JP7183185B2 - self-adhesive dental composite resin - Google Patents

Description

The present invention relates to self-adhesive dental composite resins. More specifically, the present invention relates to a self-adhesive dental composite resin that has high surface hardness, good dischargeability from a container, moderately suppressed fluidity of the paste, and hardly drips when applied in the oral cavity.

Conventionally, dental adhesives and dental composite resins have been commonly used for restoration of dental caries and accompanying defects. Restorative treatments are performed according to the following procedure. First, after a carious portion is shaved to form a cavity, a dental adhesive is applied to the cavity, and then visible light is applied to the site where the adhesive is applied to cure the adhesive. Next, the hardened adhesive layer is filled with a dental composite resin, and finally the filled dental composite resin is irradiated with visible light to harden it.

In the restoration method described above, two materials, a dental adhesive and a dental composite resin, are used. It is beginning to be put to practical use as a material that omits the use of adhesives and reduces the number of operating steps in restorative treatment.

The self-adhesive dental composite resin consists of a polyfunctional polymerizable monomer and filler for imparting mechanical strength, and a polymerization initiator for improving hardening properties, which are the components of conventional dental composite resin. In order to impart adhesiveness to the material, it contains as a component a polymerizable monomer having an acidic group, which has been conventionally used in dental adhesives (for example, Patent Documents 1 and 2).

(Meth)acrylates are generally used as polymerizable monomers blended in dental composite resins. In order to improve the resistance, a polymerizable monomer having an acidic group such as a phosphoric acid group or a carboxyl group is blended.

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

JP 2008-260752 A Japanese Patent Publication No. 2015-507610

However, when a silica filler or the like that does not react with the acidic component described in Patent Documents 1 and 2 is used, although the reaction between the filler and the acidic component is suppressed, the fluidity of the paste increases, so it is not applicable to the oral cavity. There was a problem that the paste dripped when it was applied.

Further, when the self-adhesive dental composite resin is directly filled into a tooth cavity, it may not be possible to push the self-adhesive dental composite resin out of a container such as a syringe containing the self-adhesive dental composite resin. A self-adhesive dental composite resin that has a discharge property that allows direct filling into a tooth cavity from a storage container such as a syringe and has a dripping property that prevents the paste from dripping when applied in the oral cavity. was difficult.

Therefore, the present invention contains a polyfunctional polymerizable monomer, a filler, and a polymerization initiator in the same manner as conventional dental composite resins, and also contains a filler that has been subjected to a specific surface treatment, so that visible light It has sufficient mechanical strength after polymerization and curing by irradiation, moderately suppresses the fluidity of the paste, does not drip easily even when applied in the oral cavity, and is self-discharging that can be directly filled from the container into the tooth cavity. An object of the present invention is to provide an adhesive dental composite resin.

The present invention includes the following inventions.
[1] Acidic group-containing (meth)acrylic polymerizable monomer (a), polyfunctional (meth)acrylic polymerizable monomer containing no acidic group (b), photopolymerization initiator (c), etc. A self-adhesive dental composite resin containing a filler (d) having an electric point of 6.0 or more and a filler (e) having an isoelectric point of less than 6.0,
The filler (e) is treated with a surface treatment agent and has an average particle size of 0.001 to 50.0 μm, and the surface treatment agent is represented by the following general formula (1)
_CH2 =C( ^R1 )-COO-( _CH2 ) _p -Si- ^R2qR3 ( ³ _-q) ( ₁ )
(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group which may have a substituent, and R ³ is a C ₁ to a _C3 alkyl group, p is an integer from 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by and 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 a C ₁ to C ₃ alkyl group which may have a substituent, and R ⁴ , R ⁵ and R at least one of ⁶ is an optionally substituted C ₁ to C ₃ alkyl group, and each of R ⁷ , R ⁸ and R ⁹ independently has a hydrogen atom or a substituent; and at least one _{of R 7 , R 8 and R 9 is a C 1 -C 3 alkyl} ^{group which may} _{have a} substituent.)
containing an organosilazane (B) represented by
A self-adhesive dental composite resin containing 0.1 to 15 parts by mass of the filler (d) per 100 parts by mass of the total amount of polymerizable monomer components.
[2] The self-adhesive dental composite resin of [1], wherein the filler (d) has an average particle size of 0.001 to 0.5 μm.
[3] 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 atom or an 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, R ⁷ , R ⁸ and Each 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] or [2] above.
[4] 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 [3], which is at least one member selected from the group consisting of 6-methacryloyloxyhexyltrimethoxysilane.
[5] 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 [4], which is at least one member selected from the group consisting of 3-pentamethyldisilazane.
[6] In the total amount of 100 parts by mass of the polymerizable monomer components, 1 to 40 parts by mass of the acidic group-containing (meth)acrylic polymerizable monomer (a), and the acidic group-free polyfunctional (Meth) containing 30 to 95 parts by mass of an acrylic polymerizable monomer (b), the photopolymerization initiator (c) of 0.001 to 0.001 to 100 parts by mass of the total amount of the polymerizable monomer component The self-adhesive dental composite according to any one of [1] to [5], containing 20 parts by mass, 0.1 to 10 parts by mass of the filler (d), and 25 to 400 parts by mass of the filler (e). resin.
[7] The self-adhesive dental composite resin of any one of [1] to [6], further comprising a polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons.
[8] The above [ 7] self-adhesive dental composite resin.
[9] The self-adhesive dental composite resin of any one of [1] to [8], further comprising a hydrophilic monofunctional polymerizable monomer (g).
[10] The hydrophilic monofunctional polymerizable monomer (g) is a hydrophilic monofunctional (meth)acrylate polymerizable monomer and a hydrophilic monofunctional (meth)acrylamide polymerizable monomer. The self-adhesive dental composite resin of [9], which is one or more selected from the group consisting of monomers.
[11] In the total amount of 100 parts by mass of the polymerizable monomer component, the content of the hydrophilic monofunctional polymerizable monomer (g) is 1 to 30 parts by mass, the above [9] or [ 10] self-adhesive dental composite resin.
[12] The self-adhesive dental material according to any one of [1] to [11], wherein the filler (e) is treated with a surface treatment agent and has an average particle size of 0.03 to 20.0 μm. composite resin.
[13] The self-adhesive dental composite resin according to any one of [1] to [12], which is a one-component type.

According to the present invention, the paste has sufficient mechanical strength after polymerization and curing by irradiation of visible light, the fluidity of the paste is moderately suppressed, it is difficult to drip even when applied in the oral cavity, and the paste is transferred from the storage container to the tooth cavity. There is provided a self-adhesive dental composite resin that can be directly filled and ejected. In addition, since it has high surface hardness, excellent abrasion resistance and polishability, and can suppress pigment deposition, it can be suitably used for dental composite resins. Furthermore, the self-adhesive dental composite resin of the present invention also has the effect that the paste properties change little during long-term storage.

FIG. 1 is an explanatory diagram of the reaction mechanism when the organosilazane (B) according to one embodiment of the present invention is 1,1,1,3,3,3-hexamethyldisilazane. FIG. 2 is an explanatory diagram regarding the filler (e) and the filler (d) in the paste, and the dispersed state of the filler (e).

The self-adhesive dental composite resin of the present invention comprises an acidic group-containing (meth)acrylic polymerizable monomer (a), an acidic group-free polyfunctional (meth)acrylic polymerizable monomer (b), A photopolymerization initiator (c), a filler (d) having an isoelectric point of 6.0 or more, and a filler (e) having an isoelectric point of less than 6.0, wherein the filler (e) is a surface treatment agent and has an average particle size of 0.001 to 50.0 μm, and the surface treatment agent has the following general formula (1)
_CH2 =C( ^R1 )-COO-( _CH2 ) _p -Si- ^R2qR3 ( ³ _-q) ( ₁ )
(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group which may have a substituent, and R ³ is a C ₁ to a _C3 alkyl group, p is an integer from 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by and 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 a C ₁ to C ₃ alkyl group which may have a substituent, and R ⁴ , R ⁵ and R at least one of ⁶ is an optionally substituted C ₁ to C ₃ alkyl group, and each of R ⁷ , R ⁸ and R ⁹ independently has a hydrogen atom or a substituent; and at least one of R ₇ , R ⁸ and R ⁹ is ^a C ₁ -C ₃ alkyl group which may have a substituent. ₎
and containing 0.1 to 15 parts by mass of the filler (d) per 100 parts by mass of the total amount of polymerizable monomer components.

