconia-sodium oxide, silica-zirconia-potassium oxide, silica-alumina-sodium oxide, or silica- Complex oxides such as alumina-potassium oxide; silicates such as calcium silicate, talc, zeolite, and montmorillonite. Among them, silica-zirconia and silica-titania are desirable for dental use from the viewpoint of refractive index and X-ray contrast.

  The shape of the inorganic particles is not particularly limited and may be appropriately selected according to the purpose of use. For example, any shape such as a spherical shape, a plate shape, a layer shape, a whisker shape, or an indefinite shape is applicable. When the dental adhesive composition is used as an adhesive composite resin, a spherical shape is preferable because the surface smoothness of the cured product is increased.

  Further, the average particle size and particle size distribution of the inorganic particles may be appropriately selected depending on the application, and are not particularly limited. The average primary particle size is preferably 0.005 to 50 μm, and more preferably 0.007 to 5 μm. When the dental adhesive composition is an adhesive composite resin or resin cement, the inorganic particles having the above average primary particle size are monodispersed without agglomeration from the viewpoint of the mechanical strength of the cured product and the paste viscosity. It is preferable. Here, the average primary particle diameter of the inorganic particles is the average value of the major axis of 300 primary particles observed for the particles measured with a transmission electron microscope or a scanning electron microscope.

  In addition, the inorganic particles may be agglomerated, particularly in the case where the dental adhesive composition is a primer and a bonding material, from the viewpoint of dispersibility in a polymerizable monomer, a solvent, paste viscosity, etc. It is a preferred embodiment to use as agglomerated particles. The average particle size of the aggregated particles is preferably 0.01 to 0.2 μm. The average particle diameter of the aggregated particles is an average particle diameter d50 measured using a laser diffraction / scattering particle size distribution meter.

In addition, the specific surface area of the inorganic particles is 80 to 400 m ² / g from the viewpoint of dispersibility in a polymerizable monomer, a solvent, etc. if the dental adhesive composition is a primer or a bonding material. Is more preferable, and it is more preferable that it is 100-300 m < ² > / g. In the case of a resin cement or an adhesive composite resin, it is preferably 0.2 to 60 m ² / g, more preferably 0.6 to 40 m ² / g from the viewpoints of operability when pasted and paste viscosity. It is more preferable that In the present invention, the specific surface area of the inorganic particles is a value measured by the BET method.

  The acidic group present on the surface of the inorganic particle corresponds to a functional group having a pKa of less than 5 and capable of dissociating active protons, as described in the acidic group-containing polymerizable monomer. Specific examples include a phosphoric acid group, a pyrophosphoric acid group, a phosphonic acid group, a thiophosphoric acid group, a carboxyl group, a sulfonic acid group, and a sulfinic acid group. From the viewpoint of stability when applied to the particle surface, a phosphoric acid group, a phosphonic acid group, a carboxyl group, and a sulfonic acid group are preferable, and since the calcium ion trapping ability is high and the adhesion to teeth is particularly high, phosphorus An acid group and a sulfonic acid group are more preferable.

These acidic groups are not only uniformly introduced over the entire surface of the inorganic particles, but may be scattered or partially introduced. The amount of acid groups present on the surface of the inorganic particles, from the viewpoint of improving the adhesion to a tooth of the dental adhesive composition is preferably at 0.3 [mu] mol / ^{m 2} or more, 1.2μmol / ^{m 2} or more It is more preferable that In addition, if the amount of acidic groups present on the surface of the inorganic particles is too large, the dental adhesive composition becomes a polymerizable monomer component containing no acidic group-containing polymerizable monomer (particularly hydrophobic). because there is a possibility that familiar becomes poor poor dispersion in the case of containing, preferably at 20 [mu] mol / ^{m 2} or less, more preferably 5 [mu] mol / ^{m 2} or less. Here, the amount of acidic groups present on the surface of the inorganic particles is such that 3 g of particles are added to 50 ml of a sodium chloride aqueous solution having a concentration of 0.5 mol / L, and the counter ions of the acidic groups are exchanged with sodium ions by stirring for 24 hours. After the protons are released, the particles are filtered off, and the obtained filtrate is obtained by neutralization titration with an aqueous sodium hydroxide solution. The specific surface area applied to determine the amount of acidic groups present on the surface of the inorganic particles is not the specific surface area of the raw inorganic particles, but the value of the inorganic particles after introducing acidic groups to the surface (BET method). ).

  Next, a method for producing inorganic particles having an acidic group on the surface, which is blended as the characteristic component in the present invention, will be described. Various methods for producing inorganic particles having acidic groups on the surface are already known. For example, inorganic particles can be converted into silane coupling agents having mercapto groups such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. By treating the resulting inorganic particles having a mercapto group on the surface with hydrogen peroxide, thereby converting the mercapto group into a sulfonic acid group. Particles can be produced.

  In the present invention, particularly suitable as a method for producing inorganic particles having an acidic group on the surface, the surface of the inorganic particle includes an acidic group or a polymerizable monomer having a functional group capable of introducing an acidic group and a polymerization initiator. When coated with a polymerizable composition and polymerized and cured to obtain polymer-coated inorganic particles, and the polymerizable composition having a functional group capable of introducing an acidic group is used. Includes a method of introducing an acidic group into the functional group. In this method, if a polymerizable monomer having an acidic group or a functional group capable of introducing an acidic group is attached to the particle surface, an acidic group can be introduced. Therefore, a silane coupling agent that needs to be reacted with a hydroxyl group. Compared with the surface treatment method using, it is advantageous because it can be widely applied regardless of the type of particles. In addition, when the monomer having an acidic group has a plurality of polymerizable groups, or when using an acidic group-containing polymerizable monomer having a plurality of polymerizable groups together with an acidic group-containing polymerizable monomer, Since the obtained cured product becomes a crosslinked polymer, it becomes a coating layer excellent in solvent resistance, acid resistance, heat resistance and the like, and it is preferable that acidic groups are not easily removed from the particle surface. On the other hand, it is known that the particle surface on which the silane coupling agent has been reacted is easily hydrolyzed by the bond between the surface hydroxyl group and the silane coupling agent.

