JP2018145133A - Self-adhesive dental composite resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a self-adhesive dental composite resin having excellent fluidity with little change in paste properties during storage while maintaining the mechanical strength obtained after polymerization curing by visible light irradiation. SOLUTION: An acidic group-containing (meth) acrylic polymerizable monomer (a), an acidic group-free polyfunctional (meth) acrylic polymerizable monomer (b), a photopolymerization initiator (c), It contains fumed silica (d), long-chain organosilicon compound (e), and filler (f) (excluding fumed silica (d)), and the filler (f) is treated with a surface treatment agent. The surface treatment agent is a silane coupling agent (A) represented by the general formula (1) and an organosilazane represented by the general formula (2), and the average particle size is 0.01 to 50.0 μm. A self-adhesive dental composite resin containing (B) and wherein the long-chain organosilicon compound (e) is a compound represented by the general formula (3). [Selection diagram] None

Description

  The present invention relates to a self-adhesive dental composite resin. More specifically, the present invention relates to a self-adhesive dental composite resin having high fluidity and little change in paste properties during long-term storage.

  In the treatment of dental caries and associated defects, restoration using a dental adhesive and a dental composite resin has been generally performed. The following procedure is used for repair treatment. First, after carving a carved portion to form a cavity, a dental adhesive is applied to the cavity, and then the area where the adhesive is applied is irradiated with visible light and cured. Next, the dental composite resin is filled on the cured adhesive layer, and finally, the filled dental composite resin is irradiated with visible light and cured.

  In the above restoration method, two materials, a dental adhesive and a dental composite resin, are used. Recently, a self-adhesive dental composite resin in which a dental composite resin has adhesive properties has been developed. It has begun to be put into practical use as a material that eliminates the use of adhesives and reduces the number of repair treatment steps.

  The self-adhesive dental composite resin is composed of a polyfunctional polymerizable monomer and filler for imparting mechanical strength, and a component of a conventional dental composite resin called a polymerization initiator for improving curability. In order to impart adhesiveness to the resin, a polymerizable monomer having an acidic group that has been used in dental adhesives is used as a component (for example, Patent Documents 1 and 2).

  As the polymerizable monomer compounded in the dental composite resin, (meth) acrylate is generally used. In order to improve this, a polymerizable monomer having an acidic group such as a phosphate group or a carboxy group is blended.

  On the other hand, self-adhesive materials such as oxides, carbonates or hydroxides of alkaline earth metals such as calcium, magnesium, and strontium, or acid-reactive fluoroaluminosilicate glass that are commonly used in dental composite resins When blended as a filler for dental composite resins, it is known that there is a problem that self-adhesion itself is impaired by causing an acid-base reaction, neutralization, salt formation, or chelate reaction with a polymerizable monomer having an acidic group. It has been. Therefore, for this problem, it has been proposed to select a filler having low reactivity with an acidic component, for example, a silica filler treated with a silane coupling agent, as a filler to be blended in a self-adhesive dental composite resin. (Patent Document 2).

  However, when silica filler or the like that does not react with the acidic component described in Patent Document 2 is used, the reaction between the filler and the acidic component is suppressed, but the paste is kept while the self-adhesive dental composite resin is stored. There was a case in which the properties of

JP 2008-260752 A Special table 2015-507610 gazette

  Therefore, the present invention maintains the mechanical strength obtained after polymerization and curing by irradiation with visible light by including a polyfunctional polymerizable monomer, a filler, and a polymerization initiator, as in the case of conventional dental composite resins. On the other hand, an object of the present invention is to provide a self-adhesive dental composite resin which has little change in paste properties during long-term storage and has excellent fluidity.

The present invention relates to the following inventions.
[1] Acidic group-containing (meth) acrylic polymerizable monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) not containing acidic group, photopolymerization initiator (c), fume Containing silica (d), long-chain organosilicon compound (e), and filler (f) (except fumed silica (d)),
The filler (f) is treated with a surface treatment agent, and the average particle size is 0.01 to 50.0 μm,
The surface treatment agent has the following general formula (1)
^{_{CH 2 = C (R 1)}} -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group optionally having substituent (s), and R ³ is a C _1- optionally having substituent (s)). C _{3 is} an alkyl group, p is an integer of 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by the following general formula (2)
R ⁴ R ⁵ R ⁶ —Si—NH—Si—R ⁷ R ⁸ R ⁹ (2)
(Wherein, R ^4, R ^5, and R ⁶ are each independently a hydrogen atom or an alkyl group which may have a substituent C ₁ -C _3, R ^4, R ^5, and R at least one of ⁶ is an alkyl group optionally C ₁ -C ₃ may have a substituent, R ^7, R ⁸ and R ⁹ each independently have a hydrogen atom or a substituent A C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a C ₁ -C ₃ alkyl group optionally having a substituent.)
Containing an organosilazane (B) represented by
The long-chain organosilicon compound (e) is represented by the following general formula (3)
^{_{CH 2 = C (R 10)}} -COO-X- (CH 2) r -Si-R 11 s R 12 (3-s) (3)
(In the formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrolyzable group which may have a substituent, R ¹² represents a C _{1 to} C ₆ hydrocarbon group, X represents an oxygen atom or a sulfur atom, where r represents an integer of 5 to 15 and s represents 2 or 3.)
A self-adhesive dental composite resin, which is a compound represented by:
[2] R ² is an unsubstituted hydrolyzable group, R ³ is an unsubstituted C ₁ -C ₃ alkyl group, and R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen An atomic or unsubstituted C ₁ -C ₃ alkyl group, at least one of R ⁴ , R ⁵ , and R ⁶ is an unsubstituted C ₁ -C ₃ alkyl group, and R ⁷ , R ⁸ and R ⁹ is independently a hydrogen atom or an unsubstituted C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ , and R ⁹ is an unsubstituted C ₁ -C ₃ alkyl group. The self-adhesive dental composite resin of [1].
[3] The self-adhesive dental composite resin of [1] or [2], wherein the apparent specific gravity of the fumed silica (d) is 20 g / l or more.
[4] The above [1] to [3], wherein the apparent specific gravity of the fumed silica (d) is 50 g / l or more, and the BET specific surface area of the fumed silica (d) is 50 m ² / g or more. One of the self-adhesive dental composite resins.
[5] The apparent specific gravity of the fumed silica (d) is 100 g / l or more, the BET specific surface area of the fumed silica (d) is 100 m ² / g or more, and the fumed silica (d) The self-adhesive dental composite resin according to any one of [1] to [4], wherein the average primary particle size is 5 to 50 nm.
[6] The self-adhesive dental composite resin according to any one of [1] to [5], wherein r in the general formula (3) is an integer of 8 to 13.
[7] The self-adhesive dental composite resin according to any one of [1] to [6], wherein s is 3 and R ¹¹ is a C _{1 to} C ₃ alkoxy group in the general formula (3).
[8] The silane coupling agent (A) is 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and The self-adhesive dental composite resin according to any one of [1] to [7], which is at least one selected from the group consisting of 6-methacryloyloxyhexyltrimethoxysilane.
[9] The organosilazane (B) is 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, and 1,1,1,3. The self-adhesive dental composite resin according to any one of [1] to [8], which is one or more selected from the group consisting of 3-pentamethyldisilazane.
[10] In 100 parts by mass of the total amount of the polymerizable monomer components, 1 to 40 parts by mass of the acidic group-containing (meth) acrylic polymerizable monomer (a), and a polyfunctional compound not containing the acidic group 30 to 95 parts by mass of the (meth) acrylic polymerizable monomer (b) is contained, and 0.001 of the photopolymerization initiator (c) is added to 100 parts by mass of the total amount of the polymerizable monomer components. -20 parts by mass, 1-60 parts by mass of the fumed silica (d), 0.01-30 parts by mass of the long-chain organosilicon compound (e), and 25-400 parts by mass of the filler (f). The self-adhesive dental composite resin according to any one of [1] to [9].
[11] The self-adhesive dental composite resin according to any one of [1] to [10], further comprising a polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton.
[12] In the total amount of the polymerizable monomer component of 100 parts by mass, the blending amount of the polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton is 0.5 to 30 parts by mass. The self-adhesive dental composite resin according to any one of 1] to [11].
[13] The self-adhesive dental composite resin according to any one of [1] to [12], further comprising a hydrophilic monofunctional polymerizable monomer (h).
[14] The self-adhesive dental composite resin according to any one of [1] to [13], further comprising a hydrophilic monofunctional polymerizable monomer (h).
[15] In the total amount of the polymerizable monomer component of 100 parts by mass, the amount of the hydrophilic monofunctional polymerizable monomer (h) is 1 to 30 parts by mass. 14] The self-adhesive dental composite resin according to any one of 14).
[16] The self-adhesive dental composite resin according to any one of [1] to [15], which is a single material type.

  According to the present invention, a self-adhesive dental composite resin having sufficient mechanical strength after polymerization curing by irradiation with visible light, high fluidity before polymerization curing, and little change in paste properties during storage for a long period of time. Is provided.

FIG. 1 is an explanatory diagram of a reaction mechanism when organosilazane (B) according to an embodiment of the present invention is 1,1,1,3,3,3-hexamethyldisilazane.

The self-adhesive dental composite resin of the present invention includes an acidic group-containing (meth) acrylic polymerizable monomer (a), a polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, Containing the photopolymerization initiator (c), fumed silica (d), long-chain organosilicon compound (e), and filler (f) (excluding fumed silica (d)), the filler (f) Is treated with a surface treatment agent and has an average particle diameter of 0.01 to 50.0 μm, and the surface treatment agent is represented by the following general formula (1):
^{_{CH 2 = C (R 1)}} -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group optionally having substituent (s), and R ³ is a C _1- optionally having substituent (s)). C _{3 is} an alkyl group, p is an integer of 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by the following general formula (2)
R ⁴ R ⁵ R ⁶ —Si—NH—Si—R ⁷ R ⁸ R ⁹ (2)
(Wherein, R ^4, R ^5, and R ⁶ are each independently a hydrogen atom or an alkyl group which may have a substituent C ₁ -C _3, R ^4, R ^5, and R at least one of ⁶ is an alkyl group optionally C ₁ -C ₃ may have a substituent, R ^7, R ⁸ and R ⁹ each independently have a hydrogen atom or a substituent A C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a C ₁ -C ₃ alkyl group optionally having a substituent.)
Containing an organosilazane (B) represented by
The long-chain organosilicon compound (e) is represented by the following general formula (3)
^{_{CH 2 = C (R 10)}} -COO-X- (CH 2) r -Si-R 11 s R 12 (3-s) (3)
(In the formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrolyzable group which may have a substituent, R ¹² represents a C _{1 to} C ₆ hydrocarbon group, X represents an oxygen atom or a sulfur atom, where r represents an integer of 5 to 15 and s represents 2 or 3.)
It is a compound represented by these.

  In the present specification, the upper limit value and the lower limit value of the numerical range (the amount of each component, the value calculated from each component, each physical property, the numerical value of the symbol of the formula, etc.) can be combined as appropriate.

Reason why the self-adhesive dental composite resin of the present invention has sufficient mechanical strength after polymerization and curing by irradiation with visible light, has high fluidity before polymerization and curing, and has little change in paste properties during long-term storage Although it is not certain, it is estimated as follows. That is, the filler (f) is a functional group represented by — (CH ₂ ) _p —OOC—C (R ¹ ) ═CH ₂ (R ¹ is a hydrogen atom) derived from the surface treatment with the silane coupling agent (A). Or p represents an integer of 1 to 13), and C _{1 to} C ₃ alkyl groups derived from surface treatment with organosilazane (B) on the surface. Since the C ₁ -C ₃ alkyl groups repel each other due to their hydrophobicity, the filler (f) is C ₁ -C even when stored for a long time as a self-adhesive dental composite resin. _It is considered that the paste properties hardly change due to the repulsive force between the _three alkyl groups, and that the paste properties are less changed. Further, since the filler (f) has — (CH ₂ ) _p —OOC—C (R ¹ ) ═CH ₂ on the surface, the polymerizable group of the polymerizable monomer in the self-adhesive dental composite resin It is considered that polymerization can be performed, the bond between the filler (f) and the polymerizable monomer interface can be further strengthened, and sufficient mechanical strength can be imparted. _{- (CH 2) p -OOC-} C (R 1) = CH 2 , the silane coupling agent (A) used having a polymerizable group, one applied by the dehydration polycondensation reaction of silanol groups, C ₁ The alkyl group of ˜C ₃ is added by a deammonification reaction of organosilazane (B). In the treatment only with a general silane coupling agent (A) known as a prior art, a silanol group (—SiOH) generated by hydrolyzing an alkoxy group of the silane coupling agent (A) and a filler (f) The silanol group (—SiOH) on the surface of the metal is chemically bonded by dehydration polycondensation. In this case, silanol groups (—SiOH) on the surface of the filler (f) or silanol groups (—SiOH) derived from the silane coupling agent (A) remain as unreacted substances (hereinafter, these remaining silanol groups Are referred to as “residual silanol groups”). In contrast, in the present invention, as shown in FIG. 1, the residual silanol group (—SiOH) on the surface of the filler (f) or the residual silanol group (—SiOH) derived from the silane coupling agent (A) and the organosilazane. The residual silanol group (—SiOH) can be hydrophobized by the deammonification reaction with (B). By this treatment with organosilazane (B) (deammonia reaction), the residual silanol groups (—SiOH) on the surface of the filler (f) or the residual silanol groups (—SiOH) derived from the silane coupling agent (A) are reduced as much as possible. It is considered possible. Accordingly, in the same material, protons generated from the acidic group-containing (meth) acrylic polymerizable monomer (a), which is an essential component from the viewpoint of imparting adhesiveness to the self-adhesive dental composite resin (H ⁺ ) or hydroxyl groups (—OH) contained in other polymerizable monomers are less likely to cause a strong interaction due to hydrogen bonds with silanol groups (—SiOH), and the paste properties during storage are reduced. It is considered stable over a long period of time.