In addition, in this specification, the notation of "(meth)acryl" is used in the sense of including both methacryl and acryl. In the present specification, the upper and lower limits of numerical ranges (the content of each component, the value calculated from each component, each physical property, numerical values of symbols in formulas, etc.) can be combined as appropriate.

The self-adhesive dental composite resin of the present invention has sufficient mechanical strength after being polymerized and cured by irradiation with visible light, and the fluidity of the paste is moderately suppressed. The reason why the paste properties change little during long-term storage is not clear, but it is presumed as follows. The filler (e) has an isoelectric point of less than 6.0 and is represented by —(CH ₂ ) _p —OOC—C(R ¹ )=CH ₂ derived from the surface treatment with the silane coupling agent (A). functional group (R ¹ is a hydrogen atom or a methyl group, and p is an integer of 1 to 13), and a C ₁ to C ₃ alkyl group derived from the surface treatment with organosilazane (B) on the surface have Since the C ₁ to C ₃ alkyl groups repel each other due to their hydrophobicity, the filler (e) is used in the self-adhesive dental composite resin to repel the C ₁ to C ₃ alkyl groups. It is difficult to agglomerate by force and keeps a separate and unbonded state. In addition, since the filler (e) 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 the polymer can be polymerized, the bond between the filler (e) and the polymerizable monomer interface can be strengthened, and sufficient mechanical strength can be imparted. —(CH ₂ ) _p —OOC-C(R ¹ )=CH ₂ is imparted by a dehydration polycondensation reaction between silanol groups using a silane coupling agent (A) having a polymerizable group, while C ₁ A ~ _C3 alkyl group is provided by the deammonification reaction of the organosilazane (B). In the treatment with only a general silane coupling agent (A) known as conventional technology, a silanol group (—SiOH) and a filler (e) produced by hydrolyzing the alkoxy group of the silane coupling agent (A) and silanol groups (--SiOH) on the surface of are chemically bonded by dehydration polycondensation. In this case, the silanol group (--SiOH) on the surface of the filler (e) or the silanol group (--SiOH) derived from the silane coupling agent (A) remains as an unreacted product (hereinafter, this remaining silanol group are referred to as "residual silanol groups"). In contrast, in the present invention, as shown in FIG. 1, residual silanol groups (—SiOH) on the surface of the filler (e) or residual silanol groups (—SiOH) derived from the silane coupling agent (A) and organosilazane The deammonification reaction with (B) can hydrophobize residual silanol groups (--SiOH). This treatment (deammonification reaction) with the organosilazane (B) minimizes residual silanol groups (--SiOH) on the surface of the filler (e) or residual silanol groups (--SiOH) derived from the silane coupling agent (A). It is possible. Therefore, 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 strong interactions with silanol groups (-SiOH) due to hydrogen bonding, and fillers (e ) maintains a highly dispersed state, and it is thought that this highly dispersed state brings high fluidity to the paste. The high fluidity of the paste has the advantage that it is easy to pour into the cavity, but the paste is not intended for treatment of gingiva and dentin other than the filling site until the paste is filled into the cavity and hardened with a visible light irradiator. I had a problem with it leaking.

It has been found that the above problem can be solved by including the filler (d) having an isoelectric point of 6.0 or higher without impairing the properties obtained by blending the filler (e). Although the detailed reason is not clear, it is presumed as follows. The filler (e) has an isoelectric point of less than 6.0, is negatively charged in the paste having a pH higher than the isoelectric point of the filler (e), and is considered to be dispersed due to its zeta potential. On the other hand, the filler (d) is charged opposite to the filler (e) in the paste having a pH equal to or higher than the isoelectric point of the filler (e), that is, positively charged, and the fillers (d) are also dispersed. It is considered that there is As shown in FIG. 2, the presence of the filler (d) and the filler (e) in the paste at the same time causes the filler (d) and the filler (e) to form and maintain an electrostatically weak association state, As a result, the fluidity of the paste is moderately suppressed, the sagging of the paste is improved, there is little change in the properties of the paste during long-term storage, and it has an ejection property that allows direct filling from the container into the tooth cavity. it is conceivable that. Moreover, as an unexpected effect, it was found that the addition of the filler (d) improves the surface hardness. Although the detailed reason is not clear, the filler (d) and the filler (e) form an electrostatic association state, and the state close to the closest packing improves the filler filling rate per unit volume of the paste. However, as a result, the surface hardness may have increased due to an increase in the amount of filler on the surface of the cured product.

First, the filler (d) having an isoelectric point of 6.0 or higher, which is used in the present invention, will be described. In the present invention, the isoelectric point of the filler indicates the pH at which the particles in the aqueous dispersion have a zeta potential of 0 mV. Zeta potential refers to values measured by laser Doppler velocimetry. In general, if the particles are electrically charged, applying an electric field to the aqueous dispersion will cause the particles to migrate towards the electrode. The moving speed of a particle is proportional to the amount of charge on the particle. Therefore, the zeta potential can be determined by measuring the moving speed of the particles. An aqueous dispersion of particles having an isoelectric point has a zeta potential of 0 mV at a certain pH when the pH is changed. Therefore, the zeta potential is traced while continuously changing the pH by adding acid or alkali to the aqueous dispersion, and the obtained measurement data is plotted with pH on the X axis and zeta potential on the Y axis. By drawing a line in consideration of the plot, the pH at which the zeta potential becomes 0 mV can be calculated, and this pH becomes the isoelectric point of the particles.

As the filler (d) in the present invention, conventionally known fillers can be used without any limitation as long as they have an isoelectric point of 6.0 or more. Metals such as alumina, zirconia, titania, zinc oxide and nickel oxide composite metal oxides such as oxides, alumina-zirconia, alumina-titania, and zirconia-titania; Among them, alumina, zirconia, and titania are more preferable, alumina and zirconia are more preferable, and alumina is most preferable. These may be used individually by 1 type, and may use 2 or more types together.

The average particle size of the filler (d) is preferably 0.001-0.5 μm, more preferably 0.003-0.4 μm, and even more preferably 0.005-0.3 μm. Within these ranges, the paste can be easily ejected from a container, has appropriate fluidity, is less likely to sag, has little change in paste properties during long-term storage, and has excellent surface hardness. In addition, in this specification, the average particle size of the filler means the average particle size of the primary particles of the filler (average primary particle size).

In the present invention, the average particle size 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 analyzer, and when the average particle size is less than 1.0 μm, it is preferable to use electron microscope observation. The particle size distribution can be measured, for example, using a 0.2% sodium hexametaphosphate aqueous solution as a dispersion medium using a laser diffraction particle size distribution analyzer (SALD-2100: manufactured by Shimadzu Corporation). For electron microscope observation, for example, a scanning electron microscope (manufactured by Hitachi, Ltd., S-4000 type) photograph of particles is taken, and the particle diameter of the particles (200 or more) observed in the unit field of view of the photograph is It can be obtained by measurement using image analysis type particle size distribution measurement software (Macview (Mountech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean 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 their particle diameters.

The content of the filler (d) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the polymerizable monomer components, from the viewpoint of excellent fluidity, sagging, and surface hardness. 0.2 parts by mass or more is preferable, and 0.3 parts by mass or more is more preferable from the viewpoint of paste properties such as appropriate fluidity and sagging of the self-adhesive dental composite resin. In addition, from the viewpoint of not impairing the adhesive strength of the self-adhesive dental composite resin and the operability of the paste, such as dischargeability from the container, it is 15 parts by mass or less per 100 parts by mass of the total amount of the polymerizable monomer component. 10 parts by mass or less is more preferable, and 8 parts by mass or less is even more preferable. Therefore, from the above viewpoint, the content of the filler (d) is 0.1 to 15 parts by mass, preferably 0.2 to 10 parts by mass, with respect to 100 parts by mass of the total amount of the polymerizable monomer components. 0.3 to 8 parts by mass is more preferable.