  In this production method, if inorganic particles having a phosphate group are produced on the surface, examples of the polymerizable monomer having a phosphate group include 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3 -(Meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate 7- (meth) acryloyloxyheptyl dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- ( T) Acryloyloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate 20- (meth) acryloyloxyicosyl dihydrogen phosphate, bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- ( (Meth) acryloyloxyhexyl] hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyl Oxynonyl] hydrogen phosphate, bis [10- (meth) acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, bis [2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl] hydrogen phosphate, and the like can be used.

  Moreover, if the inorganic particle which has a phosphonic acid group on the surface is manufactured, as a polymerizable monomer which has a phosphoric acid group, 2- (meth) acryloyloxyethyl phenylphosphonate, 5- (meth) acryloyl, for example Oxypentyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) Acrylyloxyhexyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl-3-phosphonoacetate, vinylphosphonic acid and the like can be used.

  Further, if inorganic particles having a carboxyl group on the surface are produced, examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, maleic acid, and succinic acid 2- (meth) acryloyloxy. Ethyl, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate and the like can be used.

  Furthermore, when producing inorganic particles having a sulfonic acid group on the surface, examples of the polymerizable monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid. Vinyl naphthalene sulfonic acid can be used.

  In addition, if the inorganic particles having an acidic group on such a surface are produced using a polymerizable monomer having a functional group capable of introducing an acidic group, the polymerizable monomer used for this is as follows. For example, if the acidic group is a sulfonic acid group, an aromatic hydrocarbon polymerizable monomer such as styrene or divinylbenzene, a polymerizable monomer having a mercapto group, or the like may be used. By polymerizing and curing the former aromatic hydrocarbon-based polymerizable monomer to obtain inorganic particles coated with an aromatic hydrocarbon-based polymer, by treating with concentrated sulfuric acid or sulfur trioxide, A sulfonic acid group can be introduced into the aromatic ring of the aromatic hydrocarbon polymer. Furthermore, the latter polymerizable monomer having a mercapto group is polymerized and cured to obtain inorganic particles coated with a mercapto group-containing polymer, and then treated with hydrogen peroxide to convert the mercapto group into a sulfonic acid group. Can be converted to In addition, in the polymerizable monomer having each acidic group, the compound in which the acidic group is a salt is also polymerized and cured to form a polymer having a salt of the acidic group, and then the acidic group is liberated. By making it, it can be used as a polymerizable monomer having a functional group capable of introducing the acidic group.

  In addition to the acidic group or the polymerizable monomer having a functional group that can be introduced into the acidic group, a crosslinkable monomer is preferably used in combination with the polymerizable composition that covers the surface of the inorganic particles. By containing a crosslinkable monomer in the polymerizable composition, as described above, the obtained cured product becomes a crosslinked polymer, and can be a coating layer excellent in solvent resistance, acid resistance, heat resistance, and the like. . The crosslinkable monomer can be appropriately used as long as it is a monomer having two or more polymerizable groups. For example, a polyfunctional fragrance such as divinylbenzene, divinylbenzene, divinylbiphenyl, trivinylbenzene, and divinylnaphthalene. Group vinyl-based polymerizable monomers; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolmethane tri (meth) acrylate, trimethylolprotan tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acryl Polyfunctional (meth) acrylic polymerizable monomers such as benzoate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, methylenebis (meth) acrylamide, hexamethylenedi (meth) acrylamide, etc. Can be mentioned.

  The amount of the crosslinkable polymerizable monomer used is desirably 0.1 to 50 parts by weight, more preferably 1 to 100 parts by weight of the polymerizable monomer having an acidic group or a functional group capable of being introduced into the acidic group. -30 parts by weight.

  After the surface of the inorganic particles is coated with the polymerizable composition, a polymerization initiator is blended in the polymerizable monomer in order to polymerize and cure the inorganic particles. The polymerization initiator may be appropriately selected from known ones according to the polymerizable monomer to be used, but is preferably a thermal polymerization initiator from the viewpoint of simplicity of the polymerization operation. Such thermal polymerization initiators include octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxylaurate. , T-hexylperoxybenzoate, di-t-butyl peroxide, and other organic peroxides, 2,2, -azobisisobutyronitrile, 2,2, -azobis- (2,4, -dimer) Azobis-based polymerization initiators such as valeronitrile). Of these, those having an appropriate half-life may be used alone or in combination of two or more depending on the polymerization temperature. The polymerization temperature is preferably from 50 to 230 ° C., but more preferably from 70 to 120 ° C. from the viewpoint of the service temperature of the treatment apparatus used, the homogeneity of the particles obtained, the heat resistance of the acidic groups introduced onto the surface, and the like.

  The amount of the polymerization initiator used is not particularly limited as long as it is an effective amount, but is generally 0.1 to 20 parts by mass, more preferably 0.5 to 100 parts by mass of the polymerizable monomer. -10 parts by mass.

  In addition, other polymerizable monomers, water, a hydrophilic solvent, and the like may be blended as optional components in the polymerizable composition that covers the surface of the inorganic particles. For example, when a polymerizable monomer having a sulfonic acid group that is a strongly hydrophilic acidic group is used, hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate are used. By adding a polymerizable monomer having water, water, alcohols, acetone, or the like, the affinity with the crosslinkable polymerizable monomer or the polymerization initiator can be improved. When water or a hydrophilic solvent is contained, if the amount used is too large, the particles tend to aggregate. Therefore, the amount used is preferably suppressed to an amount that maintains the powder properties of the inorganic particles (does not become paste or liquid) when the polymerizable composition is brought into contact with the inorganic particles. Generally, it is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total polymerizable monomer contained in the polymerizable composition.

  Furthermore, additives, such as a polymerization inhibitor, a polymerization inhibitor, and an ultraviolet absorber, can be appropriately added to the polymerizable composition.