On the other hand, the blending of the filler (f) makes the paste property stable for a long time, but it becomes a paste with strong shapeability due to the C ₁ -C ₃ alkyl group on the surface of the filler (f), and the fluidity is low. A problem was found that it was scarce and difficult for the surgeon to handle. In order to solve this problem, the fumed silica (d) and the long-chain silane coupling agent (e) are contained at the same time, so that it is obtained by blending the filler (f) such as paste property stability during storage over a long period of time. It became clear that it could be solved without damaging the properties. Although the detailed reason is not certain, it is estimated as follows. Since fumed silica (d) has a very small average primary particle diameter of 5 to 50 nm, it can be considered that fluidity can be imparted to the paste by the bearing effect when it is present between the fumed silica (d) and the filler (f). . Furthermore, in addition to the filler (f) and fumed silica (d), a paste composition in which particles are contained in a polymerizable monomer due to the surface active effect by blending the long-chain organosilicon compound (e). It is considered that the bearing effect, that is, “slip” can be improved.

  For the above reasons, the self-adhesive dental composite resin containing fumed silica (d), long-chain organosilicon compound (e), and filler (f) has sufficient mechanical strength and fluidity. It is considered that there is little change in paste properties during long-term storage.

  First, the fumed silica (d) used in the present invention will be described.

  Fumed silica (d) is a silica produced by dry process by combustion hydrolysis using silicon tetrachloride as a precursor. Fumed silica is a kind of amorphous silica and is also called dry silica. Combining fumed silica (d) with long-chain organosilicon compound (e) provides excellent fluidity without compromising paste property stability during long-term storage of the composition containing filler (f) can do.

The BET specific surface area of the fumed silica (d) (BET: specific surface area by Brunauer-Emmett-Teller method) is preferably 25 m ² / g or more, more preferably 50 m ² / g or more, from the viewpoint of imparting fluidity. 100 m ² / g or more is more preferable. Further, from the viewpoint of not impairing the fluidity of the self-adhesive dental composite resin, 400 m ² / g or less is preferable, 350 m ² / g or less is more preferable, and 250 m ² / g or less is more preferable. Therefore, from the point of view, BET specific surface area of the fumed silica (d) is preferably 25~400m ² / g, more preferably 50~350m ² / g, more preferably 100 to 250 m ² / g.

  The average primary particle size of the fumed silica (d) is preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more from the viewpoint of not impairing fluidity. Further, from the viewpoint of imparting fluidity, 50 nm or less is preferable, 30 nm or less is more preferable, and 20 nm or less is more preferable. Therefore, from the above viewpoint, the average primary particle size of fumed silica (d) is preferably 5 to 50 nm, more preferably 7 to 30 nm, and even more preferably 10 to 30 nm.

  The pH of the fumed silica (d) is preferably 3.0 or more, more preferably 3.5 or more, and further preferably 4.0 or more from the viewpoint of not promoting the dehydration condensation reaction of the long-chain organosilicon compound (e). preferable. Moreover, 10.0 or less are preferable, 9.0 or less are more preferable, and 8.0 or less are further more preferable from a viewpoint which suppresses reaction with an acidic group containing (meth) acrylic-type polymerizable monomer (a). Therefore, from the above viewpoint, the pH of the fumed silica (d) is preferably 3.0 to 10.0, more preferably 3.5 to 9.0, and even more preferably 4.0 to 8.0.

  The apparent specific gravity of the fumed silica (d) is preferably 20 g / l or more, more preferably 50 g / l or more, and further preferably 120 g / l or more, from the viewpoint of suppressing an increase in viscosity when blended. Further, from the viewpoint of higher fluidity imparting effect to the paste due to the bearing effect, it is preferably 300 g / l or less, more preferably 290 g / l or less, and even more preferably 280 g / l or less. Therefore, from the above viewpoint, the apparent specific gravity of the fumed silica (d) is preferably 20 to 300 g / l, more preferably 50 to 290 g / l, and further preferably 120 to 280 g / l.

The fumed silica (d) preferably has a BET specific surface area of 50 to 350 m ² / g and an apparent specific gravity of 50 to 290 g / l from the viewpoint of obtaining higher fluidity. Is more preferably 100 to 250 m ² / g, apparent specific gravity is 120 to 280 g / l, BET specific surface area is 100 to 250 m ² / g, and pH is 4.0 to 8.0. More preferably, the apparent specific gravity is 120 to 280 g / l, the BET specific surface area is 100 to 250 m ² / g, the average primary particle size is 7 to 30 nm, and the pH is 4.0 to 8.0. And an apparent specific gravity of 120 to 280 g / l is particularly preferable.

In addition, the measuring method of the said chemical property of fumed silica (d) is as follows.
BET specific surface area (m ² / g): According to the BET method described in JIS Z 8830: 2013 or ISO 9277: 2010, a specific surface area measuring device (trade name: BELSORP-mini-II, constant capacity gas adsorption method ( Nitrogen adsorption / desorption measurement), manufactured by Microtrack Bell Co., Ltd.).
Average primary particle size (nm): A photograph of a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) of the sample was taken, and the particle diameter of particles (200 or more) observed in the unit field of view of the photograph was It calculates | requires by measuring using image-analysis type | formula particle size distribution measurement software (Macview (Mounttech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic average value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter.
pH: 4 parts by mass of a sample is dispersed at room temperature with respect to 100 parts by mass of distilled water to obtain a 4% by mass aqueous dispersion. Next, the pH in the 4% by mass aqueous dispersion is measured with a desktop pH meter (F71) manufactured by Horiba, Ltd. The method is based on ISO 787-9: 1981 except that a 4% by mass aqueous dispersion is used.
Apparent specific gravity: Measured according to the method according to ISO 787-11: 1981 and calculated as the tapped density (also referred to as tamped density) by the following formula.

  When the fumed silica (d) is combined with the long-chain organosilicon compound (e), fluidity can be imparted to the paste by the bearing effect, and stability of paste properties during storage over a long period of time can be imparted. From the point which can do, 1 mass part or more is preferable with respect to 100 mass parts of polymerizable monomers, 2 mass parts or more are more preferable, and 9 mass parts or more are further from the point from which the more excellent paste property stability is obtained. preferable. Further, from the viewpoint of not impairing the fluidity of the self-adhesive dental composite resin, 60 parts by mass or less is preferable, 50 parts by mass or less is more preferable, and 40 parts by mass or less is preferable with respect to 100 parts by mass of the polymerizable monomer. Further preferred. Therefore, from the above viewpoint, the amount of fumed silica (d) is preferably 1 to 60 parts by weight, more preferably 2 to 50 parts by weight, and 9 to 40 parts by weight with respect to 100 parts by weight of the polymerizable monomer. Part is more preferred.

  The fumed silica (d) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include at least one organometallic compound selected from the group consisting of an organosilicon compound, an organotitanium compound, an organozirconium compound, and an organoaluminum compound. When two or more kinds of organometallic compounds are used, the surface treatment layer may be a mixture of two or more kinds of organometallic compounds, or may be a surface treatment layer having a multilayer structure in which two or more kinds of organometallic compound layers are laminated. Good.

Examples of the organosilicon compound include organosilazane (B) or a compound represented by (W) _n SiY _4-n (W is a substituted or unsubstituted C _{1 to} C ₁₂ ). a hydrocarbon group, Y is C ₁ -C ₄ alkoxy group, hydroxy group, a halogen atom or a hydrogen atom, n is when there are a plurality of .W and Y is 0, 1, 2 or 3, Each may be the same or different.)

  Specifically, 1,1,1,3,3,3-hexamethyldisilazane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3 , 3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ -Glycidoxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- ( Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldi Lorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω- (meth) acryloyloxyalkyltrimethoxysilane (the number of carbon atoms between the (meth) acryloyloxy group and the silicon atom: 3 to 12, Example, 3-methacryloyloxypropyltrimethoxysilane, etc.), ω- (meth) acryloyloxyalkyltriethoxysilane (the number of carbon atoms between the (meth) acryloyloxy group and the silicon atom: 3-12, for example, 3-methacryloyl) Oxypropyltriethoxysilane, etc.).

  The fumed silica (d) is preferably structurally modified after being treated with the surface treatment agent and then heat-treated. Here, structurally modifying means increasing the apparent specific gravity without greatly changing the BET specific surface area, the average primary particle diameter, and the pH.

  The means for structural modification is not particularly limited as long as the apparent specific gravity can be increased without greatly changing the BET specific surface area, the average primary particle diameter, and the pH. Structural modification can be achieved by first spraying with water, then spraying with a surface treatment, optionally further mixing and then heat treating.

  The water used may be made acidic (pH 1-6) with an acid (for example hydrochloric acid), and when several surface treatment agents are used, these surface treatment agents may be used simultaneously. However, they may be used separately once or as a mixture. One or more surface treatment agents may be dissolved in a suitable solvent such as water, ethanol, or isopropyl alcohol. Mixing may continue for an additional 5 to 30 minutes after spraying is complete.

  Furthermore, this mixture is heat-treated at a temperature of 20 to 400 ° C. for 0.1 to 6 hours, and the heat treatment can be performed under a protective gas, for example, in a nitrogen atmosphere.

  Since the structurally modified fumed silica (d) has a high apparent specific gravity, the structurally modified fumed silica and the polymerizable monomer are mixed in the same amount. The dental composition formulated with the fumed silica (d) modified to (a self-adhesive dental composite resin) is compared with the dental composition formulated with the structurally unmodified fumed silica. , The increase in viscosity can be greatly suppressed. That is, the structurally modified fumed silica (d) can be blended in a larger amount than the structurally unmodified fumed silica, and the fluidity imparting effect to the paste by the bearing effect can be achieved. It can be greatly improved.

From the above viewpoint, the apparent specific gravity of the structurally modified fumed silica (d) is preferably 100 to 300 g / l, more preferably 110 to 290 g / l, and still more preferably 120 to 280 g / l. A commercial item can be used for fumed silica (d). In particular, as a commercially available product of structurally modified fumed silica (d), for example, AEROSIL (registered trademark) R 7200 (surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m ² / g, average primary particle size: 12 nm, pH: 4.5, apparent specific gravity: 230 g / l, manufactured by EVONIK INDUSTRIES, AEROSIL® R 8200 (surface treatment agent: 1,1,1,3,3) , 3-hexamethyldisilazane, BET specific surface area: 155 m ² / g, average primary particle size: 12 nm, pH: 5.5, apparent specific gravity: 140 g / l, manufactured by EVONIK INDUSTRIES), AEROSIL (registered trademark) R 9200 (a surface treatment agent: dimethyldichlorosilane, BET specific surface area: 170m ² / g, average primary particle diameter: 12 nm, pH: 4.0, apparent specific gravity: 00g / l, and the like is EVONIK INDUSTRIES Co., Ltd.), and the like.

  Next, the long chain organosilicon compound (e) used in the present invention will be described.

The long-chain organosilicon compound (e) is represented by the following general formula (3).
^{_{CH 2 = C (R 10)}} -CO-X- (CH 2) r -Si-R 11 s R 12 (3-s) (3)
(In the formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrolyzable group which may have a substituent, R ¹² represents a C _{1 to} C ₆ hydrocarbon group, X represents an oxygen atom or a sulfur atom, where r represents an integer of 5 to 15 and s represents 2 or 3.)

  By combining the long-chain organosilicon compound (e) represented by the general formula (3) with the fumed silica (d), the paste property stability during long-term storage of the composition containing the filler (f) is impaired. And excellent fluidity can be imparted.

Examples of the hydrolyzable group optionally having a substituent for R ¹¹ include a linear or branched alkoxy group, a chlorine atom, or an isocyanate group (—N═C═O). As the alkoxy group, those of C _{1 to} C ₁₀ are preferable, those of C _{1 to} C ₆ are more preferable, and those of C _{1 to} C ₃ are more preferable in consideration of hydrolyzability. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and the like. The hydrolyzable group for R ¹¹ may be unsubstituted. Examples of the substituent for R ¹¹ include the same substituents that the hydrolyzable group for R ² may have.