The filler (d) is preferably treated with a surface treating agent. Such a surface treatment agent is selected from the group consisting of an acidic group-containing (meth)acrylic polymerizable monomer (a) described later, and/or an organic silicon compound, an organic titanium compound, an organic zirconium compound, and an organic aluminum compound. and at least one organometallic compound. When two or more organometallic compounds are used, the surface treatment layer may be a mixture of two or more organometallic compounds, or may be a surface treatment layer having a multi-layer structure in which two or more organometallic compound layers are laminated. good.

Examples of the organosilicon compound include compounds represented by (W) _n SiY _4-n (wherein W is a C ₁ to C ₁₂ substituted or unsubstituted hydrocarbon group, Y is C ₁ to _C4 alkoxy group, hydroxy group, halogen atom or hydrogen atom, and n is 0, 1, 2 or 3. When there are a plurality of W and Y, they may be the same or different. .).

Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, 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-methacryloyloxypropylmethyldimethoxysilane, γ -methacryloyloxypropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(amino ethyl)-γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, Methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω-(meth)acryloyloxyalkyltrimethoxysilane (Number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12, e.g., 3-methacryloyloxypropyltrimethoxysilane, etc.), ω-(meth)acryloyloxyalkyltriethoxysilane ((meth)acryloyl Number of carbon atoms between oxy group and silicon atom: 3 to 12, eg, 3-methacryloyloxypropyltriethoxysilane, etc.).

Among these, a coupling agent having a functional group capable of copolymerizing with the polymerizable monomer component, such as ω-(meth)acryloyloxyalkyltrimethoxysilane (carbon between the (meth)acryloyloxy group and the silicon atom) number: 3 to 12), ω-(meth)acryloyloxyalkyltriethoxysilane (number of carbon atoms 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 compounds include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, and zirconyl acetate.

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

The shape of the filler (d) is not particularly limited, and may be appropriately selected according to the properties desired to be enhanced in the dental composite resin. Specifically, it can be used as a powder of amorphous or spherical particles. . When the amorphous filler (d) having an isoelectric point of 6.0 or more is used, the mechanical strength and abrasion resistance are particularly excellent, and the spherical filler (d) having an isoelectric point of 6.0 or more is used. When used, it is particularly excellent in polishing lubricity and lubricating durability. A commercially available product may be used as the reactive filler (d) in the present invention.

Next, the filler (e) having an isoelectric point of less than 6.0 used in the present invention will be described.

The filler (e) has —(CH ₂ ) _p —OOC—C(R ¹ )=CH ₂ and C ₁ -C ₃ alkyl groups on its surface. The C ₁ -C ₃ alkyl groups repel each other due to their hydrophobicity. Therefore, the filler (e) of the present invention does not easily aggregate even in the self-adhesive dental composite resin due to the repulsive force between the C ₁ -C ₃ alkyl groups, and does not easily aggregate even in the powder state.

The filler (e) has an isoelectric point of less than 6.0, is treated with a surface treatment agent, and has an average particle size of 0.001 to 50.0 μm. ) and the organosilazane (B) represented by the general formula (2), any known filler used in dental composite resins can be used without any limitation. used. As the filler (e) before being treated with the surface treatment agent, various glasses [mainly composed of silica and containing oxides of heavy metals, boron, aluminum, etc. within a range satisfying an isoelectric point of less than 6.0. contains. For example, glass powder of general composition such as liquid phase synthetic amorphous silica, fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (Pyrex (registered trademark) glass); barium glass, Dental glass powders such as strontium borosilicate glass, lanthanum glass ceramics, and fluoroaluminosilicate glass], composite oxides such as silica-titania and silica-zirconia, calcium fluoride with a core-shell structure whose surface is coated with silica, silica core-shell structure ytterbium fluoride surface-coated with silica, core-shell structure yttrium fluoride surface-coated with silica, core-shell structure calcium phosphate surface-coated with silica, core-shell structure sulfuric acid surface-coated with silica Barium, silica-coated core-shell zirconium dioxide, silica-coated core-shell titanium dioxide, silica-coated core-shell hydroxyapatite. Among these, various glasses such as various silicas, composite oxides such as silica-titania and silica-zirconia, and silica on the surface can be efficiently reacted with the silane coupling agent (A) or the organosilazane (B). core-shell structure calcium fluoride surface-coated with silica, core-shell structure ytterbium fluoride surface-coated with silica, core-shell structure yttrium fluoride surface-coated with silica, core-shell structure calcium phosphate surface-coated with silica , silica-coated core-shell structure barium sulfate, silica-coated core-shell zirconium dioxide, silica-coated core-shell titanium dioxide, silica-coated core-shell structure Ytterbium fluoride having a core-shell structure coated with hydroxyapatite silica and yttrium fluoride having a core-shell structure coated with silica are suitable. These may be used individually by 1 type, and may use 2 or more types together.

The average particle size of the filler (e) is 0.001 to 50.0 μm, preferably 0.01 to 50.0 μm, more preferably 0.03 to 20.0 μm, and 0.05 to 10.0 μm. More preferably, 0.05 to 5 μm is particularly preferable, and 0.05 to 1 μm is most preferable. Within these ranges, sufficient mechanical strength is obtained, the paste does not become sticky, no problems arise in operability, and the cured product is excellent in polishing lubricity and lubricating durability.

In addition, since the filler (e) used in the present invention does not aggregate easily, it can be easily washed with water. Therefore, the filler (e) used in the present invention has an acid-base reaction with the acidic group-containing (meth)acrylic polymerizable monomer (a), or the content of ionic impurities such as alkali metals that undergo chelate reactions. can be reduced.

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

By treating the surface with the silane coupling agent (A) represented by the general formula (1), hydroxyl groups present on the surface of the filler (e) are substituted with functional groups derived from the silane coupling agent (A). be.

The order of surface treatment of the filler (e) is not particularly limited. For example, the filler (e) is surface-treated by sequentially adding the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2). may be added at the same time for surface treatment. For example, the filler (e) may first be reacted with the silane coupling agent (A) represented by the general formula (1), and then reacted with the organosilazane (B) represented by the general formula (2). Alternatively, the filler (e) is first reacted with the organosilazane (B) represented by the general formula (2), then reacted with the silane coupling agent (A) represented by the general formula (1), and then The organosilazane (B) represented by general formula (2) may be reacted.

As a method of surface treatment of the filler (e), a method of bonding a silane coupling agent (A) represented by general formula (1) to the surface of the filler (e) by dehydration polycondensation reaction, and a method of general formula (2 ) is not particularly limited as long as it is a method of binding the organosilazane (B) represented by the above to the surface of the filler (e) by a deammonification reaction. For example, while stirring the filler (e) in a mixing tank, a solution of each surface treatment agent diluted with a solvent is sprayed, and the mixture is heated and dried in the tank for a certain period of time while stirring; filler (e) and surface treatment. For example, the agent is stirred and mixed in a solvent, and then dried by heating. Examples of the solvent include, but are not particularly limited to, alcoholic solvents such as methanol, ethanol and isopropanol, water, and mixed solvents thereof. The heating temperature is not particularly limited, but may be about 30 to 90.degree.

In general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrolyzable group optionally having a substituent. R ³ is an optionally substituted C ₁ -C ₃ alkyl group. p is an integer of 1 to 13, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6. q is 2 or 3, with 3 being preferred.

The hydrolyzable group that may have a substituent for R ² is not particularly limited, but examples of hydrolyzable groups include methoxy, ethoxy, n-propoxy, isopropoxy, n- C ₁ to C ₆ linear or branched alkoxy groups such as butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group and isohexyloxy group; A chlorine atom or an isocyanate group may be mentioned. Considering hydrolyzability, the alkoxy group as a hydrolyzable group should be a C ₁ to C ₄ linear alkoxy group selected from methoxy, ethoxy, n-propoxy, and n-butoxy groups. is more preferred, and a C ₁ to C ₃ linear alkoxy group is even more preferred. The hydrolyzable group of ^R2 may be unsubstituted. As the silane coupling agent (A), in the general formula (1), R ¹ is a methyl group, R ² is an unsubstituted C ₁ to C ₆ linear or branched alkoxy group, and R ³ is an unsubstituted C ₁ to C ₃ alkyl group, p is 2 to 10, q is 2 or 3, R ¹ is a methyl group, and R ² is an unsubstituted C ₁ C ₄ straight or branched alkoxy group, p is 2 to 8, q is 3, more preferably R ¹ is methyl group, R ² is unsubstituted C ₁ to More preferred are C ₃ straight or branched chain alkoxy groups, where p is 2-6 and q is 3.