The coating amount of the polymerizable composition on the surface of the inorganic particles is not particularly limited, but may be appropriately adjusted so that the amount of acidic groups introduced into the surface of the inorganic particles is within the preferable range. The specific coating amount of the polymerizable composition is generally unrelated to the specific surface area and particle diameter of the inorganic particles used, but generally 0.1 to 2 mg / m 2 per unit specific surface area of the inorganic particles. ² is preferred. The inorganic particles are coated with the polymerizable composition. When the coating amount is too large, aggregation of particles becomes severe. Therefore, it is more preferable to coat with 0.3 to 1 mg / m ² per unit specific surface area of the inorganic particles. preferable. The coating of the polymerizable composition may be carried out over the entire surface so that the surface of the inorganic particles is not exposed. However, when the coating is carried out at a coating amount suitable for introduction of such acidic groups, The surface state is presumed to be a state in which the coated portion and the portion where the surface of the inorganic particles is exposed without being coated are mixed in a sea island shape or the like.

  The coating method of the polymerizable composition on the surface of the inorganic particles is not particularly limited. For example, an acidic group or a polymerizable monomer having a functional group that can be introduced into the acidic group (or an optional component is added thereto) And the inorganic particles are brought into contact with each other under stirring. In addition, a method of adding a polymerizable monomer having an acidic group or a functional group that can be introduced into the acidic group to the inorganic particles by spraying or dropping is also suitable. A known spray nozzle or the like can be suitably used for spraying. In the case of dripping, it is preferable to use a drip tube having a small diameter or connect an injection needle or a capillary tube to the tip of the tube so that the droplet becomes small. The addition rate is desirably about 1 to 5 ml / min per 100 g of inorganic particles from the viewpoint of preventing particle aggregation. Although the temperature condition of addition is not particularly limited, 0-40 ° C. is necessary from the viewpoint of sufficiently spreading the polymerizable monomer between the inorganic particles and preventing the polymerizable monomer from causing thermal polymerization. preferable.

  The polymerization and curing of the polymerizable monomer covering the surface of the inorganic particles is preferably carried out by heating the particles with stirring. Further, it is desirable to proceed the reaction in an atmosphere of an inert gas such as nitrogen or argon. As an apparatus capable of performing polymerization while satisfying such conditions, for example, an autoclave, a granulator, and the like can be used in addition to a powder stirring apparatus such as a Henschel mixer, a Ladige mixer, a rocking mixer, and a drum mixer. The pressure in the reaction vessel is not particularly limited, and may be pressurized, normal pressure, or reduced pressure. Although depending on the kind of the polymerizable monomer used, a normal pressure or a slightly pressurized state is preferable among them. Slightly pressurized means that when the added polymerizable monomer and other optional components are heated from room temperature, some of them become steam, and the pressure inside the reaction vessel rises. The pressure is approximately 0.005 to 0.2 MPa. The polymerization time may be appropriately set according to the other conditions as described above, and is generally about 30 to 180 minutes.

  As described above, inorganic particles coated with an acid group or a polymer having a functional group capable of introducing an acid group can be obtained. The coating of the inorganic particles with the polymer is not only in the state of covering the outer surface, but also in the case where the particles have pores, the state of covering the wall surfaces of the pores or the pores. It includes the state that exists so as to fill, and also the state in which they are combined.

  When inorganic particles coated with a polymer having a functional group capable of introducing an acidic group are obtained, the acidic group may be introduced into the functional group by a conventional method as described above. Moreover, the manufacturing method demonstrated above has described the processing method by the dry type which suppressed the usage-amount of the solvent to the small quantity even if it used. Inorganic particles having acidic groups on the surface may be produced by a wet method, but the dry method requires separation of the resulting polymer-coated particles from the solvent and drying compared to a wet method using a large amount of solvent. There is no advantage.

b2) Other inorganic fillers In the dental adhesive composition of the present invention, the inorganic filler component may use only inorganic particles having acidic groups on the surface, but the treatment of imparting acidic groups to the surface may be performed. You may mix and use the normal inorganic filler which has not been given. In particular, when used in adhesive composite resins and dental resin cements, these are paste-like and highly blended with inorganic fillers, so it is preferable to use them together with inorganic fillers that do not introduce acidic groups on the surface. .

  As these inorganic fillers, the particles listed as the core particles with the inorganic particles having an acidic group on the surface can be preferably used. The same is true for silicon oxides. Further, glasses such as lanthanum glass, barium glass, strontium glass, silicate glass, and fluoroaluminosilicate glass can also be suitably used.

  In order to improve familiarity and improve mechanical properties when these inorganic fillers contain an acidic group-free polymerizable monomer (especially hydrophobic) as a polymerizable monomer component, You may perform the surface treatment which improves hydrophobicity. Examples of such surface treatment agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, dimethyldimethoxysilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, and vinyltris (β-methoxyethoxy). Silane, γ-methacryloyloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, silane coupling agents such as γ-glycidoxypropyltrimethoxysilane, silazanes such as hexamethyldisilazane, cyclic siloxane, silicone oil, Titanate coupling agents, aluminate coupling agents, zirco-aluminate coupling agents, and the like are preferably used.

  In addition, when the use of the dental adhesive composition is an adhesive composite resin or a dental resin cement, since it is chemically bonded to the polymerizable monomer and the mechanical strength is improved, γ-methacryloyl is particularly preferred. It is more preferable to use a silane coupling agent having a (meth) acryloxy group such as oxypropyltrimethoxysilane.

[(C) water]
When the dental adhesive composition of the present invention is used for an application to adhere to teeth even if it does not contain water, it is removed by an acidic group-containing polymerizable monomer due to moisture in the oral cavity at the contact interface. The ash (etching) action proceeds well. Furthermore, the inclusion of water is preferable because the decalcification (etching) action of the tooth is enhanced, the affinity for the tooth is also enhanced, and the adhesive force with the tooth is greatly improved. In particular, it is effective to add water to the dental primer and the dental bonding material.

  The water to be blended is desirably free of impurities, and it is preferable to use distilled water or ion exchange water.

[(D) Polymerization initiator]
In the dental adhesive composition of the present invention, when the use is a dental bonding material, an adhesive composite resin, and a dental resin cement, a polymerization initiator is blended. The polymerization initiator is classified into a chemical polymerization type and a photopolymerization type, and may be appropriately selected according to the purpose. Usually, a chemical polymerization initiator is used for a dental resin cement, and a photopolymerization initiator is used for a dental bonding material, an adhesive composite resin, and a dental resin cement.