Examples of the hydrocarbon group C ₁ -C ₆ of R ^12, for example, an alkyl group of C ₁ -C _6, alkenyl radicals in C ₂ -C _6, alkynyl group C ₂ -C _6, the C ₃ -C ₆ A cycloalkyl group etc. are mentioned. X is preferably an oxygen atom. r is preferably an integer of 8 to 13. s is preferably 3.

Of the long-chain organosilicon compound (e) represented by the general formula (3), R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a C ₁ -C ₃ alkoxy group, and s is 3. A compound in which r is an integer of 8 to 13 is preferred.

  Specific examples of the long-chain organosilicon compound (e) represented by the general formula (3) include 3- (meth) acryloyloxypropyltrimethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (Meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyltrimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meta ) Acrylyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane, 12- (meth) acryloyloxidedecyltrimethoxysilane, 13- (meth) Acryloyloxytridecyltrimethoxysilane, 14- (meth) acryloyloxytetradecyltrimethoxysilane, 15- (meth) acryloyloxypentadecyltrimethoxysilane, 16- (meth) acryloyloxycetyltrimethoxysilane, 17- ( Suitable examples include (meth) acryloyloxyheptadecyltrimethoxysilane, 18- (meth) acryloyloxystearyltrimethoxysilane, and the like. These may be used alone or in combination of two or more. Among these, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, and 7- (meth) acryloyloxyheptyltrimethoxy are advantageous in that the effect of imparting fluidity of the paste is great. Silane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane 12- (meth) acryloyloxidedecyltrimethoxysilane, 13- (meth) acryloyloxytridecyltrimethoxysilane, 14- (meth) acryloyloxytetradecyltrimethoxysilane, 15- (meth) a Liloyloxypentadecyltrimethoxysilane is preferred, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- ( More preferred are (meth) acryloyloxyundecyltrimethoxysilane, 12- (meth) acryloyloxidedecyltrimethoxysilane, 13- (meth) acryloyloxytridecyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxyundecyltrimethoxysilane and 12- (meth) acryloyloxidedecyltrimethoxysilane are more preferable.

  The amount of the long-chain organosilicon compound (e) is such that when combined with fumed silica (d), fluidity can be imparted to the paste and paste property stability during storage over a long period of time can be imparted. In terms of 100 parts by mass of the polymerizable monomer, 0.01 parts by mass or more is preferable, 0.1 parts by mass or more is more preferable, and 1.0 part by mass can be imparted to the paste with better fluidity. The above is more preferable. Further, from the viewpoint that the curability affecting the adhesive strength or bending strength of the self-adhesive dental composite resin is not significantly reduced, 30 parts by mass or less is preferable with respect to 100 parts by mass of the polymerizable monomer. The amount is more preferably 14 parts by weight or less, more preferably 14 parts by weight or less from the viewpoint that more excellent property stability of the paste and higher adhesive strength can be obtained. Therefore, from the above viewpoint, the blending amount of the long-chain organosilicon compound (e) is preferably 0.01 to 30 parts by mass and more preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Preferably, 1.0 to 14 parts by mass is more preferable.

  Moreover, the compounding quantity of a long-chain organosilicon compound (e) can give the paste property stability in the point which can provide fluidity | liquidity to a paste, and long-term storage, when combined with a fumed silica (d). From the viewpoint, it is preferable that the amount is less than the amount of fumed silica (d), that is, [the amount of long-chain organosilicon compound (e) / the amount of fumed silica (d)] <1. As a mass ratio of the blending amount of the long-chain organosilicon compound (e) and the fumed silica (d), the long-chain organosilicon compound (e): fumed silica (d) = 1.0: 1.1 -1.0: 15.0 is preferable, 1.0: 1.5-1.0: 13.0 is more preferable, and 1.0: 1.9 because it is possible to impart better fluidity to the paste. More preferably -1.0: 11.0.

  Next, the filler (f) (excluding fumed silica (d)) used in the present invention will be described.

The filler (f) has — (CH ₂ ) _p —OOC—C (R ¹ ) ═CH ₂ and a C _{1 to} C ₃ alkyl group on the surface. C ₁ -C ₃ alkyl groups repel each other due to their hydrophobicity. Therefore, the filler (f) of the present invention hardly aggregates in the self-adhesive dental composite resin due to the repulsive force between the C ₁ -C ₃ alkyl groups, and also hardly aggregates in the powder state.

  As the filler (f), a silane coupling agent (A) that has been treated with a surface treatment agent, has an average particle diameter of 0.01 to 50.0 μm, and the surface treatment agent is represented by the formula (1). As long as it contains the organosilazane (B) represented by the formula (2), any known filler used for dental composite resins can be used without any limitation. As the filler (f), various glasses [containing silica as a main component and containing oxides such as heavy metals, boron, and aluminum as necessary. For example, glass powder having a general composition such as fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (pyrex (registered trademark) glass); barium glass (GM27884, 8235, manufactured by Schott, E2000, E3000, manufactured by ESSTECC), strontium borosilicate glass (E4000, manufactured by ESSTECC), lanthanum glass ceramics (GM31684, manufactured by Schott), fluoroaluminosilicate glass (GM35429, G018-091, G018-117, Shot) Dental glass powder], various ceramics, composite oxides such as silica-titania, silica-zirconia, diatomaceous earth, kaolin, clay mineral (montmorillonite, etc.), activated clay, synthetic zeolite, mica Calcium fluoride, ytterbium fluoride, yttrium fluoride, core-shell structure calcium fluoride coated with silica, core-shell structure ytterbium fluoride coated with silica, core-shell structure coated with silica Yttrium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, core-shell structure calcium phosphate coated with silica, core-shell structure barium sulfate coated with silica, surface coated with silica Examples thereof include zirconium dioxide having a core / shell structure, titanium dioxide having a core / shell structure whose surface is coated with silica, and hydroxyapatite having a core / shell structure whose surface is coated with silica. Among these, the surface was coated with various glasses, composite oxides such as silica-titania, silica-zirconia, and silica from the point that they can efficiently react with the silane coupling agent (A) or the organosilazane (B). Core-shell structure calcium fluoride, silica-coated core-shell structure ytterbium fluoride, silica-coated core-shell structure yttrium fluoride, silica-coated core-shell calcium phosphate, silica surface Coated core-shell barium sulfate, silica-coated core-shell structured zirconium dioxide, silica-coated core-shell structured titanium dioxide, silica-coated core-shell structured hydroxyapatite silica Coat the surface Ytterbium fluoride of the core-shell structure, yttrium fluoride of the core-shell structure coated with silica are preferred. These may be used alone or in combination of two or more.

  The average particle diameter of the filler (f) is 0.01 to 50.0 μm, preferably 0.03 to 20.0 μm, and more preferably 0.05 to 10.0 μm. Within these ranges, sufficient mechanical strength can be obtained, the paste is not sticky, the operability is not problematic, and the hardened product is excellent in polishing smoothness or smooth durability. In addition, in this specification, the average particle diameter of a filler means the average particle diameter (average primary particle diameter) of the primary particle of a filler.

  The average particle diameter of the filler can be determined by particle size distribution measurement or electron microscope observation. When the average particle size is 1.0 μm or more, it is preferable to use a particle size distribution measuring device, and when the average particle size is less than 1.0 μm, it is preferable to use electron microscope observation. Specifically, the particle size distribution can be measured by, for example, a laser diffraction particle size distribution measuring apparatus (SALD-2100: manufactured by Shimadzu Corporation) using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium. Specifically, the electron microscope observation is, for example, taking a scanning electron microscope (S-4000 type, manufactured by Hitachi, Ltd.) photograph of particles, and measuring the particle diameter of particles (200 or more) observed in the unit field of view of the photograph. It can be determined by measuring using image analysis type particle size distribution measurement software (Macview (Mounttech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic average value of the longest length and the shortest length of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter.

  Further, since the filler (f) used in the present invention hardly aggregates, it can be easily washed with water. For this reason, the filler (f) used in the present invention is an amount of an ionic impurity such as an acid-base reaction or chelate reaction with an acid group-containing (meth) acrylic polymerizable monomer (a). Can be reduced.

  The filler (f) is obtained by surface-treating the filler (f) with a silane coupling agent (A) represented by the formula (1) and an organosilazane (B) represented by the formula (2).

  By surface-treating with the silane coupling agent (A) represented by the above formula (1), the hydroxyl group present on the surface of the filler (f) is substituted with a functional group derived from the silane coupling agent (A). .

  The order of the surface treatment of the filler (f) is not particularly limited. For example, the filler (f) may be surface-treated by adding them in order with the silane coupling agent (A) represented by the formula (1) and the organosilazane (B) represented by the formula (2). In addition, the surface treatment may be performed at the same time. For example, first, the filler (f) may be reacted with the silane coupling agent (A) represented by the above formula (1), and then the organosilazane (B) represented by the above formula (2) may be reacted. Alternatively, first, the organosilazane (B) represented by the formula (2) is reacted with the filler (f), then the silane coupling agent (A) represented by the formula (1) is reacted, and then the above formula. The organosilazane (B) represented by (2) may be reacted.

  As a surface treatment method of the filler (f), a method of binding the silane coupling agent (A) represented by the above formula (1) to the surface of the filler (f) by a dehydration polycondensation reaction, and the above formula (2) If it is the method of couple | bonding the organosilazane (B) represented by this to the surface of a filler (f) by deammonia reaction, it will not specifically limit. For example, a method of spraying a solution obtained by diluting each surface treatment agent with a solvent while stirring the filler (f) in a mixing tank, and heating and drying in the tank for a certain time while continuing the stirring; filler (f) and surface treatment Examples thereof include a method of stirring and mixing the agent in a solvent and then drying by heating. Although it does not specifically limit as said solvent, Alcohol solvents, such as methanol, ethanol, isopropanol, water, or these mixed solvents are mentioned. Although the said heating temperature is not specifically limited, About 30-90 degreeC may be sufficient.

In the above formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrolyzable group which may have a substituent. R ³ is a C ₁ -C ₃ alkyl group which may have a substituent. p is an integer of 1-13, 2-10 are preferable, 2-8 are more preferable, and 2-6 are more preferable. q is 2 or 3, and 3 is preferable.

The hydrolyzable group which may have a substituent for R ² is not particularly limited, but examples of the hydrolyzable group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- butoxy, sec- butoxy, isobutoxy, tert- butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, linear or branched alkoxy group of C ₁ -C _6, such as iso-hexyloxy group; A chlorine atom or an isocyanate group is mentioned. In consideration of hydrolyzability, the alkoxy group as the hydrolyzable group should be a C _{1 to} C ₄ linear alkoxy group of any one of a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Is more preferable, and a C ₁ -C ₃ linear alkoxy group is more preferable. The hydrolyzable group for R ² may be unsubstituted. In the formula (1), R ¹ is a methyl group, R ² is an unsubstituted C ₁ -C ₆ linear or branched alkoxy group, and R ³ is an unsubstituted C ₁ -C ₃ alkyl group. A silane coupling agent (A) wherein p is 2 to 10 and q is 2 or 3, R ¹ is a methyl group, and R ² is unsubstituted C _{1 to} C ₄ . A silane coupling agent (A) which is a linear or branched alkoxy group, p is 2 to 8, and q is 3, more preferably, R ¹ is a methyl group, and R ² is unsubstituted. More preferred is a silane coupling agent (A) which is a C _{1 to} C ₃ linear or branched alkoxy group, p is 2 to 6, and q is 3.

Examples of the C ₁ -C ₃ alkyl group optionally having substituents R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a methyl group, an ethyl group, n -A propyl group and an isopropyl group are mentioned. The alkyl groups of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may each independently be unsubstituted. The alkyl group for R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably a methyl group or an ethyl group, and more preferably a methyl group. At least one of R ⁴ , R ⁵ , and R ⁶ is an optionally substituted C ₁ -C ₃ alkyl group, and two of these optionally have a substituent C _1- may be an alkyl group of C _3, all three may be an alkyl group optionally C ₁ -C ₃ may have a substituent. At least one of R ⁷ , R ^8, and R ⁹ is an optionally substituted C ₁ -C ₃ alkyl group, and these two optionally have a substituent C ₁ -C it may be ₃ alkyl group, and all three may be an alkyl group optionally C ₁ -C ₃ may have a substituent.

Examples of the substituent of the hydrolyzable group of R ² and the alkyl group of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include a halogen atom (a fluorine atom, a chlorine atom, bromine atom, iodine atom), a carboxy group, hydroxy group, amino group, C ₁ -C ₆ alkyl group mono- or di-substituted amino group, an acyl group, and a C ₁ -C ₆ alkyl group. The number of substituents is not particularly limited, and the number of substituents of the R ² hydrolyzable group is 1 to 5. The number of substituents on the alkyl group of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is one, two or three.