Examples of the optionally substituted C ₁ to C ₃ alkyl groups of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include methyl group, ethyl group, n -Propyl group, isopropyl group. 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, more preferably a methyl group. At least one of R ⁴ , R ⁵ and R ⁶ is an optionally substituted C ₁ to C ₃ alkyl group, and two of these are optionally substituted C ₁ to It may be a C ₃ alkyl group, or all three may be C ₁ to C ₃ alkyl groups optionally having a substituent. At least one of R ⁷ , R ⁸ and R ⁹ is an optionally substituted C ₁ -C ₃ alkyl group, and two of these are optionally substituted C ₁ -C ₃ alkyl groups, or all three may be C ₁ to C ₃ alkyl groups optionally having a substituent.

Examples of substituents of the hydrolyzable group for R ² and the alkyl groups for R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), a carboxy group, a hydroxy group, an amino group, an amino group mono- or di-substituted with _a C ₁ -C 6 alkyl group, an acyl group, a C ₁ -C ₆ alkyl group, and the like. The number of substituents is not particularly limited, and the number of substituents of the hydrolyzable group of R ² is 1-5. The number of substituents of the alkyl groups of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is 1, 2 or 3.

Specific examples of the silane coupling agent (A) represented by the general formula (1) include (meth)acryloyloxymethyltrimethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, 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)acryloyloxyundecyltri Methoxysilane, 11-(meth)acryloyloxyundecyldichloromethylsilane, 11-(meth)acryloyloxyundecyltrichlorosilane, 11-(meth)acryloyloxyundecyldimethoxymethylsilane, 12-(meth)acryloyloxyundecyltri methoxysilane, 13-(meth)acryloyloxytridecyltrimethoxysilane, and the like. These may be used individually by 1 type, and can also be used in combination of 2 or more types as appropriate. Among these, when the alkylene group represented by —(CH ₂ ) _p — is moderately long, it has a good compatibility with the polymerizable monomer in the self-adhesive dental composite resin, and the self-adhesive dental composite resin is obtained. From the point that the content of the included filler (e) can be sufficiently increased, and if the alkylene group represented by -(CH ₂ ) _p - is appropriately short, the hydrophobicity will not become too strong and the adhesive strength will increase. , 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, 6-methacryloyloxyhexyltrimethoxysilane, and 3- More preferred is methacryloyloxypropyltrimethoxysilane.

The organosilazane (B) represented by the general formula (2) includes hydroxyl groups present on the surface of the filler (e) and hydroxyl groups derived from the silane coupling agent (A) represented by the general formula (1). It is preferable to use one having a small molecular weight, although any one can be used as long as it is bound by the deammonification reaction. Specifically, hexaethyldisilazane, hexan-propyldisilazane, hexaisopropyldisilazane, 1,1,2,2-tetramethyl-3,3-diethyldisilazane, 1,1,3,3-tetra methyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane, etc.; Disilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane and the like are preferred.

The amount of treatment with the silane coupling agent (A) represented by the general formula (1) in the filler (e) is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the filler (e) before surface treatment. , more preferably 1 to 10 parts by mass, particularly preferably 2 to 8 parts by mass. If the amount is less than 0.5 parts by mass, sufficient polymerizable groups cannot be imparted to the surface of the filler (e), and the mechanical strength may decrease.

The molar ratio of the silane coupling agent (A) and the organosilazane (B) in the surface treatment of the filler (e) is silane coupling agent (A):organosilazane (B)=1:1 to 1:20. is preferred, and 1:2 to 1:10 is more preferred. If the amount of the organosilazane (B) is less than the silane coupling agent (A), aggregation in the paste may proceed and transparency may not be ensured during storage. If the amount of the organosilazane (B) represented by the general formula (2) exceeds 20 mols per 1 mol of the coupling agent (A), the hydrophobicity becomes strong and sufficient adhesive strength may not be obtained. be.

In the surface treatment, a polymerization inhibitor may be added to suppress polymerization of the silane coupling agent (A) represented by general formula (1). Known polymerization inhibitors 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 (e) is substantially only the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2). Those containing are preferable. Substantially containing only the silane coupling agent (A) represented by the general formula (1) and the organosilazane (B) represented by the general formula (2) is represented by the general formula (1) The content of the surface treatment agent other than the silane coupling agent (A) and the organosilazane (B) represented by the general formula (2) is less than 1.0% by mass, preferably less than 0.5% by mass. and more preferably less than 0.1% by mass.

Furthermore, as the filler (e), it is preferable to solidify the filler (e) after surface treatment. Solidification is a step of precipitating the filler (e) after surface treatment with a mineral acid, washing and/or dehydrating (eg drying) the precipitate with water to obtain a solid of the filler (e). As described above, conventional fillers surface-treated only with the silane coupling agent (A) represented by the general formula (1) are very prone to agglomerate, so it is very difficult to re-disperse them once solidified. Have difficulty. However, since the filler (e) of the present invention is hard to aggregate, even if it is solidified, it is difficult to aggregate. As described above, by washing the filler (e) with water, the filler (e) containing less ionic impurities such as alkali metals can be easily produced. By using the filler (e) with less ionic impurities, the repulsive force between the alkyl groups described above can be maintained for a longer period of time, and the high transparency of the paste can be maintained for a longer period of time. Protons (H ⁺ ) generated from the polymerizable monomer (a), hydroxyl groups (—OH) contained in other polymerizable monomers, and very few remaining silanol groups interact with ionic impurities. The probability can also be further reduced, further suppressing changes in the transparency and properties of the paste. In the washing step, washing is preferably repeated until the electrical conductivity of the water extracted from the filler (e) (for example, the water in which the filler (e) is immersed at 121° C. for 24 hours) is 50 μS/cm or less. .

Mineral acids used for solidification include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, with hydrochloric acid being particularly preferred. Although the mineral acid may be used as it is, it is preferably used as an aqueous mineral acid solution. The mineral acid concentration in the aqueous mineral acid solution is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. The amount of the aqueous mineral acid solution can be about 6 to 12 times the weight of the filler (e) to be washed.

Washing with the mineral acid aqueous solution can be performed multiple times. Washing with a mineral acid aqueous solution is preferably carried out by stirring after the filler (e) is immersed in the mineral acid aqueous solution. Moreover, it may be allowed to stand for 1 hour to 24 hours, further 72 hours in the immersed state. Stirring may be continued or may not be performed when the mixture is left to stand. When washing in an aqueous mineral acid solution, it can be heated to room temperature or higher. Thereafter, the filler (e) 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 the mass basis). Examples include ion-exchanged water, distilled water, pure water, and the like. Washing with water may be performed by filtering after dispersing and suspending the filler (e) in the same manner as washing with an aqueous mineral acid solution, and water is continuously passed through the filtered filler (e). may The end time of washing with water may be determined by the electrical 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 (e) is 1 ppm or less. , the time when the concentration of alkali metal in the extracted water becomes 5 ppm or less. In addition, when washing with water, it is also possible to heat to room temperature or higher.

Drying of the filler (e) can be carried out by a conventional method. For example, it may be heated or left under reduced pressure (vacuum). A heating device and a decompression device are not particularly limited, and known ones can be used.

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

The content of the filler (e) has sufficient mechanical strength after polymerization and curing by visible light irradiation, and the paste has excellent property stability 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, and even more preferably 100 parts by mass or more because the self-adhesive dental composite resin has higher mechanical strength with respect to 100 parts by mass of the total amount of the components. . Also, from the viewpoint of not impairing the paste operability such as adhesive strength and consistency of the self-adhesive dental composite resin, it is preferably 400 parts by mass or less, and 350 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. is more preferable, and 300 parts by mass or less is even more preferable. Therefore, from the above viewpoint, the content of the filler (e) is preferably 25 to 400 parts by mass, more preferably 50 to 350 parts by mass, and more preferably 100 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer. More preferred. The filler (d) and the filler (e) form an electrostatic association state, and the properties such as the sagging of the paste, the surface hardness, and the ejection property are excellent, so the mass ratio of the filler (d) to the filler (e) The filler (d):filler (e) ratio is preferably 0.05 :100 to 15:100, more preferably 0.1 :100 to 10:100, and still more preferably 0.5 :100 to 5:100.