  The chemical polymerization initiator is composed of a combination of two or more components, and each component is distributed to each package of the dental adhesive composition prepared by dividing into two or more packages, and each package is mixed at the time of use ( It generates radicals when they are in contact. For example, organic peroxides / amines, organic peroxides / amines / organic sulfinic acids, organic peroxides / amines / aryl borates, aryl borates / acidic compounds, and barbituric acid derivatives / copper compounds / What consists of various combinations, such as a halogen compound, is mentioned.

  In the present invention, chemical polymerization initiators composed of organic peroxides / amines and organic peroxides / amines / aryl borates are preferred because high adhesive strength to teeth can be obtained and handling is easy. It is. Typical organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide; 2,5-dimethylhexane-2,5-dihydroperoxide Hydroperoxides such as oxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide; acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3, 5, 5- Diacyl peroxides such as trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide; di-t-butyl peroxide Id, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2 Dialkyl peroxides such as 1,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t- Peroxyketals such as butylperoxy) valeric acid-n-butyl ester; α-cumylperoxyneodecanoate, t-butylperococineodecane , T-butylperoxypivalate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2- Ethyl hexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate Peroxyesters such as t-butylperoxybenzoate and t-butylperoxymaleic acid; di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butyl Tilhexyl) peroxydicarbonate, diisopropylperoxydicarbonate , Di -n- propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, etc. peroxydicarbonate such as diallyl peroxydicarbonate and the like. Among these organic peroxides, benzoyl peroxide is particularly preferably used from the viewpoint of radical generation ability and stability.

  On the other hand, the amines combined with the organic peroxide are not particularly limited, and examples thereof include secondary or tertiary aromatic amines in which an amino group is bonded to an aromatic group such as an aryl group or a pyridyl group. . For example, examples of the secondary aromatic amine that can be suitably used include N-methylaniline, N- (2-hydroxyethyl) aniline, N-methyl-p-toluidine, and the like. Examples of the tertiary aromatic amine that can be suitably used include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N- Methyl-N- (2-hydroxyethyl) aniline, N, N-di (2-hydroxyethyl) aniline, p-bromo-N, N-dimethylaniline, p-chloro-N, N-dimethylaniline, N, N -Dimethyl-p-toluidine, N, N-diethyl-p-toluidine, p-tolyldiethanolamine, N-methyl-N- (2-hydroxyethyl) -p-toluidine, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone P-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester N, N-dimethylanthranic acid methyl ester, p-dimethylaminophenethyl alcohol, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine and the like can be mentioned.

  Among these amines, p-tolyldiethanolamine and N, N-dimethyl-p-toluidine are particularly preferably used from the viewpoint of curability.

  The aryl borate is a borate compound having 1 to 4 boron-aryl bonds in one molecule, and preferably a borate compound having 3 to 4 boron-aryl bonds in one molecule.

  Specifically, salts of borates having 3 or 4 boron-aryl bonds in one molecule, for example, metal salts such as sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium Salts, ammonium salts such as tetraethylammonium salt, tributylammonium salt, triethanolammonium salt, pyridinium salts such as methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, or methylquinolinium salt, ethylquinolinium salt, butylchi A quinolinium salt such as a norinium salt can be given. Here, as a borate compound having three boron-aryl bonds in one molecule, monoalkyltriphenylboron, monoalkyltris (p-chlorophenyl) boron, monoalkyltris (p-fluorophenyl) boron, monoalkyl Tris (3,5-bistrifluoromethyl) phenyl boron, 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-butyl) Oxy phenyl) boron, monoalkyl tris (p- octyloxyphenyl) boron, a monoalkyl tris (m-octyloxyphenyl) boron can be exemplified. In addition, borate having four boron-aryl bonds in one molecule includes 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-octi) It can be exemplified oxyphenyl) boron. In the above borate, alkyl is either n-butyl, n-octyl or n-dodecyl.

  Among these aryl borates, a triethanolammonium salt of tetraphenylboron is particularly preferably used from the viewpoint of curability.

  In the chemical polymerization initiator composed of organic peroxide / amines, the amines should be used in an amount of 0.01 to 4 mol, particularly 0.05 to 3 mol, per 1 mol of the organic peroxide.

  In the organic peroxide / amines / aryl borates, the amines are used in an amount of 0.01 to 4 moles, particularly 0.05 to 3 moles per mole of the organic peroxide. It may be used in an amount of 01 to 3 mol, in particular 0.05 to 2 mol.

  As the photopolymerization initiator, those that generate radicals when irradiated with light of 380 to 500 nm, which is often used as an irradiation wavelength of a dental irradiator, are preferable. Examples of such photodeposition initiators include α-ketocarbonyl compounds and acyl phosphine oxide compounds.

  Examples of the α-ketocarbonyl compound include α-diketone, α-ketoaldehyde, and α-ketocarboxylic acid ester. Specifically, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl, 4,4′-dimethoxybenzyl, 4,4′-diethoxybenzyl, 4,4′-oxybenzyl, 4,4 ′ Α-diketones such as dichlorobenzyl, 4,4′-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, camphorquinonesulfonic acid ester, camphorquinonecarboxylic acid ester or 2,2′-cyclohexanedione, methyl Examples include α-ketoaldehydes such as glioxal and phenylglyoxal, α-ketocarboxylic acid esters such as methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate and butyl phenylpyruvate.

  Of these α-ketocarbonyl compounds, α-diketones are preferably used from the standpoint of stability and the like. Among α-diketones, diacetyl, benzyl or camphorquinone is more preferable, and camphorquinone is particularly preferable.

  Examples of the acylphosphine oxide compound include benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2, Examples include 4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  Among the photopolymerization initiators described above, α-ketocarbonyl compounds are more preferable from the viewpoint of the depth of curing. These photopolymerization initiators may be used alone or in combination of two or more.