Specific examples of the silane coupling agent (A) represented by the above formula (1) include (meth) acryloyloxymethyltrimethoxysilane, 2- (meth) acryloyloxyethyltrimethoxysilane, and 3- (meth) acryloyl. Oxypropyltrimethoxysilane, 4- (meth) acryloyloxybutyltrimethoxysilane, 5- (meth) acryloyloxypentyltrimethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 7- (meth) acryloyloxyheptyl Trimethoxysilane, 8- (meth) acryloyloxyoctyltrimethoxysilane, 9- (meth) acryloyloxynonyltrimethoxysilane, 10- (meth) acryloyloxydecyltrimethoxysilane, 11- (meth) acryloyloxy Ndecyltrimethoxysilane, 11- (meth) acryloyloxyundecyldichloromethylsilane, 11- (meth) acryloyloxyundecyltrichlorosilane, 11- (meth) acryloyloxyundecyldimethoxymethylsilane, 12- (meth) acryloyl Examples thereof include oxide decyltrimethoxysilane and 13- (meth) acryloyloxytridecyltrimethoxysilane. These can be used individually by 1 type or in combination of 2 or more types. Among these, when the alkylene group represented by — (CH ₂ ) _p — is moderately long, it has good compatibility with the polymerizable monomer in the self-adhesive composite resin and is included in the self-adhesive dental composite resin. filler (f) sufficiently Fuyaseru point the amount of and - (CH _{2) p} - alkylene group represented by is not too reasonably short hydrophobic strong, from the viewpoint of adhesive strength is increased, 2 -Methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, 6-methacryloyloxyhexyltrimethoxysilane are preferred, and 3-methacryloyloxy More preferred is propyltrimethoxysilane.

  Any organosilazane (B) may be used as long as it binds to the hydroxyl group present on the surface of the filler (f) and the hydroxyl group derived from the silane coupling agent (A) by a deammonification reaction, but the one having a small molecular weight is used. Is preferred. Specifically, hexaethyldisilazane, hexa-n-propyldisilazane, hexaisopropyldisilazane, 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetra Examples include methyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane, and the like. 1,1,3,3-tetramethyl Disilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane and the like are preferable.

  The amount of treatment with the silane coupling agent (A) in the filler (f) is preferably 0.5 to 15 parts by mass and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the filler (f) before the surface treatment. Preferably, 2 to 8 parts by mass is particularly preferable. When the amount is less than 0.5 part by mass, a sufficient polymerizable group cannot be imparted on the surface of the filler (f), and the mechanical strength may be lowered.

  The molar ratio of the silane coupling agent (A) and the organosilazane (B) in the surface treatment of the filler (f) is silane coupling agent (A): organosilazane (B) = 1: 1 to 1:20. It is preferable that the ratio is 1: 2 to 1:10. If the organosilazane (B) is less than the silane coupling agent (A), aggregation may proceed in the paste, and transparency during the storage period may not be ensured. In addition, 1 mol of the silane coupling agent (A) On the other hand, when organosilazane (B) exceeds 20 mol, there is a possibility that the hydrophobicity becomes strong and sufficient adhesive strength cannot be obtained.

  In the surface treatment, a polymerization inhibitor may be added to suppress the polymerization of the silane coupling agent (A). As the polymerization inhibitor, known ones such as 3,5-dibutyl-4-hydroxytoluene (BHT) and p-methoxyphenol (methoquinone) can be used.

  The surface treatment agent used for the surface treatment of the filler (f) substantially contains only the silane coupling agent (A) represented by the formula (1) and the organosilazane (B) represented by the formula (2). Those are preferred. Substantially containing only the silane coupling agent (A) and the organosilazane (B) means that the amount of the surface treatment agent other than the silane coupling agent (A) and the organosilazane (B) is 1.0 mass. Means less than 0.5%, preferably less than 0.5% by weight, more preferably less than 0.1% by weight.

Furthermore, what made the filler (f) after surface treatment solidify as a filler (f) is preferable. Solidification is a step in which the filler (f) after the surface treatment is precipitated with a mineral acid, and the precipitate is washed with water and / or dehydrated (for example, dried) to obtain a solid matter of the filler (f). As described above, since the filler surface-treated only with a general silane coupling agent (A) is very flocculated, it is very difficult to disperse again after solidifying once. However, since the filler (f) of the present invention hardly aggregates, it is difficult to aggregate even if solidified, and it is easy to redisperse even if aggregated. In addition, as above-mentioned, a filler (f) with few ionic impurities, such as an alkali metal, can be easily manufactured by wash | cleaning a filler (f) with water. By using the filler (f) with a small amount of ionic impurities, the repulsive force between the alkyl groups described above can be maintained longer, the high transparency of the paste can be maintained longer, and the acidic group-containing (meth) acrylic polymerization Interaction between protons (H ⁺ ) generated from the polymerizable monomer (a) or hydroxyl groups (—OH) contained in other polymerizable monomers and very few residual silanol groups and ionic impurities The possibility can be further reduced, and changes in transparency and properties of the paste can be further suppressed. In the cleaning step, it is preferable to repeat the cleaning until the electrical conductivity of the extracted water of the filler (f) (for example, water in which the filler (f) is immersed at 121 ° C. for 24 hours) becomes 50 μS / cm or less. .

  Examples of the mineral acid used for solidification include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and hydrochloric acid is particularly preferable. The mineral acid may be used as it is, but is preferably used as a mineral acid aqueous solution. The concentration of the mineral acid in the mineral acid aqueous solution is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The amount of the mineral acid aqueous solution can be about 6 to 12 times based on the mass of the filler (f) to be cleaned.

  The cleaning with the mineral acid aqueous solution can be performed a plurality of times. Washing with the aqueous mineral acid solution is preferably performed after the filler (f) is immersed in the aqueous mineral acid solution. Further, it may be left in the immersed state for 1 to 24 hours, and further for about 72 hours. When it is allowed to stand, stirring may be continued or not stirred. When washing in the mineral acid-containing liquid, it can be heated to room temperature or higher. Thereafter, the filler (f) is filtered and washed with water. It is preferable that the water used for washing does not contain ions such as alkali metals (for example, 1 ppm or less on a mass basis). For example, ion exchange water, distilled water, pure water or the like. Washing with water may be performed after the filler (f) is dispersed and suspended, and then filtered, as in the case of washing with an aqueous mineral acid solution, and water is continuously passed through the filtered filler (f). May be. The end of washing with water may be determined by the electric conductivity of the extracted water described above, or may be the time when the alkali metal concentration in the waste water after washing the filler (f) becomes 1 ppm or less. The alkali metal concentration of the extracted water may be set to 5 ppm or less. When washing with water, it can be heated to a room temperature or higher.

  The filler (f) can be dried by a conventional method. For example, it may be left under heating or reduced pressure (vacuum). A heating apparatus and a pressure reduction apparatus are not specifically limited, A well-known thing can be used.

  As a method of dehydrating the filler (f) other than drying, after adding a water-based organic solvent having a boiling point higher than water to the water-containing filler (f), a mixed material that is soluble in the water-based organic solvent is mixed. Then, a method for removing water can be used. Examples of the aqueous organic solvent include propylene glycol monomethyl ether (propylene glycol-1-methyl ether, boiling point of about 119 ° C .; propylene glycol-2-methyl ether, boiling point of about 130 ° C.), butanol (boiling point of 117.7 ° C.), N-methyl. -2-pyrrolidone (boiling point of about 204 ° C.), γ-butyrolactone (boiling point of about 204 ° C.) and the like.

  In the self-adhesive dental composite resin of the present invention, the blending amount of the filler (f) with respect to 100 parts by mass of the total amount of polymerizable monomer components has sufficient mechanical strength after polymerization and curing by visible light irradiation. In addition, from the viewpoint of excellent property stability of the paste during long-term storage before polymerization and curing, it is preferably 25 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the polymerizable monomer. 100 mass parts or more is more preferable from the point which the adhesive dental composite resin has a higher mechanical strength. In addition, from the viewpoint of not impairing the operability of the paste such as the adhesive strength and consistency of the self-adhesive dental composite resin, 400 parts by mass or less is preferable with respect to 100 parts by mass of the polymerizable monomer, and 350 parts by mass or less. Is more preferable, and 300 parts by mass or less is even more preferable. Therefore, from the above viewpoint, the blending amount of the filler (f) is preferably 25 to 400 parts by mass, more preferably 50 to 350 parts by mass, and 100 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Further preferred.

  Next, the acidic group-containing (meth) acrylic polymerizable monomer (a) used in the present invention will be described. In the present invention, the (meth) acrylic polymerizable monomer means a (meth) acrylate polymerizable monomer and / or a (meth) acrylamide polymerizable monomer.

  The acidic group-containing (meth) acrylic polymerizable monomer (a) is an essential component for the self-adhesive dental composite resin of the present invention to exhibit adhesiveness. The acidic group-containing (meth) acrylic polymerizable monomer (a) has an action of decalcifying the tooth substance. The acidic group-containing (meth) acrylic polymerizable monomer (a) has at least one acidic group such as a phosphoric acid group, a phosphonic acid group, a pyrophosphoric acid group, a carboxylic acid group and a sulfonic acid group, and acryloyl. A polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, an acrylamide group, and a methacrylamide group. From the viewpoint of adhesion to teeth, the acidic group-containing (meth) acrylic polymerizable monomer (a) has any one of acryloyl group, methacryloyl group, acrylamide group or methacrylamide group as a polymerizable group. It is preferably monofunctional. Specific examples include the following.

  Examples of the phosphoric acid group-containing (meth) acrylic polymerizable monomer 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- (meth) acryloyloxydecyl dihydrogen phosphate, 1- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxy hexadecyl dihydrogen phosphate, 20- (meth) acryloyloxyeicosyl Dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acryloyloxyethyl- (4-methoxyphenyl) Phosphoric acid group-containing monofunctional (meth) acrylates such as hydrogen phosphate and 2- (meth) acryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate , Acid chlorides thereof, alkali metal salts, ammonium salts, and amine salts; 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) acryloyloxynonyl] hydrogen phosphate, bis [10- (meta ) Acryloyloxydecyl] hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl dihydrogen phosphate and other phosphate group-containing bifunctional (meth) acrylate compounds, their acid chlorides, alkali metal salts, Examples thereof include ammonium salts and amine salts.

  Examples of the phosphonic acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acryloyloxyethylphenylphosphonate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate, 6- ( (Meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexylphosphonoacetate, 10- (meth) acryloyloxy Examples include decylphosphonoacetate, acid chlorides thereof, alkali metal salts, ammonium salts, and amine salts.

  Examples of the (meth) acrylic polymerizable monomer containing a pyrophosphate group include bis [2- (meth) acryloyloxyethyl pyrophosphate], bis [4- (meth) acryloyloxybutyl pyrophosphate], and bis pyrophosphate. [6- (meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, acid chlorides thereof, alkali metal salts, ammonium Examples thereof include salts and amine salts.

  Examples of the carboxylic acid group-containing (meth) acrylic polymerizable monomer include (meth) acrylic acid, 4- [2-[(meth) acryloyloxy] ethoxycarbonyl] phthalic acid, and 4- (meth) acryloyloxy. Ethyl trimellitic acid, 4- (meth) acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyl Oxydecyloxycarbonylphthalic acid and acid anhydrides thereof; 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1, 1-octanedicarboxylic acid, 10- (meth) Acryloyloxy-1,1-decane dicarboxylic acid, 11- (meth) acryloyloxy-1,1-undecane dicarboxylic acid, their acid chlorides, alkali metal salts, ammonium salts, and amine salts thereof.

  Examples of the sulfonic acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl (meth) acrylate, acid chlorides thereof, and alkali metal salts. , Ammonium salts, and amine salts.

Among the acidic group-containing (meth) acrylic polymerizable monomers (a), phosphoric acid group-containing (meth) acrylic polymerizable monomers, pyrophosphate group-containing (meth) acrylic polymerizable monomers , And a carboxylic acid group-containing (meth) acrylic polymerizable monomer is preferable because it expresses better adhesion to the tooth, and in particular, a phosphate group-containing (meth) acrylic polymerizable monomer, And a carboxylic acid group-containing (meth) acrylic polymerizable monomer is preferred. Among them, a phosphoric acid group-containing (meth) acrylate monofunctional polymerizable monomer or a carboxylic acid having an alkylene group of alkyl or C ₆ -C ₂₀ in C ₆ -C ₂₀ principal chain in the molecule The (meth) acrylate-based polymerizable monomer is more preferable, and the phosphate group-containing (meth) acrylate-based monofunctional polymerizable monomer having a C _{8 to} C ₁₂ alkylene group as a main chain in the molecule is further included. preferable. Further, 10-methacryloyloxydecyl dihydrogen phosphate, 4- (meth) acryloyloxyethyl trimellitic acid and 4- (meth) acryloyloxyethyl trimellitic anhydride are preferable, and 10-methacryloyloxydecyl dihydrogen phosphate is preferable. Most preferred.

  The acidic group-containing (meth) acrylic polymerizable monomer (a) may be used alone or in combination of two or more. The blending amount of the acidic group-containing (meth) acrylic polymerizable monomer (a) is not particularly limited as long as the effect of the present invention is exhibited, but the total amount of the polymerizable monomer component from the viewpoint of higher adhesive strength. In 100 mass parts, the range of 1-40 mass parts is preferable, The range of 2-20 mass parts is more preferable, The range of 4-20 mass parts is the most preferable. In the present specification, the blending amount of a certain polymerizable monomer in 100 parts by mass of the total amount of the polymerizable monomer component means that the total amount of the polymerizable monomer component is 100% by mass. It means the blending amount (% by mass) of the polymerizable monomer. Therefore, the total amount of each polymerizable monomer component does not exceed 100 parts by mass.