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 exhibiting adhesiveness of the self-adhesive dental composite resin of the present invention. The acidic group-containing (meth)acrylic polymerizable monomer (a) has the effect of demineralizing 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 pyrophosphate group, a carboxylic acid group, 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, or a methacrylamide group. From the viewpoint of adhesion to dentin, the acidic group-containing (meth)acrylic polymerizable monomer (a) has any one of an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group as a polymerizable group. It is preferably monofunctional. Specific examples include the following.

Phosphate group-containing (meth)acrylic polymerizable monomers include, for example, 2-(meth)acryloyloxyethyl dihydrogenphosphate, 3-(meth)acryloyloxypropyl dihydrogenphosphate, 4-(meth)acryloyloxy Butyl dihydrogen phosphate, 5-(meth) acryloyloxypentyl dihydrogen phosphate, 6-(meth) acryloyloxyhexyl dihydrogen phosphate, 7-(meth) acryloyloxyheptyl dihydrogen phosphate, 8-(meth) acryloyloxyoctyl dihydrogen phosphate gen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydecyl dihydrogen phosphate Phosphate, 16-(meth)acryloyloxyhexadecyldihydrogen phosphate, 20-(meth)acryloyloxyeicosyldihydrogenphosphate, 2-(meth)acryloyloxyethylphenylhydrogenphosphate, 2-(meth)acryloyloxyethyl- Phosphate groups such as 2-bromoethylhydrogen phosphate, 2-(meth)acryloyloxyethyl-(4-methoxyphenyl)hydrogenphosphate, 2-(meth)acryloyloxypropyl-(4-methoxyphenyl)hydrogenphosphate containing monofunctional (meth)acrylate compounds, their acid chlorides, alkali metal salts, ammonium salts, and amine salts; bis[2-(meth)acryloyloxyethyl]hydrogen phosphate, bis[4-(meth)acryloyl oxybutyl]hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl]hydrogenphosphate, bis[8-(meth)acryloyloxyoctyl]hydrogenphosphate, bis[9-(meth)acryloyloxynonyl]hydrogen Phosphate, bis[10-(meth)acryloyloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, and other phosphoric acid group-containing bifunctional (meth)acrylate compounds, acid chlorides thereof substances, alkali metal salts, ammonium salts, and amine salts.

Phosphonic acid group-containing (meth)acrylic polymerizable monomers include, for example, 2-(meth)acryloyloxyethylphenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-( meth) acryloyloxyhexyl-3-phosphonopropionate, 10-(meth) acryloyloxyhexyl-3-phosphonopropionate, 6-(meth) acryloyloxyhexylphosphonoacetate, 10-(meth) acryloyloxy Decylphosphonoacetate, acid chlorides thereof, alkali metal salts, ammonium salts, amine salts and the like.

Pyrophosphate group-containing (meth)acrylic polymerizable monomers include, for example, bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bispyrophosphate [6-(meth)acryloyloxyhexyl], bis[8-(meth)acryloyloxyoctyl] pyrophosphate, bis[10-(meth)acryloyloxydecyl] pyrophosphate, their acid chlorides, alkali metal salts, ammonium salts, amine salts and the like.

Carboxylic acid group-containing (meth)acrylic polymerizable monomers include, for example, (meth)acrylic acid, 4-[2-[(meth)acryloyloxy]ethoxycarbonyl]phthalic acid, 4-(meth)acryloyloxy Ethyl trimellitic acid, 4-(meth)acryloyloxybutyloxycarbonyl phthalate, 4-(meth)acryloyloxyhexyloxycarbonyl phthalate, 4-(meth)acryloyloxyoctyloxycarbonyl phthalate, 4-(meth)acryloyl Oxydecyloxycarbonyl phthalic 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-decanedicarboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, acid chlorides, alkali metal salts and ammonium salts thereof , and amine salts.

Examples of sulfonic acid group-containing (meth)acrylic polymerizable monomers 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 monomer (a), a phosphoric acid group-containing (meth)acrylic polymerizable monomer and a pyrophosphate group-containing (meth)acrylic polymerizable monomer , and carboxylic acid group-containing (meth)acrylic polymerizable monomers are preferable because they exhibit superior adhesive strength to tooth substance, in particular, phosphoric acid group-containing (meth)acrylic polymerizable monomers, and carboxylic acid group-containing (meth)acrylic polymerizable monomers are preferred. Among them, a phosphoric acid group-containing (meth)acrylate-based monofunctional polymerizable monomer or carboxylic acid group having a C ₆ to C ₂₀ alkyl group or a C ₆ to C ₂₀ alkylene group as a main chain in the molecule (Meth)acrylate-based polymerizable monomers are more preferred, and phosphoric acid group-containing (meth)acrylate-based monofunctional polymerizable monomers having a C ₈ to C ₁₂ alkylene group as a main chain in the molecule are further preferred. preferable. Also preferred are 10-methacryloyloxydecyldihydrogen phosphate, 4-(meth)acryloyloxyethyltrimellitic acid and 4-(meth)acryloyloxyethyltrimellitic anhydride, most preferred is 10-methacryloyloxydecyldihydrogenphosphate. .

The acidic group-containing (meth)acrylic polymerizable monomer (a) may be blended alone or in combination of two or more. The content 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. In 100 parts by mass, the range is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, even more preferably 3 to 20 parts by mass, and most preferably 4 to 20 parts by mass. In the present specification, the content of a certain polymerizable monomer in the total amount of 100 parts by mass of the polymerizable monomer component means that the total amount of the polymerizable monomer component is 100% by mass. It means the content (% by mass) of the polymerizable monomer. Therefore, the total amount of each polymerizable monomer component does not exceed 100 parts by mass.

Next, the polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group used in the present invention will be described. The polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group has no acidic group in the molecule and has at least two polymerizable groups. The polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group has the effect of improving the handleability or mechanical strength of the self-adhesive dental composite resin of the present invention. group compound-based bifunctional polymerizable monomers, aliphatic compound-based bifunctional polymerizable monomers, tri- or higher functional polymerizable monomers, and the like.

Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis((meth)acryloyloxyphenyl)propane, 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 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2 , 2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxy Dipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl) -2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2, bifunctional (meth)acrylate compounds such as 2-bis(4-(meth)acryloyloxypropoxyphenyl)propane and 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane;

Examples of aliphatic compound-based bifunctional polymerizable monomers include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 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 bifunctional (meth)acrylate compounds such as (3-methacryloyloxy-2-hydroxypropoxy)ethane;

Examples of trifunctional or higher polymerizable monomers include 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 Trifunctional or higher (meth)acrylate compounds such as (meth)acrylates and 1,7-diacryloyloxy-2,2,6,6-tetra(meth)acryloyloxymethyl-4-oxaheptane can be mentioned. Among these, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred.

Among the polyfunctional (meth)acrylic polymerizable monomers (b) containing no acidic group, from the viewpoint of mechanical strength or handleability, aromatic compound-based bifunctional polymerizable monomers, and fatty A bifunctional polymerizable monomer based on a group compound is preferably used. Examples of aromatic compound-based bifunctional polymerizable monomers include 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (commonly known as “Bis-GMA”), and 2, 2-bis(4-methacryloyloxypolyethoxyphenyl)propane (having an average number of added moles of ethoxy groups of 2.6, commonly known as “D-2.6E”) is preferred. Examples of aliphatic compound-based bifunctional polymerizable monomers include glycerol di(meth)acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (commonly known as “TEGDMA”), neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,10-decanediol 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) containing no acidic group may be blended alone or in combination of two or more. The content of the polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group is not particularly limited as long as the effect of the present invention is exhibited, but the dental composition (self-adhesive dental composite resin) 30 to 95 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer components in the self-adhesive dental composite resin because of its high permeability into the tooth structure, excellent adhesive strength, and sufficient strength. , more preferably 40 to 90 parts by mass, even more preferably 50 to 85 parts by mass, and most preferably 60 to 80 parts by mass.

The self-adhesive dental composite resin of the present invention may further contain a polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons as a polymerizable monomer component. Since the polyfunctional (meth)acrylamide polymerizable monomer (f) having at least one or more amide protons has at least one or more amide protons, it has high hydrophilicity and penetrates into the collagen layer of dentin. Since it is easy to use and has multiple polymerizable groups in the molecule, it exhibits extremely high curability together with other components of the self-adhesive dental composite resin, resulting in higher adhesion to dentin. can get.