  When a photopolymerization initiator is used as the polymerization initiator, it is preferable to use a polymerization accelerator in combination in order to improve the polymerization initiation ability and promote the polymerization reaction. In particular, when an α-ketocarbonyl compound is used as a photopolymerization initiator, it is effective to incorporate a reducing compound such as amines. When amines are specifically exemplified, tertiary aromatic amines shown as those combined with organic peroxides in the above-described chemical polymerization initiator can be preferably used.

  Among these, since the basicity is relatively low and the neutralization reaction with the acidic group of the acidic group-containing polymerizable monomer contained in the composition hardly occurs, the corresponding ammonium ion pKa in 25 ° C. water It is preferable to use an amine compound having a value of 9 or less, particularly preferably a pKa value of 7 or less. Such low basic amines generally correspond to tertiary aromatic amine compounds, and may be appropriately selected from those exemplified above. Among them, p-dimethylaminobenzoic acid ethyl ester is preferably used.

  The compounding amount of the amines used in combination with these photopolymerization initiators is generally 0.1 to 10 times, more preferably 0.3 to 5 times that of the photopolymerization initiator.

[Dental adhesive composition]
The dental adhesive composition of the present invention can be obtained by sufficiently kneading predetermined amounts of each of the above components and various optional components and defoaming under reduced pressure as necessary. The blending amount of each component is not particularly limited, and an effective amount may be blended according to the use of the dental adhesive composition. If the acidic group-containing polymerizable monomer a1) is used in combination with the non-acidic group-containing polymerizable monomer a2), the acidic group-containing polymerizable monomer in (A) the polymerizable monomer component a1) is contained in a range of 5% by mass or more, more preferably in a range of 5 to 60% by mass, particularly preferably in a range of 10 to 40% by mass from the viewpoint of improving the adhesive strength to both enamel and dentin. Is preferred. In addition, the inorganic particle b1) having an acidic group on the surface, which is a characteristic component of the present invention, is (A) an acidic group-containing polymerizable monomer in order to sufficiently exhibit the effect of improving adhesion to teeth. It is good to mix 5 parts by mass or more, particularly preferably 15 parts by mass or more, and most preferably 20 parts by mass or more with respect to 100 parts by mass of the polymerizable monomer component comprising the body. Moreover, even if it mix | blends too much, since an effect will reach a peak and a composition will become high viscosity, A) It is with respect to 100 mass parts of polymerizable monomer components containing an acidic group containing polymerizable monomer. It is preferable to blend at a ratio of 500 parts by mass or less, particularly 300 parts by mass or less.

  Furthermore, if the compounding amount of other optional components is generalized, when (B) the inorganic filler b2) is used in combination with the inorganic particles b1) having acidic groups on the surface as the inorganic filler component, The total amount of the composition is so high that the composition becomes highly viscous. Therefore, the lower limit of the preferred blending amount of the inorganic particles b1) having acidic groups on the surface is satisfied, but partly within the range not exceeding the upper limit. It is preferable to blend in place of.

  In addition, when there is too much (C) water, since there is a tendency to decrease the mechanical strength of the cured product and the storage stability of the composition, considering the balance with the blending effect, (A) acidic group-containing polymerization It is preferable to use it in the range of 110 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer component containing the polymerizable monomer. Further, (D) the polymerization initiator is not particularly limited as long as it is an effective amount, but (A) based on 100 parts by mass of the polymerizable monomer component containing the acidic group-containing polymerizable monomer. The amount is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight.

According to the application of the dental adhesive composition, if a preferable composition is shown,
(A) a polymerizable monomer component comprising an acidic group-containing polymerizable monomer a1),
(B) It becomes a composition containing the inorganic filler component which contains the inorganic particle b1) which has an acidic group on the surface, and (C) water. The blending ratio of each component is
(A) With respect to 100 parts by mass of the polymerizable monomer component comprising 5% by mass or more of the acidic group-containing polymerizable monomer a1),
(B) The inorganic filler component is 5 to 35 parts by mass, of which 5 parts by mass or more are occupied by the inorganic particles b1) having acidic groups on the surface.
(C) It is suitable that it is 15-110 weight part of water. Furthermore, it is desirable to add a hydrophilic organic solvent to these dental primers in order to improve operability and improve water dispersibility. For example, an organic solvent such as acetone, ethanol or isopropyl alcohol is preferably used because it has high volatility and can be easily dried as described below. The content of the hydrophilic organic solvent is preferably 20 to 400 parts by mass and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer component (A) described above.

Further, when the use of the dental adhesive composition is a dental bonding material, a preferred composition is
(A) a polymerizable monomer component comprising an acidic group-containing polymerizable monomer a1),
(B) It becomes a composition containing the inorganic filler component which contains the inorganic particle b1) which has an acidic group on the surface, and (D) a polymerization initiator. The blending ratio of each component is
(A) With respect to 100 parts by mass of the polymerizable monomer component comprising 5% by mass or more of the acidic group-containing polymerizable monomer a1),
(B) The inorganic filler component is 5 to 35 parts by mass, and among these, 5 parts by mass or more is occupied by the inorganic particles b1) having acidic groups on the surface. (D) It is an effective amount of the polymerization initiator. Is preferred. Furthermore, it is preferable that these dental bonding materials contain (C) water in order to enhance the self-etching ability, and the blending amount thereof is based on 100 parts by mass of the above-described (A) polymerizable monomer component. It is preferably 2 to 25 parts by weight. Furthermore, it is preferable that the dental bonding material contains the same amount of hydrophilic organic solvent as in the case of the dental primer.

Furthermore, when the use of the dental adhesive composition is an adhesive composite resin, the preferred composition is
(A) a polymerizable monomer component comprising an acidic group-containing polymerizable monomer a1),
(B) It becomes a composition containing the inorganic filler component which contains the inorganic particle b1) which has an acidic group on the surface, and (D) a polymerization initiator. The blending ratio is based on 100 parts by mass of the polymerizable monomer component comprising 5% by mass or more of (A) acidic group-containing polymerizable monomer a1).
(B) The inorganic filler component is 100 to 500 parts by mass (more preferably 120 to 300 parts by mass), of which 15 parts by mass or more are occupied by the inorganic particles b1 having acidic groups on the surface (D). An effective amount of polymerization initiator is preferred. Furthermore, it is preferable that these adhesive composite resins also contain (C) water in order to enhance the self-etching ability, and the blending amount thereof is based on 100 parts by mass of the above-described (A) polymerizable monomer component. The amount is preferably 0.5 to 10 parts by weight.