  Then, the polyfunctional (meth) acrylic-type polymerizable monomer (b) which does not contain the acidic group used by this invention is demonstrated. The polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group has at least two polymerizable groups without having an acidic group in the molecule. The polyfunctional (meth) acrylic polymerizable monomer (b) which does not contain an acidic group has an effect of improving the handleability or mechanical strength of the self-adhesive dental composite resin of the present invention. An aliphatic compound-based bifunctional polymerizable monomer, an aliphatic compound-based bifunctional polymerizable monomer, a tri- or higher functional polymerizable monomer, and the like.

  Examples of the aromatic compound-based bifunctional polymerizable monomer include 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth) acryloyloxy-). 2-hydroxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane (average of ethoxy groups) Having an addition mole number of 2.6), 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, , 2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acrylo Ruoxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) Acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxy Phenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxy) Bifunctional (meta) such as isopropoxyphenyl) propane Acrylate compounds, and the like.

  Examples of the aliphatic compound-based bifunctional polymerizable monomer include glycerol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene. Glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) di (meth) acrylate, 1,2-bis (3-methacryl Yloxy-2-hydroxypropoxy) bifunctional such as ethane (meth) acrylate compounds, and the like.

  Examples of the trifunctional or higher polymerizable monomer include, for example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetra (Meth) acrylates and trifunctional or higher (meth) acrylate compounds such as 1,7-diaacryloyloxy-2,2,6,6-tetra (meth) acryloyloxymethyl-4-oxaheptane are exemplified. Among these, N, N ′-(2,2,4-trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate is preferable.

  Among the polyfunctional (meth) acrylic polymerizable monomers (b) not containing the acidic group, from the viewpoint of mechanical strength or handleability, aromatic compound-based bifunctional polymerizable monomers, and An aliphatic compound-based bifunctional polymerizable monomer is preferably used. Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (commonly referred to as “Bis-GMA”), and 2, 2-bis (4-methacryloyloxypolyethoxyphenyl) propane (having an average addition mole number of ethoxy groups of 2.6, commonly called “D-2.6E”) is preferable. Examples of the aliphatic compound-based bifunctional polymerizable monomer include glycerol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly referred to as “TEGDMA”), neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, and 2,2,4-trimethyl Hexamethylene bis (2-carbamoyloxyethyl) dimethacrylate (commonly known as “UDMA”) is preferred.

  Among the polyfunctional (meth) acrylic polymerizable monomers (b) containing no acidic group, Bis-GMA, D-2.6E, TEGDMA, and UDMA are more preferable, and Bis-GMA, UDMA, and TEGDMA are more preferable. .

  The polyfunctional (meth) acrylic polymerizable monomer (b) that does not contain an acidic group may be used alone or in combination of two or more. The blending amount of the polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group is not particularly limited as long as the effect of the present invention is exhibited, but a dental composition (self-adhesive dental composite resin) 30-95 parts by mass in 100 parts by mass of the total amount of polymerizable monomer components in the self-adhesive dental composite resin, because of its high permeability to tooth and excellent adhesive strength, and sufficient strength. It is. The range of 40-90 mass parts is preferable, the range of 50-85 mass parts is more preferable, and the range of 60-80 mass parts is the most preferable.

  The self-adhesive dental composite resin of the present invention may further contain a polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton as a polymerizable monomer component. The polyfunctional (meth) acrylamide polymerizable monomer (g) having at least one amide proton has high hydrophilicity because it has at least one amide proton and penetrates into the collagen layer of dentin. Easily and has multiple polymerizable groups in the molecule, so it has a very high curability together with other components of self-adhesive dental composite resin, so it has higher adhesion to dentin can get.

  As the polyfunctional (meth) acrylamide polymerizable monomer (g), the polyfunctional (meth) acrylamide polymerizable monomer (g1) represented by the following general formula (4), represented by the following general formula (5): And the polyfunctional (meth) acrylamide polymerizable monomer (g2) and the polyfunctional (meth) acrylamide polymerizable monomer (g3) represented by the following general formula (6).

Wherein R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a methyl group, t is an integer of 1 to 6, and X ¹ and X ² are each independently substituted. have a group which is linear or branched alkylene group which may C ₁ ~C _8.)

(In the formula, R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a methyl group, u is 2 or 3, and X ³ and X ⁴ each independently have a substituent. C ₁ -C ₈ linear or branched alkylene groups that may be present.)

(Wherein, Z is an aliphatic group or an aromatic group of linear or branched optionally C ₁ -C ₈ may have a substituent, wherein the aliphatic group, -O -, - S -, - CO -, - CO -O -, - O-CO -, - NR 18 -, - CONR 18 -, - NR 18 -CO -, - CO-O-NR 18 -, - O-CONR ¹⁸ - and -NR ¹⁸ -CO-NR ¹⁸ - which may be interrupted by at least one bonding group selected from the group consisting .R ¹⁸ is optionally C ₁ may have a hydrogen atom or a substituent It represents a linear or branched chain aliphatic group of -C _8.)

R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ are preferably hydrogen atoms from the viewpoints of adhesion to the tooth and polymerization curability. t is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. u is preferably 3.

Examples of the C ₁ -C ₈ linear or branched alkylene group which may have a substituent of X ¹ , X ² , X ³ and X ⁴ include, for example, a methylene group, a methylmethylene group, an ethylene group 1-methylethylene group, 2-methylethylene group, trimethylene group, 1-ethylethylene group, 2-ethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, 1-propylethylene group, 2-propylethylene group, 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group 1,1,2-trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 3-ethyltrimethylene group 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1-methyltetramethylene group Methylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, pentamethylene group, 1-butylethylene group, 2-butylethylene group, 1-methyl-1-propylethylene group, 1-methyl-2-propylethylene group, 2-methyl-2-propylethylene group, 1,1-diethylethylene group, 1,2-diethylethylene group, 2,2-diethylethylene group, 1-ethyl-1, 2-dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3 Methyl pentamethylene group, 4-methyl-pentamethylene group, 5-methyl-pentamethylene group, hexamethylene group and the like.

Examples of the substituent for X ¹ , X ² , X ³ , and X ⁴ include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group, hydroxy group, amino group, C _{1 to} C _8. mono- or di-substituted amino group with an alkyl group, an acyl group, an acyloxy group, an amide group, C ₂ -C ₈ alkoxycarbonyl group, C ₁ -C ₈ alkoxy group, C ₁ -C ₈ alkylthio group, C ₁ -C _{An 8} alkyl group is preferable, and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a C _{1 to} C ₈ alkyl group, and the like are more preferable. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, and isopentyl. Group, n-hexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group and the like. The alkyl group, the alkyl group of C ₁ -C ₄ straight or branched chain. The number of substituents is not particularly limited, and may be about 1 to 8, preferably 1, 2, or 3.

The C ₁ -C ₈ aliphatic group optionally having a substituent represented by Z is a saturated aliphatic group (an alkylene group, a cycloalkylene group (for example, 1,4-cyclohexylene group, etc.)). , An unsaturated aliphatic group (alkenylene group, alkynylene group) may be used, and a saturated aliphatic group (alkylene group) is preferable from the viewpoint of availability or production and chemical stability. Z is preferably a linear or branched C _{1 to} C ₄ aliphatic group which may have a substituent, from the viewpoint of adhesion to teeth and polymerization curability, and has a substituent. It is more preferably a linear or branched C _{2 to} C ₄ aliphatic group that may be used. Examples of the C ₁ -C ₈ alkylene group include those similar to X ¹ , X ² , X ³ , and X ⁴ .

  Examples of the aromatic group optionally having a substituent represented by Z include an aryl group and an aromatic heterocyclic group. As the aromatic group, an aryl group is preferable to an aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5-membered ring or a 6-membered ring. As the aryl group, for example, a phenyl group is preferable. Examples of aromatic heterocyclic groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, furazane, triazole, pyran, and pyridine. Groups, pyridazine groups, pyrimidine groups, pyrazine groups, and 1,3,5-triazine groups. Of the aromatic groups, a phenyl group is particularly preferred.

As the aliphatic group for R ^{18, any} of a saturated aliphatic group (alkyl group) and an unsaturated aliphatic group (alkenyl group, alkynyl group) may be used. Ease of availability or production and chemical stability From the viewpoint, a saturated aliphatic group (alkyl group) is preferable. Examples of the alkyl group include C ₁ -C ₈ alkyl groups similar to those described as substituents for X ¹ , X ² , X ³ , and X ⁴ . R ¹⁸ is more preferably a linear or branched C _{1 to} C ₄ alkyl group optionally having a hydrogen atom or a substituent, and a linear or branched optionally having a hydrogen atom or a substituent. More preferred are C ₁ -C ₃ alkyl groups in the chain.

  The aliphatic group of Z may be interrupted by at least one linking group described above. That is, at least one of the bonding groups may be inserted into the aliphatic group. When the aliphatic group of Z is interrupted by the linking group, the number of linking groups is not particularly limited, but may be about 1 to 10, preferably 1, 2, or 3. More preferably one or two. In the above formula (5), it is preferable that the aliphatic group of Z is not interrupted by the continuous linking group. That is, it is preferable that the bonding group is not adjacent. Examples of the linking group include -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, and -CO-O-. More preferred is at least one linking group selected from the group consisting of NH-, -O-CO-NH- and -NH-CO-NH-, -O-, -S-, -CO-, -NH-, Particularly preferred is at least one linking group selected from the group consisting of —CO—NH— and —NH—CO—.

Specific examples of the polyfunctional (meth) acrylamide polymerizable monomer (g1) represented by the above formula (4) are not particularly limited, but include the following.

  Among these, from the viewpoint of adhesiveness to the tooth and polymerization curability, the compound (g1-1), the compound (g1-3), the compound (g1-5), and the compound (g1-7) are preferable, and the compound (g1- 1) and compound (g1-5) are more preferable, and compound (g1-5) is most preferable from the viewpoint of high hydrophilicity related to the penetration of dentin into the collagen layer.

Although it does not specifically limit as a specific example of the polyfunctional (meth) acrylamide polymerizable monomer (g2) represented by the said Formula (5), The thing shown below is mentioned.

  Among these, from the viewpoint of adhesiveness to the tooth and polymerization curability, the compound (g2-1), the compound (g2-3), the compound (g2-5), and the compound (g2-7) are preferable, and the compound (g2- 1) and compound (g2-3) are more preferable, and compound (g2-1) is most preferable from the viewpoint of high hydrophilicity related to the penetration of dentin into the collagen layer.

  Specific examples of the polyfunctional (meth) acrylamide polymerizable monomer (g3) represented by the above formula (6) (hereinafter also referred to as asymmetric polyfunctional (meth) acrylamide polymerizable monomer (g3)). Although it does not specifically limit as above, What is shown below is mentioned.

  Among these, N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N- (1-ethyl- (2-methacryloyloxy) from the viewpoint of adhesion to teeth and polymerization curability Ethyl) acrylamide and N- (2- (2-methacryloyloxyethoxy) ethyl) acrylamide are more preferable, and N-methacryloyloxyethylacrylamide, N- from the viewpoint of high hydrophilicity related to penetration of dentin into the collagen layer. Most preferred is methacryloyloxypropylacrylamide.

  The polyfunctional (meth) acrylamide polymerizable monomer (g) having at least one amide proton may be used alone or in combination of two or more. For example, a group consisting of a polyfunctional (meth) acrylamide polymerizable monomer (g3), a polyfunctional (meth) acrylamide polymerizable monomer (g1), and a polyfunctional (meth) acrylamide polymerizable monomer (g2) A combination with one or more polymerizable monomers selected from may be used. The blending amount of the polyfunctional (meth) acrylamide polymerizable monomer (g) is not particularly limited as long as the effects of the present invention can be obtained. In a part, the range of 0.5-30 mass parts is preferable, The range of 2-25 mass parts is more preferable, The range of 3-20 mass parts is the most preferable.

  The self-adhesive dental composite resin of the present invention may further contain or exclude a hydrophilic monofunctional polymerizable monomer (h) as a polymerizable monomer component. The hydrophilic monofunctional polymerizable monomer (h) is a monofunctional polymerizable monomer other than (a), (b) and (g) having a solubility in water at 25 ° C. of 5% by mass or more. The solubility is preferably 10% by mass or more, more preferably 15% by mass or more. By including the hydrophilic monofunctional polymerizable monomer (h), higher adhesive force can be obtained for dentin.

  The hydrophilic monofunctional polymerizable monomer (h) has at least one hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, and an amide group. As the hydrophilic monofunctional polymerizable monomer (h), 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl Hydrophilic monofunctional (meth) acrylate polymerizable monomers such as (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-trimethylammoniumethyl (meth) acryl chloride; N-methylol (meta ) Acrylamide, N-hydroxyethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, 4 -(Meth) acryloyl Hydrophilic monofunctional (meta) such as ruphorin, N-trihydroxymethyl-N-methyl (meth) acrylamide, and monofunctional (meth) acrylamide polymerizable monomer represented by the following general formula (7) ) Acrylic polymerizable monomers.