Examples of the polyfunctional (meth)acrylamide polymerizable monomer (f) include a polyfunctional (meth)acrylamide polymerizable monomer (f1) represented by the following general formula (3), and a polyfunctional (meth)acrylamide polymerizable monomer (f1) represented by the following general formula (4). and a polyfunctional (meth)acrylamide polymerizable monomer (f2) represented by the following general formula (5).

（式中、Ｒ^１０、Ｒ^１１、及びＲ^１２はそれぞれ独立して、水素原子又はメチル基であり、ｓは１～６の整数であり、Ｘ^１、及びＸ^２はそれぞれ独立して、置換基を有していてもよいＣ_１～Ｃ_８の直鎖又は分岐鎖のアルキレン基である。）

(wherein R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group, s is an integer of 1 to 6, X ¹ and X ² are each independently substituted is a C ₁ to C ₈ linear or branched alkylene group optionally having a group.)

（式中、Ｒ^１３、及びＲ^１４はそれぞれ独立して、水素原子又はメチル基であり、ｔは２又は３であり、Ｘ^３、及びＸ^４はそれぞれ独立して、置換基を有していてもよいＣ_１～Ｃ_８の直鎖又は分岐鎖のアルキレン基である。）

(wherein R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, t is 2 or 3, X ³ and X ⁴ each independently have a substituent is a C ₁ to C ₈ linear or branched alkylene group that may be

（式中、Ｚは置換基を有していてもよいＣ_１～Ｃ_８の直鎖又は分岐鎖の脂肪族基又は芳香族基であって、前記脂肪族基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＮＲ^１５－、－ＣＯ－ＮＲ^１５－、－ＮＲ^１５－ＣＯ－、－ＣＯ－Ｏ－ＮＲ^１５－、－Ｏ－ＣＯＮＲ^１５－及び－ＮＲ^１５－ＣＯ－ＮＲ^１５－からなる群より選ばれる少なくとも１個の結合基によって中断されていてもよい。Ｒ^１５は、水素原子又は置換基を有していてもよいＣ_１～Ｃ_８の直鎖又は分岐鎖の脂肪族基を表す。）

(Wherein, Z is a C ₁ to C ₈ linear or branched aliphatic or aromatic group which may have a substituent, and the aliphatic group is —O—, —S -, -CO-, -CO-O-, -O-CO-, -NR ^{15 -, -CO-NR 15 -} , -NR ¹⁵ -CO-, -CO-O-NR ¹⁵ -, -O-CONR ¹⁵ — and —NR ¹⁵ —CO—NR ¹⁵ — R ¹⁵ may be interrupted by at least one bonding group selected from the group consisting of a hydrogen atom or C ₁ optionally having a substituent represents a linear or branched aliphatic group of ~ _C8 .)

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms from the viewpoint of adhesion to tooth substance and polymerization curability. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. Preferably t is three.

The optionally substituted C ₁ to C ₈ linear or branched alkylene groups of X ¹ , X ² , X ³ and X ⁴ include, for example, a methylene group, a methylmethylene group and 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, 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-methylpentamethylene group, 4-methylpentamethylene group, 5-methylpentamethylene group, hexamethylene group and the like. be done.

Examples of substituents of X ¹ , X ² , X ³ and X ⁴ include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group, hydroxy group, amino group, C ₁ to C ₈ Amino group, acyl group, acyloxy group, amido group, C ₂ -C ₈ alkoxycarbonyl group, C ₁ -C ₈ alkoxy group, C ₁ -C ₈ alkylthio group, C ₁ -C mono- or di-substituted with alkyl group ₈ alkyl groups are preferred, and halogen atoms (fluorine, chlorine, bromine and iodine atoms), C ₁ -C ₈ alkyl groups and the like are more preferred. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group and isopentyl. group, n-hexyl group, n-heptyl group, 2-methylhexyl group, n-octyl group and the like. The alkyl group is preferably a linear or branched C ₁ -C ₄ alkyl group. The number of substituents is not particularly limited, and may be about 1 to 8, preferably 1, 2 or 3.

The optionally substituted C ₁ to C ₈ aliphatic group represented by Z is a saturated aliphatic group (alkylene group, cycloalkylene group (eg, 1,4-cyclohexylene group, etc.)) , an unsaturated aliphatic group (alkenylene group, alkynylene group), preferably a saturated aliphatic group (alkylene group) from the viewpoint of availability or ease of 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 adhesiveness to tooth substance and polymerization curability, and has a substituent. It is more preferably a linear or branched C ₂ -C ₄ aliphatic group which may be substituted. Examples of the C ₁ to C ₈ alkylene groups include those similar to X ¹ , X ² , X ³ and X ⁴ .

The optionally substituted aromatic group represented by Z includes, for example, an aryl group and an aromatic heterocyclic group. As the aromatic group, an aryl group is more preferable than an aromatic heterocyclic group. The heterocyclic ring in the aromatic heterocyclic group is generally unsaturated. The aromatic heterocycle is preferably a 5- or 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. Among the aromatic groups, a phenyl group is particularly preferred.

The aliphatic group for R ¹⁵ may be either a saturated aliphatic group (alkyl group) or an unsaturated aliphatic group (alkenyl group, alkynyl group). A saturated aliphatic group (alkyl group) is preferred from the viewpoint. Examples of the alkyl group include the same C ₁ -C ₈ alkyl groups as those described as the substituents for X ¹ , X ² , X ³ and X ⁴ . R ¹⁵ is more preferably a hydrogen atom or an optionally substituted linear or branched C ₁ to C ₄ alkyl group, and a hydrogen atom or an optionally substituted linear or branched Chain C ₁ -C ₃ alkyl groups are more preferred.

Said aliphatic group of Z may be interrupted by at least one linking group as defined above. That is, at least one bonding group 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. Moreover, in the above formula (5), the aliphatic group of Z is preferably not interrupted by the continuous bonding groups. That is, it is preferable that the bonding groups are not adjacent to each other. As the binding group, -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, -CO-O- At least one bonding group selected from the group consisting of NH-, -O-CO-NH- and -NH-CO-NH- is more preferred, and -O-, -S-, -CO-, -NH-, At least one linking group selected from the group consisting of -CO-NH- and -NH-CO- is more preferred.

Specific examples of the polyfunctional (meth)acrylamide polymerizable monomer (f1) represented by the above formula (3) are not particularly limited, but include the following.

Among these, the compound (f1-1), the compound (f1-3), the compound (f1-5), and the compound (f1-7) are preferable from the viewpoint of adhesiveness to tooth substance and polymerization curability, and the compound (f1- 1), the compound (f1-5) is more preferable, and the compound (f1-5) is most preferable from the viewpoint of high hydrophilicity related to penetration into the collagen layer of dentin.

Specific examples of the polyfunctional (meth)acrylamide polymerizable monomer (f2) represented by formula (4) are not particularly limited, but include the following.

Among these, the compound (f2-1), the compound (f2-3), the compound (f2-5), and the compound (f2-7) are preferable from the viewpoint of adhesiveness to tooth substance and polymerization curability, and the compound (f2- 1), compound (f2-3) is more preferable, and compound (f2-1) is most preferable from the viewpoint of high hydrophilicity related to penetration into the collagen layer of dentin.

Specific examples of the polyfunctional (meth)acrylamide polymerizable monomer (f3) represented by the above formula (5) (hereinafter also referred to as an asymmetric polyfunctional (meth)acrylamide polymerizable monomer (f3)) Although not particularly limited, examples thereof include those shown below.

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

The polyfunctional (meth)acrylamide polymerizable monomer (f) having at least one or more amide protons may be used alone or in combination of two or more. For example, a polyfunctional (meth)acrylamide polymerizable monomer (f3), a group consisting of a polyfunctional (meth)acrylamide polymerizable monomer (f1) and a polyfunctional (meth)acrylamide polymerizable monomer (f2) It may be a combination with one or more polymerizable monomers selected from. The content of the polyfunctional (meth)acrylamide polymerizable monomer (f) is not particularly limited as long as the effect of the present invention is exhibited, but in 100 parts by mass of the total amount of the polymerizable monomer components, 0.5 to 0.5 The range is preferably 30 parts by mass, more preferably 2 to 25 parts by mass, even more preferably 2.5 to 28 parts by mass, and most preferably 3 to 20 parts by mass.