Furthermore, when the use of the dental adhesive composition is a dental resin cement, the preferred composition is
(A) a polymerizable monomer component comprising an acidic group-containing polymerizable monomer a1),
(B) It becomes a composition containing the inorganic filler component which contains the inorganic particle b1) which has an acidic group on the surface, and (D) a polymerization initiator. The blending ratio is based on 100 parts by mass of the polymerizable monomer component comprising 5% by mass or more of (A) acidic group-containing polymerizable monomer a1).
(B) The inorganic filler component is 100 to 500 parts by mass (more preferably 120 to 300 parts by mass), of which 30 parts by mass or more are occupied by the inorganic particles b1 having acidic groups on the surface (D). An effective amount of polymerization initiator is preferred. Furthermore, it is preferable that these dental resin cements contain (C) water in order to enhance the self-etching ability, and the blending amount thereof is based on 100 parts by mass of the above-described (A) polymerizable monomer component. The amount is preferably 0.5 to 10 parts by weight.

  In the case of dental resin cement, the polymerization initiator is usually a chemical polymerization type, or a combination of the chemical polymerization type and a photopolymerization type. As described above, the chemical polymerization type polymerization initiator is composed of two or more components, and these are mixed at the time of use so that the polymerization initiating ability is exhibited. It will be divided into the above. In this case, one package contains the acidic group-containing polymerizable monomer a1) and the inorganic particles b1) having acidic groups on the surface, and the other package contains no acidic group-containing polymerizable monomer. In view of storage stability, it is preferable to divide the composition so that b2) and other inorganic fillers b2) are contained.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not restrict | limited to these Examples. First, the compounds used, their abbreviations, and methods for measuring each physical property value will be described.
(1) Compounds used and their abbreviations [acidic group-containing polymerizable monomer]
PM: a mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate in a ratio of 2: 1 by mass MHP: 6-methacryloxyhexyl dihydrogen phosphate and Mixture in which bis (2-methacryloyloxyhexyl) hydrogen phosphate is mixed at a mass ratio of 2: 1 [acid group-free polymerizable monomer]
HEMA: 2-hydroxyethyl methacrylate Bis-GMA: 2,2′-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane 3G: triethylene glycol dimethacrylate [inorganic particles]
F1: Fumed silica (Reorosil QS-102 manufactured by Tokuyama Corporation, average primary particle size 0.01 μm).
F2: Spherical silica-zirconia (average particle size 0.4 μm) surface-treated with γ-methacryloyloxypropyltrimethoxysilane and spherical silica-titania (average particle size 0.08 μm) γ-methacryloyloxypropyltrimethoxy A mixture obtained by mixing a surface-treated product with silane at a mass ratio of 7: 3 [photopolymerization initiator]
CQ: camphorquinone BPO: benzoyl peroxide [amines]
DMBE: ethyl p-N, N-dimethylaminobenzoate DEPT: p-tolyldiethanolamine [arylborates]
PBTEOA: Triethanolammonium salt of tetraphenylboron [volatile hydrophilic organic solvent]
Acetone [Polymerization inhibitor]
BHT: 2,6-di-t-butyl-p-cresol

(2) Measuring method of each physical property value [Average primary particle diameter of inorganic particles]
The average primary particle diameter of the inorganic particles was the average value of the major diameters of 300 primary particles observed for the particles measured with a transmission electron microscope or a scanning electron microscope.

[Specific surface area of inorganic particles]
The specific surface area applied to determine the amount of acidic groups present on the surface of the inorganic particles was determined by the BET method (one-point method) using a specific surface area measuring device (manufactured by Shimadzu Corporation: Flowsorb 2-2300 type). The powder used in the measurement was previously dried in a nitrogen gas flow at 100 ° C. for 1 hour.

[Method for measuring the amount of acidic groups present on the surface of inorganic particles]
The amount of acidic groups present on the surface of the inorganic particles was determined by adding 3 g of particles to 50 ml of a 0.5 mol / L sodium chloride aqueous solution and stirring for 24 hours to exchange protons of the acidic groups with sodium ions and thereby protons. After the release, the particles are filtered, and the obtained filtrate is a value obtained by neutralization titration with an aqueous sodium hydroxide solution.

[Adhesive strength test method]
(Adhesive strength test when the dental adhesive composition is a dental primer)
The bovine anterior teeth removed within 24 hours after slaughter were polished with water-resistant abrasive paper P600 under water injection, and the enamel and dentin planes were cut out so as to be parallel and flat with the labial surface. Next, compressed air was blown onto the machined plane for about 10 seconds to dry. Next, a double-sided tape having a hole with a diameter of 3 mm is affixed to this plane, and a paraffin wax having a hole with a thickness of 0.5 mm and a diameter of 8 mm is placed at the center of the hole of the double-sided tape previously attached, A simulated cavity was formed by fixing the center of the paraffin wax hole together. A dental primer was applied to the simulated cavity, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Furthermore, a dental bonding material (3 MESPE Scotch Bond) is applied on the surface, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Further, a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) Was irradiated with visible light for 10 seconds. Further, a composite resin (Esterite Sigma Quick manufactured by Tokuyama Dental Co., Ltd.) was filled, pressed with a polyester sheet, and then cured by irradiation with visible light for 10 seconds after filling to prepare an adhesion test piece.

  Resin cement (Bistite II made by Tokuyama Dental Co., Ltd.) was applied to the upper surface of the cured composite resin body of the above-mentioned adhesion test piece, and a cylindrical SUS attachment having a diameter of 8 mm and a length of 25 mm was further adhered. After the resin cement was cured at 37 ° C. for 15 minutes, the test piece was immersed in water at 37 ° C. for 24 hours. Thereafter, the test piece was pulled at a crosshead speed of 1 mm / min using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), and the tensile adhesive strength between the tooth and the cured composite resin was measured. Tensile bond strength was measured for each of the four test pieces for each example or each comparative example. The average value of the four times of tensile adhesive strength was used as the adhesive strength of the corresponding Example or Comparative Example.