Wherein R ¹⁸ and R ¹⁹ are each independently a linear or branched C ₁ -C ₃ alkyl group which may have a substituent, and R ²⁰ is a hydrogen atom or a methyl group. is there.)

Examples of the substituent for R ¹⁸ and R ¹⁹ include the same substituents as those for X ¹ , X ² , X ³ , and X ⁴ . The alkyl groups of the C ₁ -C ₃ in the R ¹⁸ and R ^19, a methyl group, an ethyl group, n- propyl group, an isopropyl group.

  Among these hydrophilic monofunctional polymerizable monomers (h), 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, diacetone (meta) are used from the viewpoint of adhesiveness to teeth. ) Hydrophilic monofunctional (meth) acrylamide polymerizable monomers represented by acrylamide and general formula (7) are preferred, and monofunctional (meth) acrylamide polymerizable properties represented by general formula (7) Monomers are more preferred. As the hydrophilic monofunctional polymerizable monomer (f), one type may be used alone, or two or more types may be used in combination.

  Among the monofunctional (meth) acrylamide polymerizable monomers represented by the general formula (7), N, N-dimethylacrylamide and N, N-diethylacrylamide are more preferable from the viewpoint of storage stability. N, N-diethylacrylamide is most preferred.

  The blending amount of the hydrophilic monofunctional polymerizable monomer (h) in the present invention is not particularly limited as long as the effects of the present invention are exerted. From the viewpoint of exhibiting sufficient adhesive strength improving effect and mechanical strength, self In 100 parts by mass of the total amount of polymerizable monomer components in the adhesive dental composite resin, a range of 1 to 30 parts by mass is preferred, a range of 2 to 28 parts by mass is more preferred, and a range of 5 to 25 parts by mass is preferred. More preferably, the range of 7-20 mass parts is especially preferable.

  The self-adhesive dental composite resin of the present invention has an acidic group-containing (meth) acrylic polymerizability within the range that does not impede the effects of the present invention in order to improve adhesive strength, handleability, and mechanical strength. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton, hydrophilic A polymerizable monomer (m) other than the monofunctional polymerizable monomer (h) may be blended. Examples of the polymerizable monomer (m) include a hydrophilic polyfunctional (meth) acrylate polymerizable monomer (m1) and / or a symmetric (meth) acrylamide compound (m2). The hydrophilic polyfunctional (meth) acrylate polymerizable monomer (m1) is a monofunctional polymer other than (a), (b) and (g) having a water solubility at 25 ° C. of 5% by mass or more. Which has a solubility of 10% by mass or more, more preferably 15% by mass or more. Examples of the hydrophilic polyfunctional (meth) acrylate polymerizable monomer (m1) include pentaerythritol di (meth) acrylate, erythritol di (meth) acrylate, mannitol di (meth) acrylate, and xylitol di (meth). Examples include acrylate and sorbitol di (meth) acrylate. Examples of the symmetric (meth) acrylamide compound (g2) include N, N′-ethylenebisacrylamide, N, N′-diethyl-1,3-propylenebisacrylamide, and the like.

  The total amount of the polymerizable monomers contained in the self-adhesive dental composite resin of the present invention is preferably less than 49.9% by mass with respect to the entire self-adhesive dental composite resin, and 44.5% by mass. % Is more preferable, and less than 40.0 mass% is more preferable. The total amount of the polymerizable monomers is preferably 9.0% by mass or more, more preferably 14.0% by mass or more, and 19.0% by mass with respect to the entire self-adhesive dental composite resin. The above is more preferable.

  The photopolymerization initiator (c) is a component that accelerates the polymerization and hardening of the self-adhesive dental composite resin. The photopolymerization initiator (c) can be selected from known photopolymerization initiators, and among them, the photopolymerization initiator used for dental use is preferably used. A photoinitiator (c) is used individually by 1 type or in combination of 2 or more types.

  Examples of the photopolymerization initiator (c) include (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, Anthraquinones, benzoin alkyl ether compounds, α-amino ketone compounds and the like can be mentioned.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and coumarins. As a result, a self-adhesive dental composite resin having excellent photocurability in the visible and near-ultraviolet region and having sufficient photocurability using any light source such as a halogen lamp, a light emitting diode (LED), or a xenon lamp can be obtained. can get.

  Examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoyl. Examples include methoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, and benzoyldi- (2,6-dimethylphenyl) phosphonate. Among these, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable.

  Examples of the 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. Among these, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide is preferable.

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

  Examples of the coumarin compound include 3,3′-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3 -Benzoyl-7-methoxycoumarin, 3-benzoyl-6-methoxycoumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoylcoumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p- Nitrobenzoyl) coumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3′-carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoylbenzo [F] Coumarin, 3-carboxycoumarin, 3-carboxy- -Methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylaminocoumarin , 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- ( 4-methoxybenzoyl) coumarin, 3- (4-nitrobenzoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- (3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxy) Coumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3 -(2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazoloyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) Coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3′-carbonylbis (7-dibutylaminocoumarin), 3, 3'-carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3,6 , 7-Tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, 10- (2-benzothiazoyl)- 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one, etc. Examples thereof include compounds described in Japanese Patent No. 3109 and Japanese Patent Laid-Open No. 10-245525. Among these, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are preferable.

  Specific examples of water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, anthraquinones, benzoin alkyl ether compounds, and α-aminoketone compounds include International Publication No. 2008/089777. The thing of description is mentioned.

  Although the compounding quantity of a photoinitiator (c) is not specifically limited, From a viewpoint of the sclerosis | hardenability etc. of the self-adhesive dental composite resin obtained, it is 0. 001-20 mass parts is preferable, 0.05-10 mass parts is more preferable, and 0.10-5 mass parts is further more preferable. When the blending amount of the photopolymerization initiator (c) is less than 0.001 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers, the polymerization does not proceed sufficiently, and the adhesive strength may be reduced. Therefore, 0.05 mass part or more is more preferable, and 0.10 mass part or more is further more preferable. On the other hand, when the blending amount of the photopolymerization initiator (c) exceeds 20 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers, it is sufficient when the polymerization performance of the photopolymerization initiator itself is low. Adhesive strength may not be obtained, and further, precipitation from the self-adhesive dental composite resin may be caused. Preferably, it is 5 parts by mass or less.

  The self-adhesive dental composite resin of the present invention can further contain a chemical polymerization initiator. As the chemical polymerization initiator, an organic peroxide is preferably used. The organic peroxide is not particularly limited, and a known one can be used. Typical organic peroxides include, for example, ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate and the like. Specific examples of these organic peroxides include those described in International Publication No. 2008/089777.

  In the self-adhesive dental composite resin of the present invention, a filler (k) that is not fumed silica (d) and not a filler (f) has an influence on the high fluidity and paste properties during storage over a long period of time. You may include in the range which is not. The filler (k) is a component for the purpose of imparting radiopacity to the self-adhesive dental composite resin, or improving the strength as a matrix or paste operability.

  As used herein, “radiopaque” refers to the ability of a solidified dental material to be distinguished from a tooth structure using standard dental x-ray equipment in a conventional manner. Radiopacity in the dental material is advantageous in certain cases where X-rays are used to diagnose dental conditions.

  As the filler (k), known fillers used for dental composite resins can be used without any limitation, and organosilazane (B) is used as a surface treatment agent and / or fumed silica (d). Is not included. Examples of the filler include various glasses [silica as a main component and, if necessary, oxides such as heavy metals, boron, and aluminum. For example, glass powder having a general composition such as fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (pyrex (registered trademark) glass); barium glass (GM27884, 8235, manufactured by Schott, E2000, E3000, manufactured by ESSTECC), strontium borosilicate glass (E4000, manufactured by ESSTECC), lanthanum glass ceramics (GM31684, manufactured by Schott), fluoroaluminosilicate glass (GM35429, G018-091, G018-117, Shot) Dental glass powder], various ceramics, composite oxides such as silica-titania, silica-zirconia, diatomaceous earth, kaolin, clay mineral (montmorillonite, etc.), activated clay, synthetic zeolite, mica Calcium fluoride, ytterbium fluoride, yttrium fluoride, core-shell structure calcium fluoride coated with silica, core-shell structure ytterbium fluoride coated with silica, core-shell structure coated with silica Yttrium fluoride, calcium phosphate, barium sulfate, zirconium dioxide, titanium dioxide, hydroxyapatite, core-shell structure calcium phosphate coated with silica, core-shell structure barium sulfate coated with silica, surface coated with silica Examples thereof include zirconium dioxide having a core / shell structure, titanium dioxide having a core / shell structure whose surface is coated with silica, and hydroxyapatite having a core / shell structure whose surface is coated with silica. These can be used alone or in combination of two or more. Among these, since X-ray opacity is manifested in a small amount and can be treated with the silane coupling agent (A), the core-shell structure ytterbium fluoride coated with silica and the core-shell structure coated with silica Yttrium fluoride is preferred.

  The average particle size of the filler (k) is preferably 0.01 to 50.0 μm, more preferably 0.05 to 20.0 μm, further preferably 0.08 to 10.0 μm, and 0.10 to 4.50 μm. Is particularly preferred. Within these ranges, sufficient mechanical strength can be obtained, the paste is not sticky, the operability is not problematic, and the cured product is excellent in polishing lubricity and lubrication durability. In addition, in this specification, the average particle diameter of a filler means the average particle diameter (average primary particle diameter) of the primary particle of a filler.

  In addition, the average particle diameter of a filler (k) can be measured like the measuring method of the average particle diameter of a filler (f).

  The filler (k) is preferably treated with a surface treatment agent. Examples of the surface treatment agent include at least one organometallic compound selected from the group consisting of an organosilicon compound, an organotitanium compound, an organozirconium compound, and an organoaluminum compound. When two or more kinds of organometallic compounds are used, the surface treatment layer may be a mixture of two or more kinds of organometallic compounds, or may be a surface treatment layer having a multilayer structure in which two or more kinds of organometallic compound layers are laminated. Good.

Examples of the organosilicon compound include compounds represented by (W) _n SiY _4-n , which are exemplified as the surface treating agent for fumed silica (d) (wherein the symbols have the same meaning as described above). ).

  Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3,3-trifluoropropyldimethoxysilane, β- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-me Acryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltri Methoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbutane Mosilane, diethylsilane, vinyltriacetoxysilane, ω- (meth) acryloyloxyalkyltrimethoxysilane (carbon number between (meth) acryloyloxy group and silicon atom: 3-12, for example, 3-methacryloyloxypropyltri Methoxysilane, etc.), ω- (meth) acryloyloxyalkyltriethoxysilane (carbon number between (meth) acryloyloxy group and silicon atom: 3-12, for example, 3-methacryloyloxypropyltriethoxysilane), etc. Is mentioned.

  Among these, a coupling agent having a functional group capable of copolymerizing with the polymerizable monomer component, for example, ω- (meth) acryloyloxyalkyltrimethoxysilane (carbon between (meth) acryloyloxy group and silicon atom). Number: 3 to 12), ω- (meth) acryloyloxyalkyltriethoxysilane (carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12), vinyltrimethoxysilane, vinyltriethoxysilane, Vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane and the like are particularly preferably used.

  Examples of the organic titanium compound include tetramethyl titanate, tetraisopropyl titanate, tetra n-butyl titanate, butyl titanate dimer, and tetra (2-ethylhexyl) titanate.

  Examples of the organic zirconium compound include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, zirconyl acetate and the like.

  Examples of the organic aluminum compound include aluminum acetylacetonate and aluminum organic acid salt chelate compounds.

  The shape of the filler (k) is not particularly limited, and may be appropriately selected according to the characteristics to be enhanced as a dental composite resin. Specifically, the filler (k) may be used as a powder of amorphous or spherical particles. it can. When the amorphous filler (k) is used, the mechanical strength and abrasion resistance are particularly excellent, and when the spherical filler (k) is used, the polishing lubricity and the sliding durability are particularly excellent. A commercial item may be used for the filler (k) in this invention.

  Although the compounding quantity of the said filler (k) is not specifically limited as long as there exists an effect of this invention, The range of 1-100 mass parts is preferable with respect to 100 mass parts of polymerizable monomers, 3-90 mass parts is preferable. The range is more preferable, and the range of 5 to 80 parts by mass is particularly preferable. Within these ranges, sufficient X-ray opacity or sufficient mechanical strength of the cured product can be obtained, and sufficient paste operability can be obtained.

  The total amount of filler (fumed silica (d), filler (f) and filler (k)) contained in the self-adhesive dental composite resin of the present invention is based on the total amount of the self-adhesive dental composite resin. 50.0% by mass or more is preferable, 55.0% by mass or more is more preferable, and 59.0% by mass or more is more preferable. The total blending amount of the filler is preferably 90.0% by mass or less, more preferably 85.0% by mass or less, and further preferably 80.0% by mass or less with respect to the entire self-adhesive dental composite resin. . When the filler contained in the self-adhesive dental composite resin of the present invention is substantially only fumed silica (d) and filler (f), the preferred blending amount is fumed silica (d) and filler ( It is good also as the total compounding quantity of f).