The self-adhesive dental composite resin of the present invention may or may not further contain a hydrophilic monofunctional polymerizable monomer (g) as a polymerizable monomer component. The hydrophilic monofunctional polymerizable monomer (g) is a monofunctional polymerizable monomer other than the above (a), the above (b), and the above (f) having a solubility in water of 5% by mass or more at 25 ° C. It means a monomer, and preferably has a solubility of 10% by mass or more, more preferably 15% by mass or more. By including the hydrophilic monofunctional polymerizable monomer (g), higher adhesion to dentin can be obtained.

The hydrophilic monofunctional polymerizable monomer (g) has at least one hydrophilic group such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxypropylene group and an amide group. Hydrophilic monofunctional polymerizable monomers (g) include 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 (meth) ) acrylamide, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, diacetone (meth) Acrylamide, 4-(meth)acryloylmorpholine, N-trihydroxymethyl-N-methyl(meth)acrylamide, and monofunctional (meth)acrylamide-based polymerizable monomers represented by the following general formula (6), etc. Hydrophilic monofunctional (meth)acrylamide-based polymerizable monomers can be mentioned.

（式中、Ｒ^１６及びＲ^１７はそれぞれ独立して、置換基を有していてもよい直鎖又は分岐鎖のＣ_１～Ｃ_３のアルキル基であり、Ｒ^１８は水素原子又はメチル基である。）

(In the formula, R ¹⁶ and R ¹⁷ are each independently a linear or branched C ₁ -C ₃ alkyl group which may have a substituent, and R ¹⁸ is a hydrogen atom or a methyl group. be.)

Examples of the substituents for R ¹⁶ and R ¹⁷ include those similar to the substituents for X ¹ , X ² , X ³ and X ⁴ . Examples of the C ₁ to C ₃ alkyl groups for R ¹⁶ and R ¹⁷ include methyl group, ethyl group, n-propyl group and isopropyl group.

Among these hydrophilic monofunctional polymerizable monomers (g), 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, diacetone (meth) ) Acrylamide and a monofunctional (meth)acrylamide-based polymerizable monomer represented by the general formula (6) are preferable, and a monofunctional (meth)acrylamide-based polymerizable monomer represented by the general formula (6) is more preferred. The hydrophilic monofunctional polymerizable monomer (g) may be used alone or in combination of two or more.

Further, among the monofunctional (meth)acrylamide-based polymerizable monomers represented by the general formula (6), N,N-dimethylacrylamide and N,N-diethylacrylamide are more preferable from the viewpoint of storage stability. , N,N-diethylacrylamide is most preferred.

The content of the hydrophilic monofunctional polymerizable monomer (g) in the present invention is not particularly limited as long as the effect of the present invention is exhibited. It is preferably in the range of 1 to 30 parts by mass, more preferably in the range of 2 to 28 parts by mass, and more preferably in the range of 5 to 25 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer components in the adhesive dental composite resin. More preferably, the range of 7 to 20 parts by mass is particularly preferable.

In the self-adhesive dental composite resin of the present invention, in order to improve adhesive strength, handleability, mechanical strength, etc., within the range that does not impair the effects of the present invention, an acidic group-containing (meth)acrylic polymerizable Monomer (a), polyfunctional (meth)acrylic polymerizable monomer containing no acidic group (b), polyfunctional (meth)acrylamide polymerizable monomer having amide protons (f), hydrophilic A polymerizable monomer (j) other than the monofunctional polymerizable monomer (g) may be blended. Examples of the polymerizable monomer (j) include a hydrophilic polyfunctional (meth)acrylate polymerizable monomer (j1) and/or a symmetrical (meth)acrylamide compound (j2). The hydrophilic polyfunctional (meth)acrylate-based polymerizable monomer (j1) has a solubility in water at 25° C. of 5% by mass or more, and is a poly(a), (b), or (f) other than It means a functional polymerizable monomer, preferably having a solubility of 10% by mass or more, and more preferably having a solubility of 15% by mass or more. Examples of the hydrophilic polyfunctional (meth)acrylate polymerizable monomer (j1) include pentaerythritol di(meth)acrylate, erythritol di(meth)acrylate, mannitol di(meth)acrylate, and xylitol di(meth) Acrylate, sorbitol di(meth)acrylate and the like. Examples of the symmetrical (meth)acrylamide compound (j2) include N,N'-ethylenebisacrylamide and N,N'-diethyl-1,3-propylenebisacrylamide. The polymerizable monomer (j) may be used singly or in combination of two or more.

The total content of polymerizable monomers contained in the self-adhesive dental composite resin of the present invention is preferably less than 49.9% by mass, more preferably 44.5% by mass, relative to the entire self-adhesive dental composite resin. % is more preferred, and less than 40.0% by mass is even more preferred. Further, the total content 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) in the present invention is a component that accelerates polymerization and hardening of the self-adhesive dental composite resin. The photopolymerization initiator (c) can be selected from known photopolymerization initiators, and among them, photopolymerization initiators used for dental applications are preferably used. The photopolymerization initiator (c) may be used alone or in combination of two or more.

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, Examples include anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like.

Among these photopolymerization initiators (c), 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 that exhibits excellent photocuring properties in the visible and near-ultraviolet regions and exhibits sufficient photocuring properties using any light source, such as a halogen lamp, a light emitting diode (LED), or a xenon lamp, has been developed. can get.

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

Examples of the bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, 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-trimethylpentylphosphine oxide and the like. Among these, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide is preferred.

Examples of the α-diketones include diacetyl, benzyl, dl-camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4′-oxybenzyl, and acenaphthenequinone. are mentioned. Among these, dl-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-7-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-methoxycoumarin), 3,3′-carbonylbis(7-acetoxycoumarin), 3,3′- carbonylbis(7-dimethylaminocoumarin), 3-(2-benzothiazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-7-(dibutylamino)coumarin, 3-(2- benzimidazolyl)-7-(diethylamino)coumarin, 3-(2-benzothiazolyl)-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-benzothiazolyl)- 2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H,5H,11H-[1]benzopyrano[6,7,8-ij]quinolidin-11-one, etc. 3109 and the compounds described in JP-A-10-245525. Among them, 3,3'-carbonylbis(7-diethylaminocoumarin) and 3,3'-carbonylbis(7-dibutylaminocoumarin) are preferred.

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 WO 2008/087977. The one described in is mentioned.

The content of the photopolymerization initiator (c) is not particularly limited, but from the viewpoint of the curability of the obtained self-adhesive dental composite resin, etc. 0.001 to 20 parts by weight is preferred, 0.05 to 10 parts by weight is more preferred, and 0.10 to 5 parts by weight is even more preferred. If the content of the photopolymerization initiator (c) is less than 0.001 parts by mass with respect to the total amount of 100 parts by mass of the polymerizable monomer components, the polymerization does not proceed sufficiently, resulting in a decrease in adhesive strength. 0.05 parts by mass or more is more preferable, and 0.10 parts by mass or more is even more preferable. On the other hand, when the content of the photopolymerization initiator (c) exceeds 20 parts by mass with respect to the total amount of 100 parts by mass of the polymerizable monomer components, if the polymerization performance of the photopolymerization initiator itself is low, sufficient 10 parts by mass or less per 100 parts by mass of the total amount of polymerizable monomer components is more preferable, and 5 parts by mass or less is even more preferable.

The self-adhesive dental composite resin of the present invention can further contain a chemical polymerization initiator. Organic peroxides are preferably used as chemical polymerization initiators. The organic peroxide is not particularly limited, and known ones can be used. Representative organic peroxides include, for example, ketone peroxides, hydroperoxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, peroxydicarbonates, and the like. Specific examples of these organic peroxides include those described in International Publication No. 2008/087977. The chemical polymerization initiators may be used singly or in combination of two or more.

In the self-adhesive dental composite resin of the present invention, the filler (i), which is neither the filler (d) nor the filler (e), is added so as to have an appropriate effect on jettability, fluidity, sagging and surface hardness. may be included as long as it is not The filler (i) has an isoelectric point of less than 6.0 and is not treated with a surface treatment agent containing both the silane coupling agent (A) and the organosilazane (B), It is a component for the purpose of imparting X-ray opacity to a self-adhesive dental composite resin, or improving strength as a matrix or paste handling.