(Adhesive strength test when the dental adhesive composition is a dental bonding material)
Similar to the adhesive strength test method in the case where the above-mentioned dental adhesive composition is a dental primer, a ground beef extraction front tooth is prepared and has a similar adhesive surface of 3 mm in diameter with double-sided tape and paraffin wax. A simulated cavity was created. A bonding material was applied to the simulated cavity, left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Visible light irradiation was performed for 10 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) to cure the bonding material. Furthermore, a composite resin (Esterite Sigma Quick manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, pressure-contacted with a polyester sheet, and then cured by irradiation with visible light for 10 seconds after filling to prepare an adhesion test piece.

  Using this adhesion test piece, the adhesion strength between the tooth and the cured composite resin was determined in the same manner as the adhesion strength test method in the case where the dental adhesive composition described above was a dental primer.

(Adhesive strength test when the dental adhesive composition is an adhesive composite resin)
In the same manner as the adhesive strength test method in the case where the dental adhesive composition is a dental primer, prepare an extracted front tooth of a polished cow, and apply a similar adhesive surface of 3 mm in diameter with double-sided tape and paraffin wax. A simulated cavity was prepared. The simulated cavity is filled with an adhesive composite resin, pressed with a polyester sheet, and 30 seconds after filling, the visible light is irradiated for 30 seconds with a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). The resin was cured to produce an adhesion test piece.

  Using this adhesive test piece, the adhesive strength between the tooth and the cured adhesive composite resin was determined in the same manner as the adhesive strength test method in the case where the dental adhesive composition was a dental primer.

(Adhesive strength test when the dental adhesive composition is a dental resin cement)
In the same manner as in the adhesion strength test method using the above-described primer, polished front teeth of cattle were prepared, and a double-sided tape having a 3 mm diameter hole was pasted on the polished plane. Take equal parts of dental resin cement paste (1) and paste (2), and paste the paste for 30 seconds into a 3 mm diameter hole made with double-sided tape. The made attachment was adhered. After holding the test piece at 37 ° C. and 100% humidity for 1 hour, it was immersed in water at 37 ° C. for 24 hours to cure the dental resin cement, thereby preparing an adhesive test piece.

  Using this adhesion test piece, the adhesion strength between the tooth and the cured dental resin cement was determined in the same manner as the adhesion strength test method in the case where the dental adhesive composition was a dental primer.

Production Example 1
50 g of fumed silica (“Leosil QS-102” manufactured by Tokuyama Co., Ltd.) powder having an average primary particle size of 0.01 μm was placed in a 1.5 L cylindrical vessel lined with polytetrafluoroethylene and stirred. . After the nitrogen gas was flowed and the air in the container was replaced with nitrogen, the stirring state was continued. After spraying a mixed liquid of 2 g of 2-methacryloxyethyl dihydrogen phosphate, 1 g of triethylene glycol dimethacrylate, and 0.25 g of t-butylperoxy-2-ethylhexanoate onto the stirred fumed silica powder, By mixing and stirring for 2 hours, the liquid was uniformly applied to the entire particle powder. Thereafter, the mixture was heated and stirred in a nitrogen atmosphere at 100 ° C. for 2 hours to polymerize the liquid on the particle surface to obtain fumed silica particles coated with a polymer having phosphate groups on the surface. It was 170 m < ² > / g when the specific surface area of the obtained fumed silica particle was measured. Moreover, it was 2.52 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 2
100 g of silica-zirconia particles (refractive index nD = 1.52) synthesized by a sol-gel method and having an average particle size of 0.2 μm are placed in a cylindrical container with an internal volume of 0.5 L lined with polytetrafluoroethylene, Stirred. The operation of introducing nitrogen gas to return to normal pressure after evacuating the air in the container was repeated five times to replace the air inside with nitrogen. After spraying a mixed liquid of 0.63 g of 2-methacryloxyethyl dihydrogen phosphate, 0.17 g of triethylene glycol dimethacrylate and 0.06 g of t-butylperoxy-2-ethylhexanoate on silica-zirconia powder By mixing and stirring for 2 hours, the liquid was uniformly blended with the whole particle powder. Thereafter, the mixture was heated and stirred in a nitrogen atmosphere at 100 ° C. for 2 hours to polymerize the liquid on the particle surface to obtain silica-zirconia particles coated with a polymer having phosphate groups on the surface.