  Next, other optional components contained in the self-adhesive dental composite resin of the present invention will be described.

  In another embodiment, the polymerization accelerator (i) is used together with the photopolymerization initiator (c) and / or the chemical polymerization initiator. Examples of the polymerization accelerator (i) used in the present invention include amines, sulfinic acids and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes. Thiol compounds, sulfites, bisulfites, thiourea compounds, and the like.

  The amines are classified 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 mono Tertiary such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Aliphatic amines, and the like. Among these, tertiary aliphatic amines are preferable from the viewpoint of curability and storage stability of the self-adhesive dental composite resin, and among these, 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, 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-tert-butylaniline, N, N-dimethyl-3,5-di-tert-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethyl) Amino) methyl benzoate, 4- (N, N-dimethylamino) propyl benzoate, 4- (N, N-dimethylamino) benzoic acid n-butoxyethyl, 4- (N, N-dimethylamino) benzoic acid 2 -(Methacryloyloxy) ethyl, 4- (N, N-dimethylamino) benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzoic acid from the viewpoint of imparting excellent curability to the self-adhesive dental composite resin. At least one selected from the group consisting of ethyl, n-butoxyethyl 4- (N, N-dimethylamino) benzoate and 4- (N, N-dimethylamino) benzophenone is preferably used.

  Specific examples of sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, bisulfites, and thiourea compounds Include those described in International Publication No. 2008/089777.

  The said polymerization accelerator (i) may mix | blend 1 type individually, and may mix | blend 2 or more types in combination. Although the compounding quantity of the polymerization accelerator (i) used for this invention is not specifically limited, From viewpoints, such as curability of the self-adhesive dental composite resin obtained, with respect to 100 mass parts of whole quantity of a polymerizable monomer. 0.001-30 mass parts is preferable, 0.01-10 mass parts is more preferable, 0.1-5 mass parts is the most preferable. The compounding amount of the polymerization accelerator (i) may be 0.05 parts by mass or more or 20 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monomers. When the blending amount of the polymerization accelerator (i) is less than 0.001 part by mass with respect to 100 parts by mass of the total amount of the polymerizable monomers, the polymerization does not proceed sufficiently and there is a risk of causing a decrease in adhesiveness. . On the other hand, when the blending amount of the polymerization accelerator (i) exceeds 30 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers, sufficient adhesion can be obtained depending on the polymerization performance of the polymerization initiator itself. Further, the polymerization accelerator (i) may be precipitated from the self-adhesive dental composite resin.

  The self-adhesive dental composite resin of the present invention may further contain a fluorine ion releasing substance (j). By compounding the fluoride ion releasing substance (j), a self-adhesive dental composite resin capable of imparting acid resistance to the tooth is obtained. Examples of the fluorine ion-releasing substance include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, and the like. The said fluorine ion releasing substance (j) may be used individually by 1 type, and may use 2 or more types together.

  A preferred embodiment of the self-adhesive dental composite resin of the present invention contains a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer contains an acidic group ( (Meth) acrylic polymerizable monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and polyfunctional (meth) acrylamide polymerizable monomer having an amide proton A self-adhesive dental composite resin containing (g) and the filler contains fumed silica (d) and filler (f) (excluding fumed silica (d)); A polymer, a photopolymerization initiator (c), and a filler, wherein the polymerizable monomer is an acidic group-containing (meth) acrylic polymerizable monomer (a), a polyfunctional compound containing no acidic group ( (Meth) acrylic polymerizable monomer (b) And a hydrophilic monofunctional polymerizable monomer (h), and the filler contains fumed silica (d) and filler (f) (excluding fumed silica (d)). Examples include self-adhesive dental composite resins.

  Another preferred embodiment includes a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer is an acidic group-containing (meth) acrylic polymerizable monomer. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton, and hydrophilicity The self-adhesive dentistry containing the monofunctional polymerizable monomer (h) and the filler containing fumed silica (d) and filler (f) (excluding fumed silica (d)) Composite resin for use.

  Furthermore, another preferred embodiment includes a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer is an acidic group-containing (meth) acrylic polymerizable monomer. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton, and hydrophilicity A polyfunctional (meth) acrylic polymerizable monomer (b) containing no monofunctional polymerizable monomer (h) and having no acidic group is an aliphatic compound-based bifunctional polymerizable monomer And the polyfunctional (meth) acrylamide polymerizable monomer (g) having the amide proton contains the polyfunctional (meth) acrylamide polymerizable monomer (g3) represented by the general formula (6). , The hydrophilic monofunctional polymerizable monomer (h) is hydrophilic monofunctional ( A) self-adhesive dental composite comprising an acrylate polymerizable monomer, wherein the filler comprises fumed silica (d) and filler (f) (excluding fumed silica (d)). Resin is mentioned.

  Furthermore, as another preferred embodiment, it contains a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer contains an acidic group-containing (meth) acrylic polymerizable compound. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton, and hydrophilic In the total amount of 100 parts by mass of the polymerizable monomer component, the acidic group-containing (meth) acrylic polymerizable monomer (a) is 1 to 1. 40 parts by mass, 30 to 95 parts by mass of a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and a polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton 0.5 to 30 parts by mass, 1 hydrophilic monofunctional polymerizable monomer (h) Contained 30 parts by weight, the filler is fumed silica (d) and a filler (f) (except fumed silica (d)) containing, include self-adhesive dental composite resin.

  In any of the preferred embodiments described above, based on the above description, the amount of each component can be appropriately changed, the type of the compound can be appropriately selected, and any component (for example, polymerization accelerator (i), chemical Polymerization initiators, polymerization inhibitors, etc.) may be added or removed.

  In addition, the self-adhesive dental composite resin of the present invention includes a pH adjuster, a polymerization inhibitor, a UV absorber, a thickener, a colorant, an antibacterial agent, a fragrance and the like as long as the effects of the present invention are not impaired. You may mix | blend.

  The self-adhesive dental composite resin of the present invention may be a single material type or a package type material type as a preferable material type. Among them, the single material type is more preferable from the viewpoint of easy operation.

  The present invention includes embodiments in which the above-described configurations are variously combined within the technical scope of the present invention as long as the effects of the present invention are exhibited.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples. The abbreviations and abbreviations used below are as follows. As the compounds used in the following Examples and Comparative Examples, commercially available products were used except when the synthesis method was described.

[Acid group-containing (meth) acrylic polymerizable monomer (a)]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate 4-META: 4- [2- (methacryloyloxy) ethoxycarbonyl] phthalic anhydride

[Polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group]
UDMA: 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate Bis-GMA: 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane D-2 .6E: 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (with an average addition mole number of ethoxy groups of 2.6)
TEGDMA: Triethylene glycol dimethacrylate

[Photopolymerization initiator (c)]
CQ: dl-camphorquinone BAPO: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Fumed silica (d)]
R 7200:
Commercially available product (trade name: AEROSIL® R 7200, surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m ² / g, average primary particle size: 12 nm, pH: 4.5, apparent Specific gravity: 230 g / l, manufactured by EVONIK INDUSTRIES) was used as it was.
R 8200:
Commercially available product (trade name: AEROSIL® R 8200, surface treatment agent: 1,1,1,3,3,3-hexamethyldisilazane, BET specific surface area: 155 m ² / g, average primary particle size: 12 nm PH: 5.5, apparent specific gravity: 140 g / l, manufactured by EVONIK INDUSTRIES) was used as it was.

[Long-chain organosilicon compound (e)]
11-MUS: 11-methacryloyloxyundecyltrimethoxysilane 8-MOS: 8-methacryloyloxyoctyltrimethoxysilane

[Short chain organosilicon compound]
3-MPS: 3-methacryloyloxypropyltrimethoxysilane

[Polyfunctional (meth) acrylamide polymerizable monomer having amide proton (g)]
TAC4: N, N ′, N ″, N ′ ″-tetraacryloyltriethylenetetramine (compound represented by the following formula (g1-5))
MAEA: N-methacryloyloxyethylacrylamide (asymmetric polyfunctional (meth) acrylamide polymerizable monomer represented by the following formula)

[Hydrophilic monofunctional polymerizable monomer (h)]
DEAA: N, N-diethylacrylamide HEMA: 2-hydroxyethyl methacrylate

[Filler (k)]
SiO ₂ coated YBF: silica-coated ytterbium fluoride commercial product (SG-YBF100WSCMP10, average particle size 110 nm, spherical particles, manufactured by Sukkyung AT) was used as it was.

[Polymerization accelerator (i)]
DABE: ethyl 4- (N, N-dimethylamino) benzoate [others]
BHT: 2,6-di-t-butyl-4-methylphenol (stabilizer (polymerization inhibitor))

(Production Example 1)
Production of Filler (f-1) As a silica particle, Snowtex OL (manufactured by Nissan Chemical Industries Ltd., average particle size 50 nm, dispersed in water and having a solid content concentration of 20%), which is a kind of colloidal silica, was prepared. Isopropanol was prepared as the alcohol. As the silane coupling agent (A), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was prepared. 1,1,1,3,3,3-hexamethyldisilazane (HMDS, manufactured by Shin-Etsu Chemical Co., Ltd., HDMS-1) was prepared as the organosilazane (B). 60 parts by mass of isopropanol is added to 100 parts by mass of slurry in which silica particles are dispersed in water at a concentration of 20% by mass, and the mixture is mixed at room temperature (about 25 ° C.) to obtain a dispersion in which silica particles are dispersed in a liquid medium. Obtained. To this dispersion, 0.48 parts by mass of 3-methacryloyloxypropyltrimethoxysilane and 0.01 parts by mass of a polymerization inhibitor (3,5-dibutyl-4-hydroxytoluene (BHT), manufactured by Kanto Chemical Co., Inc.) were added. And at 72C for 72 hours. By this step, the hydroxyl group present on the surface of the silica particles was surface-treated with the silane coupling agent (A). At this time, 3-methacryloyloxypropyltrimethoxysilane was calculated and added so that a necessary amount of hydroxyl groups (partially) remained without being surface-treated. Next, 0.78 parts by mass of 1,1,1,3,3,3-hexamethyldisilazane was added to the mixture, and the mixture was allowed to stand at 40 ° C. for 72 hours. Through this step, the silica particles were surface-treated to obtain a silica particle material. As the surface treatment progresses, the silica particles that have become hydrophobic cannot stably exist in water and isopropanol, and aggregate and precipitate. The molar ratio of the surface treatment agent 3-methacryloyloxypropyltrimethoxysilane to hexamethyldisilazane was 2: 5. 2.6 parts by mass of 35% aqueous hydrochloric acid was added to the total amount of the mixture obtained after the surface treatment to precipitate the silica particle material. The precipitate was filtered with a filter paper (Advantech 5A). The filtration residue (solid content) was washed with pure water and then vacuum dried at 100 ° C. to obtain a filler (f-1).

(Production Example 2)
Manufacture of filler (f-2) Except that 1,1,1,3,3,3-hexamethyldisilazane was 2.8 parts by mass, it was all the same as the synthesis method of filler (f-1). Thus, a filler (f-2) was produced. The molar ratio of the surface treatment agent 3-methacryloyloxypropyltrimethoxysilane to hexamethyldisilazane was 2:18.

(Production Example 3)
Synthesis of TAC4 Triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd., 21.9 g, 0.15 mol), triethylamine (75.9 g, 0.75 mol), p-methoxyphenol (3.7 mg, 0.03 mmol) in a 1 L four-necked flask ), 250 mL of dichloromethane was charged, stirred, and cooled to an internal temperature of 2 ° C. 100 mL of a dichloromethane solution of acrylic acid chloride (67.9 g, 0.75 mol) was added dropwise at 5 ° C. or less over 2 hours. After dropping, the mixture was stirred for 24 hours at room temperature. The reaction solution was filtered, the insoluble matter was washed with dichloromethane, and concentrated under reduced pressure at 35 ° C. or lower. The resulting concentrated residue was purified using silica gel column chromatography (developing solvent: ethyl acetate: methanol = 4: 1). After the column purification, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a white solid. LC / MS analysis and ¹ H-NMR measurement were performed, and the obtained white solid was confirmed to be the target compound from the position of the signal and the integrated value. The yield was 12.7 g, and the yield was 23.3%.

MS m / z: 363 (M + H) ^+
1 H-NMR (270 MHz D ₂ O): δ 3.37 (m, 6H), 3.57 (m, 6H), 5.66 (m, 4H), 6.07 (m, 6H), 6.56 (M, 2H) (ppm)

(Production Example 4)
Synthesis of MAEA In a 10 L four-necked flask, hydroxyethyl acrylamide (manufactured by Kojin Film & Chemicals, 172.7 g, 1.5 mol), triethylamine (167 g, 1.65 mol), p-methoxyphenol (38 mg, 0.3 mmol), Anhydrous tetrahydrofuran 1500 mL was charged, stirred, and cooled to an internal temperature of −10 ° C. 700 mL of anhydrous tetrahydrofuran solution of methacrylic acid chloride (172.5 g, 1.65 mol) was added dropwise at 5 ° C. or less over 2 hours. After dropping, the mixture was stirred for 24 hours at room temperature. The reaction solution was filtered, and the insoluble material was washed with ethyl acetate. The filtrate was concentrated under reduced pressure, and the residue was dissolved in ethyl acetate. A small amount of insoluble matter was removed by filtration through Celite, and the filtrate was washed with saturated brine: purified water (1: 1). The organic layer was dried over anhydrous sodium sulfate and then concentrated at 35 ° C. or lower under reduced pressure. The resulting concentrated residue was purified using silica gel column chromatography (developing solvent: ethyl acetate). After column purification, the solvent was distilled off under reduced pressure using a rotary evaporator to obtain a pale yellow liquid. LC / MS analysis and ¹ H-NMR measurement were performed, and it was confirmed from the position of the signal and the integrated value that the obtained pale yellow liquid was the target compound. The yield was 201.2 g, and the yield was 73.3%.

MS m / z: 184 (M + H) ^+
1 H-NMR (270 MHz CDCl ₃ ): δ 1.94 (m, 3H), 3.62 (m, 2H), 4.28 (m, 2H), 5.58 (m, 1H), 5.66 ( m, 1H), 6.08 (s, 1H), 6.10 (m, 1H), 6.11 (m, 1H), 6.28 (m, 1H) (ppm)

(Examples 1-21 and Comparative Examples 1-6)
Using materials such as the above-described production examples, among components shown in Tables 1 to 3, components other than fumed silica (d), filler (f), and filler (k) (powder) are used at room temperature. After mixing to obtain a uniform liquid component, the obtained liquid component and the powdered components of fumed silica (d), filler (f) and (k) were kneaded, whereby the self of Examples 1-21 An adhesive dental composite resin and the dental composite resins (pastes) of Comparative Examples 1 to 6 were prepared. Next, using these dental composite resins, the consistency, paste leveling property, tensile bond strength to dentin, and bending strength were measured according to the methods described later. Tables 1 to 3 show the compounding ratio (parts by mass) and test results of this dental composite resin.

[Consistency]
The prepared dental composite resin pastes of Examples and Comparative Examples were vacuum degassed and then filled into a polyolefin resin syringe (inner diameter 8 mm × length 63 mm clear film Majesty LV container) and allowed to stand at 25 ° C. for 2 hours. The placed sample was used as a sample for consistency test. 0.5 mL of the sample was weighed and placed in a constant temperature room at 25 ° C. (humidity 40%) so that the sample was raised to the center of a glass plate (5 cm × 5 cm). A 40 g glass plate (5 cm × 5 cm) was placed thereon, the major axis and minor axis of the sample after 120 seconds were measured through the glass plate, the arithmetic average of both was calculated, and the consistency (mm) was obtained. The major axis of the sample means the longest diameter among the diameters passing through the center of the sample, and the minor axis of the sample means a diameter perpendicular to the major axis of the sample among diameters passing through the center of the sample. The dental composite resin paste was degassed in vacuum, filled into a polyolefin resin syringe, and then left in a thermostat kept at 60 ° C. for 64 hours. The value measured by the above-described method using the dental composite resin paste after standing was defined as the consistency after storage at 60 ° C. for 64 hours.

[Paste leveling]
The paste leveling property, which is an index of paste fluidity, was evaluated as follows. The dental composite resin paste was vacuum degassed and filled into a polyolefin resin syringe. Next, the syringe was allowed to stand for 64 hours in a thermostat maintained at 60 ° C., and then a needle tip having a needle thickness of 20 G (gauge) was attached to the syringe. Then, in a 37 degreeC environment, it fractionated on 20 mg kneaded paper, and evaluated according to the following evaluation criteria by visually observing the paste.
A: The corner of the paste disappears within 1 second. B: The corner of the paste disappears within 5 seconds. C: The corner of the paste does not disappear even after 10 or more passes. , A or B paste.

[Tensile bond strength to dentin]
The lip surface of the bovine mandibular anterior teeth was polished with # 80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain an adherent sample in which the flat surface of dentin was exposed. The obtained adherend sample was further polished with # 1000 silicon carbide paper (Nihon Kenshi Co., Ltd.) under running water. After polishing, the surface water was dried by air blowing. An adhesive tape having a round hole with a diameter of 3 mm and having a thickness of about 150 μm was attached to the smooth surface after drying to define the adhesion area.

  The round holes were filled with the prepared dental composite resin pastes of Examples and Comparative Examples and covered with a release film (polyester). Subsequently, the application surface of the dental composite resin was smoothed by placing and pressing a slide glass on the release film. Subsequently, the dental composite resin is irradiated with light for 10 seconds using a visible light irradiator for dental polymerization (trade name: Pencure 2000, manufactured by Morita) through the release film, and the dental The composite resin was cured to obtain a cured product.

  A stainless steel cylindrical rod (diameter: 7 mm, length: 2. mm) was used on the surface of the cured product of the obtained dental composite resin using a commercially available dental resin cement (trade name: Panavia 21, manufactured by Kurarenorita Dental Co., Ltd.). One end face (circular cross section) of 5 cm) was bonded to prepare a sample for adhesion test. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. A total of five samples for the adhesion test were prepared and allowed to stand for 24 hours in a thermostat maintained at 37 ° C.

  The tensile bond strength of the sample for the adhesion test was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value was taken as the tensile bond strength.

[Bending strength]
The prepared dental composite resin pastes of Examples and Comparative Examples were vacuum degassed and then filled into a stainless steel mold (dimensions 2 mm × 2 mm × 25 mm), and the top and bottom were pressed with a slide glass, and visible light for dental polymerization A cured product was obtained by irradiating light on both sides of the slide glass with an irradiator (trade name: Pencure 2000, manufactured by Morita) for 10 seconds for 1 point and 5 points on each side. About each Example and the comparative example, 5 hardened | cured material was produced respectively, and after taking out this hardened | cured material from a metal mold | die, it stored for 24 hours in 37 degreeC distilled water. Using the cured product after storage as a test sample, using a precision universal testing machine (trade name: AGI-100, manufactured by Shimadzu Corporation), bending strength under the conditions of a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. The average value of the measured values of each sample was calculated, and the bending strength was obtained.

  As shown in Tables 1 and 2, in the self-adhesive dental composite resin (Examples 1 to 21) according to the present invention, the difference between the consistency immediately after preparation and the consistency after storage at 60 ° C. for 64 hours is 5.5 mm or less. And the consistency hardly changed. Moreover, it was a favorable result also about the paste leveling property after 60 degreeC preservation | save for 64 hours. Furthermore, the tensile bond strength of 9.6 MPa or more was exhibited for dentin, and the strength of 98.2 MPa or greater was developed for bending strength.

  As shown in Table 3, for fumed silica (d) and long-chain organosilicon compound (e), both were not blended, or either one was not blended, Comparative Examples 1, 2, 3, 5 and In the dental composite resin of No. 6, paste leveling properties were not ensured immediately after adjustment or after storage at 60 ° C. for 64 hours. Further, in Comparative Examples 2, 3 and 6 containing only one of fumed silica (d) and long-chain organosilicon compound (e), the difference in consistency becomes remarkably large, and the property stability of the paste is obtained. There wasn't.

  In addition, the consistency of the dental composite resin of Comparative Example 4 in which the short-chain organosilicon compound (e) was blended instead of the long-chain organosilicon compound (e) significantly changed after storage at 60 ° C. for 64 hours.

  The self-adhesive dental composite resin of the present invention can be used by first forming a cavity and then directly filling and photocuring the self-adhesive dental composite resin in the treatment of tooth loss and caries. .

Claims (16)

Acid group-containing (meth) acrylic polymerizable monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) not containing acid group, photopolymerization initiator (c), fumed silica ( d), containing a long-chain organosilicon compound (e), and a filler (f) (excluding fumed silica (d)),
The filler (f) is treated with a surface treatment agent, and the average particle size is 0.01 to 50.0 μm,
The surface treatment agent has the following general formula (1)
^{_{CH 2 = C (R 1)}} -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group optionally having substituent (s), and R ³ is a C _1- optionally having substituent (s)). C _{3 is} an alkyl group, p is an integer of 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by the following general formula (2)
R ⁴ R ⁵ R ⁶ —Si—NH—Si—R ⁷ R ⁸ R ⁹ (2)
(Wherein, R ^4, R ^5, and R ⁶ are each independently a hydrogen atom or an alkyl group which may have a substituent C ₁ -C _3, R ^4, R ^5, and R at least one of ⁶ is an alkyl group optionally C ₁ -C ₃ may have a substituent, R ^7, R ⁸ and R ⁹ each independently have a hydrogen atom or a substituent A C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a C ₁ -C ₃ alkyl group optionally having a substituent.)
Containing an organosilazane (B) represented by
The long-chain organosilicon compound (e) is represented by the following general formula (3)
^{_{CH 2 = C (R 10)}} -COO-X- (CH 2) r -Si-R 11 s R 12 (3-s) (3)
(In the formula, R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ is a hydrolyzable group which may have a substituent, R ¹² represents a C _{1 to} C ₆ hydrocarbon group, X represents an oxygen atom or a sulfur atom, where r represents an integer of 5 to 15 and s represents 2 or 3.)
A self-adhesive dental composite resin, which is a compound represented by: R ² is an unsubstituted hydrolyzable group, R ³ is an unsubstituted C ₁ -C ₃ alkyl group, and R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom or an alkyl group of C ₁ -C ₃ substituents, R ^4, R ^5, and at least one of R ⁶ is an alkyl group of C ₁ -C ₃ unsubstituted, R ^7, R ⁸ and R ⁹ each independently a hydrogen atom or an unsubstituted C ₁ -C ₃ alkyl group, R ^7, R ^8, and at least one of R ⁹ is an alkyl group of C ₁ -C ₃ unsubstituted, The self-adhesive dental composite resin according to claim 1.   The self-adhesive dental composite resin according to claim 1 or 2, wherein the apparent specific gravity of the fumed silica (d) is 20 g / l or more. The apparent specific gravity of the fumed silica (d) is 50 g / l or more, and the BET specific surface area of the fumed silica (d) is 50 m ² / g or more. The self-adhesive dental composite resin as described. The apparent specific gravity of the fumed silica (d) is 100 g / l or more, the BET specific surface area of the fumed silica (d) is 100 m ² / g or more, and the average primary particles of the fumed silica (d) The self-adhesive dental composite resin according to any one of claims 1 to 4, having a diameter of 5 to 50 nm.   The self-adhesive dental composite resin according to any one of claims 1 to 5, wherein r in the general formula (3) is an integer of 8 to 13. The self-adhesive dental composite resin according to any one of claims 1 to 6, wherein s is 3 in the general formula (3) and R ¹¹ is a C _{1 to} C ₃ alkoxy group.   The silane coupling agent (A) is 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and 6-methacryloyl. The self-adhesive dental composite resin according to any one of claims 1 to 7, which is one or more selected from the group consisting of oxyhexyltrimethoxysilane.   The organosilazane (B) is 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, and 1,1,1,3,3-penta The self-adhesive dental composite resin according to any one of claims 1 to 8, which is one or more selected from the group consisting of methyldisilazane.   In 100 parts by mass of the total amount of the polymerizable monomer components, 1 to 40 parts by mass of the acidic group-containing (meth) acrylic polymerizable monomer (a), and polyfunctional (meth) not containing the acidic group. It contains 30 to 95 parts by mass of the acrylic polymerizable monomer (b), and 0.001 to 20 parts by mass of the photopolymerization initiator (c) with respect to 100 parts by mass of the total amount of the polymerizable monomer components. 1 to 60 parts by mass of the fumed silica (d), 0.01 to 30 parts by mass of the long-chain organosilicon compound (e), and 25 to 400 parts by mass of the filler (f). The self-adhesive dental composite resin according to any one of 1 to 9.   Furthermore, the self-adhesive dental composite resin of any one of Claims 1-10 containing the polyfunctional (meth) acrylamide polymerizable monomer (g) which has an amide proton.   The total amount of the polymerizable monomer component is 100 parts by mass, and the blending amount of the polyfunctional (meth) acrylamide polymerizable monomer (g) having an amide proton is 0.5 to 30 parts by mass. Self-adhesive dental composite resin.   The self-adhesive dental composite resin according to any one of claims 1 to 12, further comprising a hydrophilic monofunctional polymerizable monomer (h).   A hydrophilic monofunctional polymerizable monomer (h) is obtained from a hydrophilic monofunctional (meth) acrylate polymerizable monomer and a hydrophilic monofunctional (meth) acrylamide polymerizable monomer. The self-adhesive dental composite resin according to claim 13, which is at least one member selected from the group consisting of:   15. The self according to claim 13 or 14, wherein the amount of the hydrophilic monofunctional polymerizable monomer (h) is 1 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer components. Adhesive dental composite resin.   The self-adhesive dental composite resin according to any one of claims 1 to 15, which is a one-material mold.