It was 12.8 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 2.11 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 3
The method described in Production Example 2 except that 0.12 g of 2-methacryloxyethyl dihydrogen phosphate, 0.033 g of triethylene glycol dimethacrylate, and 0.012 g of t-butylperoxy-2-ethylhexanoate were used. After processing, 100 g of silica-zirconia particles having phosphate groups on the surface was obtained. The specific surface area of the obtained silica-zirconia particles was measured and found to be 14.6 m ² / g. Moreover, it was 0.35 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 4
The method described in Production Example 2 except that 0.3 g of 2-methacryloxyethyl dihydrogen phosphate, 0.08 g of triethylene glycol dimethacrylate, and 0.03 g of t-butylperoxy-2-ethylhexanoate were used. After processing, 100 g of silica-zirconia particles having phosphate groups on the surface was obtained. It was 14.1 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 0.91 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 5
The method described in Production Example 2 except that 0.4 g of 2-methacryloxyethyl dihydrogen phosphate, 0.11 g of triethylene glycol dimethacrylate, and 0.04 g of t-butylperoxy-2-ethylhexanoate were used. After processing, 100 g of silica-zirconia particles having phosphate groups on the surface was obtained. It was 13.5 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 1.27 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 6
Treated by the method described in Production Example 2 except that 1 g of 2-methacryloxyethyl dihydrogen phosphate, 0.27 g of triethylene glycol dimethacrylate, and 0.1 g of t-butylperoxy-2-ethylhexanoate were used. 100 g of silica-zirconia particles having phosphoric acid groups on the surface were obtained. It was 12.1 m < ² > / g when the specific surface area of the obtained silica zirconia particle was measured. Moreover, it was 3.54 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 7
Silica-zirconia particles treated with the method described in Production Example 2 except that 0.32 g of vinylphosphonic acid is used instead of 0.63 g of 2-methacryloxyethyl dividroxyphosphate, and the surface has phosphonic acid groups. 100 g was obtained. It was 13.2 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 2.05 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 8
Production Example except that 0.47 g of 2-methyl-2-methacrylamide propane sulfonic acid, 0.13 g of 2-hydroxyethyl methacrylate and 0.1 g of water are used instead of 0.63 g of 2-methacryloxyethyl dividroxyphosphate The silica-zirconia particle which processed by the method described in 2 and has a sulfonic acid group on the surface was obtained. It was 13.3 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 1.35 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 9
Production Example except that 0.81 g of 2-methyl-2-methacrylamide propane sulfonic acid, 0.22 g of 2-hydroxyethyl methacrylate and 0.17 g of water are used instead of 0.63 g of 2-methacryloxyethyl dividroxyphosphate The silica-zirconia particle which processed by the method described in 2 and has a sulfonic acid group on the surface was obtained. It was 12.1 m < ² > / g when the specific surface area of the obtained silica zirconia particle was measured. Moreover, it was 2.54 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Production Example 10
The silica-zirconia particles having a carboxyl group on the surface were obtained by treating with the method described in Production Example 5 except that 0.26 g of methacrylic acid was used instead of 0.63 g of 2-methacryloxyethyl dividroxyphosphate. It was. It was 13.9 m < ² > / g when the specific surface area of the obtained silica-zirconia particle was measured. Moreover, it was 1.94 micromol / m < ² > when the amount of acidic groups which existed on the surface was measured.

Examples 1 and 2
Using the inorganic particles b1) having acidic groups on the surface produced in Production Example 1, dental primers having the compositions shown in Table 1 were prepared. About each obtained dental primer, the adhesive strength test method in case the dental adhesive composition is a dental primer was implemented. The results are shown in Table 1, respectively.

Comparative Example 1
In Example 2, instead of using the inorganic particles b1) having an acidic group on the surface produced in Production Example 1, fumed silica that has not been subjected to surface treatment (“Leosil QS-102” manufactured by Tokuyama Corporation) is used. A dental primer was prepared in the same manner except that the same amount was used. About the obtained dental primer, the adhesive strength test method in case a dental adhesive composition is a dental primer was implemented. The results are shown in Table 1.

Examples 3-4
Using the inorganic particles b1) having acidic groups on the surface produced in Production Example 1, dental bonding materials having the compositions shown in Table 2 were prepared. About each obtained dental bonding material, the adhesive strength test method in case the dental adhesive composition is a dental bonding material was implemented. The results are shown in Table 2, respectively.

Comparative Example 2
In Example 4, instead of using the inorganic particles b1) having an acidic group on the surface produced in Production Example 2, fumed silica ("Leosil QS-102" manufactured by Tokuyama Corporation) that has not been subjected to surface treatment is used. A dental bonding material was prepared in the same manner except that the same amount was used. About the obtained dental bonding material, the adhesive strength test method in case the dental adhesive composition is a dental bonding material was implemented. The results are shown in Table 2.

Examples 5 to 21
Using the inorganic particles b1) having acidic groups on the surface produced in any of Production Examples 2 to 10, adhesive composite resins having the compositions shown in Table 3 were prepared. About each obtained adhesive composite resin, the adhesive strength test method in case the dental adhesive composition is an adhesive composite resin was implemented. The results are shown in Table 3, respectively.

Comparative Examples 3-4
In Examples 8 and 10, instead of using the inorganic particles b1) having acidic groups on the surface produced in Production Example 2, particles F2 having methacryloxy groups on the surface are used, and the total amount of the particles F2 is 230 masses. Adhesive composite resins were prepared in the same manner except for using a part. About each obtained adhesive composite resin material, the adhesive strength test method in case the dental adhesive composition is a dental bonding material was implemented. The results are shown in Table 3, respectively.

Examples 22-38
Dental which consists of paste (1) having the composition shown in Table 4 and paste (2) having the composition shown in Table 5 using inorganic particles b1) having acidic groups on the surface produced in any of Production Examples 2 to 10. Resin cement was prepared for each. About each obtained dental resin cement, the adhesive strength test method in case the dental adhesive composition is a dental resin cement was implemented. The results are shown in Table 6, respectively.

Comparative Examples 5-6
In Examples 25 and 27, instead of using the inorganic particles b1) having acidic groups on the surface produced in Production Example 2, particles F2 having methacryloxy groups on the surface were used, and the total amount of the particles F2 was 115 mass. Dental resin cements were respectively prepared in the same manner except for partial use. About each obtained dental resin cement material, the adhesive strength test method in case the dental adhesive composition is a dental resin cement was implemented. The results are shown in Table 6, respectively.

Claims (10)

Polymeric monomer component (A) comprising acidic group-containing polymerizable monomer a1) and inorganic filler component (B) comprising inorganic particles b1) having acidic groups on the surface
A dental adhesive composition comprising: The dental adhesive composition according to claim 1, wherein the inorganic particles b1) having an acidic group on the surface are inorganic particles coated with a cured product of a polymerizable monomer having an acidic group. The dental group according to claim 1 or 2, wherein the acidic group of the inorganic particles b1) having an acidic group on the surface is at least one selected from a phosphoric acid group, a phosphonic acid group, a sulfonic acid group, and a carboxyl group. Adhesive composition. The dental adhesive composition according to any one of claims 1 to 3, wherein the acidic group of the acidic group-containing polymerizable monomer a1) is a phosphoric acid group. Furthermore, the dental adhesive composition as described in any one of Claims 1-4 formed by containing water (C). A dental primer comprising the dental adhesive composition according to claim 5. Furthermore, the dental adhesive composition according to any one of claims 1 to 5, comprising a polymerization initiator (D). A dental bonding material comprising the dental adhesive composition according to claim 7. An adhesive composite resin comprising the dental adhesive composition according to claim 7. A dental resin cement comprising the dental adhesive composition according to claim 7.