As used herein, "radio-opacity" refers to the ability of a hardened dental material to be distinguished from tooth structures using standard dental X-ray equipment in a conventional manner. Radiopacity in dental materials is advantageous in certain cases where X-rays are used to diagnose dental conditions.

As the filler (i), any known fillers used in dental composite resins can be used without any limitation, other than those corresponding to the fillers (d) and (e). Examples of the filler include liquid-phase synthetic amorphous silica, fumed silica, fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (Pyrex (registered trademark) glass), and other common fillers. glass powders with different compositions; dental glass powders such as barium glass, strontium borosilicate glass, lanthanum glass ceramics, and fluoroaluminosilicate glass; composite oxides such as silica-titania and silica-zirconia; Core-shell structure calcium fluoride, core-shell structure ytterbium fluoride surface-coated with silica, core-shell structure yttrium fluoride surface-coated with silica, core-shell structure calcium phosphate surface-coated with silica, surface with silica barium sulfate with a core-shell structure coated with , zirconium dioxide with a core-shell structure with a surface coated with silica, titanium dioxide with a core-shell structure with a surface coated with silica, and hydroxyapatite with a core-shell structure with a surface coated with silica. be done. These may be used individually by 1 type, respectively, and can also use 2 or more types together. Among these, those having a silica surface are preferable from the viewpoint of being able to be treated with the silane coupling agent (A) and forming a weak electrostatic association state with the filler (d) having an isoelectric point of 6.0 or higher. Therefore, fumed silica, silica-coated core-shell ytterbium fluoride, and silica-coated core-shell yttrium fluoride are suitable.

The average particle size of the filler (i) is preferably 0.001 to 50.0 μm, more preferably 0.005 to 20.0 μm, still more preferably 0.008 to 10.0 μm, and 0.01 to 4.50 μm. is particularly preferred. Within these ranges, sufficient mechanical strength is obtained, the paste does not become sticky, no problem occurs in operability, and the cured product is excellent in polishing lubricity and lubricity durability.

The average particle size of the filler (i) can be measured in the same manner as the method for measuring the average particle sizes of the filler (d) and the filler (e).

The filler (i) is preferably treated with a surface treating agent. Such surface treatment agents include at least one organometallic compound selected from the group consisting of organosilicon compounds, organotitanium compounds, organozirconium compounds, and organoaluminum compounds. The silane coupling agent (A) and Surface treatment agents containing both the organosilazane (B) are excluded. When two or more organometallic compounds are used, the surface treatment layer may be a mixture of two or more organometallic compounds, or may be a surface treatment layer having a multi-layer structure in which two or more organometallic compound layers are laminated. good.

Examples of the organosilicon compound include the compound represented by (W) _n SiY _4-n exemplified as the surface treatment agent for the filler (d) (wherein the symbols have the same meanings as above).

Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, 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-methacryloyloxypropylmethyldimethoxysilane, γ -methacryloyloxypropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(amino ethyl)-γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, Methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethylbromosilane, diethylsilane, vinyltriacetoxysilane, ω-(meth)acryloyloxyalkyltrimethoxysilane (Number of carbon atoms between (meth)acryloyloxy group and silicon atom: 3 to 12, e.g., 3-methacryloyloxypropyltrimethoxysilane, etc.), ω-(meth)acryloyloxyalkyltriethoxysilane ((meth)acryloyl Number of carbon atoms between oxy group and silicon atom: 3 to 12, eg, 3-methacryloyloxypropyltriethoxysilane, etc.).

Among these, a coupling agent having a functional group capable of copolymerizing with the polymerizable monomer component, such as ω-(meth)acryloyloxyalkyltrimethoxysilane (a carbon between the (meth)acryloyloxy group and the silicon atom) number: 3 to 12), ω-(meth)acryloyloxyalkyltriethoxysilane (number of carbon atoms 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 compounds include zirconium isopropoxide, zirconium n-butoxide, zirconium acetylacetonate, and zirconyl acetate.

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

The shape of the filler (i) is not particularly limited, and may be appropriately selected according to the properties desired to be enhanced as a dental composite resin. Specifically, it can be used as a powder of amorphous or spherical particles. . When the amorphous filler (i) is used, the mechanical strength and abrasion resistance are particularly excellent, and when the spherical filler (i) is used, the polishing lubricity and lubricating durability are particularly excellent. A commercially available product may be used as the filler (i) in the present invention.

The content of the filler (i) is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably in the range of 1 to 100 parts by mass, and in the range of 3 to 90 parts by mass, with respect to 100 parts by mass of the polymerizable monomer. is more preferable, and a range of 5 to 80 parts by mass is particularly preferable. Within these ranges, sufficient X-ray opacity of the cured product or sufficient mechanical strength can be obtained, and sufficient paste operability can be obtained.

The self-adhesive dental composite resin of the present invention can preferably use the fumed silica as a filler (i) for the purpose of imparting leveling to the paste. The fumed silica is silica produced in a dry process by combustion hydrolysis using silicon tetrachloride as a precursor, and may or may not be blended in the self-adhesive dental composite resin of the present invention. , may be added for the purpose of adjusting the leveling properties of the paste. In addition, the leveling property of the paste is the property that the edge of the paste taken out from the container disappears due to its own weight.

The BET specific surface area (specific surface area according to the BET (Brunauer-Emmett-Teller) method) of the fumed silica is preferably 25 m ² /g or more, more preferably 50 m ² /g or more, from the viewpoint of imparting leveling properties to the paste. 100 m ² /g or more is more preferable. From the viewpoint of not impairing the leveling property of the self-adhesive dental composite resin, it is preferably 400 m ² /g or less, more preferably 350 m ² /g or less, and even more preferably 250 m ² /g or less. Therefore, from the above viewpoint, the BET specific surface area of fumed silica is preferably 25 to 400 m ² /g, more preferably 50 to 350 m ² /g, even more preferably 100 to 250 m ² /g.

From the viewpoint of not impairing the leveling property of the paste, the average primary particle size of the fumed silica is preferably 5 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more. From the viewpoint of imparting leveling properties to the paste, the thickness is preferably 50 nm or less, more preferably 30 nm or less, and even more preferably 20 nm or less. Therefore, from the above viewpoint, the average primary particle size of fumed silica 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 is preferably 3.0 or higher, more preferably 3.5 or higher, and 4.0 or higher from the viewpoint of not affecting other components in the self-adhesive dental composite resin of the present invention. is more preferred. From the viewpoint of suppressing reaction with the acidic group-containing (meth)acrylic polymerizable monomer (a), it is preferably 10.0 or less, more preferably 9.0 or less, and even more preferably 8.0 or less. Therefore, from the above viewpoint, the pH of fumed silica 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 is preferably 20 g/L or more, more preferably 50 g/L or more, and even more preferably 120 g/L or more, from the viewpoint of suppressing an increase in viscosity when blended. In addition, from the viewpoint that the effect of imparting fluidity to the paste by the bearing effect is higher, 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 fumed silica (d) is preferably 20 to 300 g/L, more preferably 50 to 290 g/L, and even more preferably 120 to 280 g/L.

That is, the fumed silica 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 paste leveling properties. More preferably, it has a specific surface area of 100 to 250 m ² /g, an apparent specific gravity of 120 to 280 g/L, a BET specific surface area of 100 to 250 m ² /g, and a pH of 4.0 to 8.0. and more preferably an apparent specific gravity of 120 to 280 g/L, a BET specific surface area of 100 to 250 m ² /g, an average primary particle size of 7 to 30 nm, and a pH of 4.0 to 8. .0 and an apparent specific gravity of 120 to 280 g/L are particularly preferred.

The method for measuring the above chemical properties of fumed silica 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 volume gas adsorption method (nitrogen adsorption and desorption measurement), Microtrac Bell Co., Ltd.).
Average primary particle size (nm):
A scanning electron microscope (manufactured by Hitachi, Ltd., model S-4000) photograph of the sample is taken, and the particle size of the particles (200 or more) observed in the unit field of view of the photograph is measured by image analysis type particle size distribution. Obtained by measurement using software (Macview (Mountech Co., Ltd.)). At this time, the particle diameter of the particles is obtained as an arithmetic mean 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 their particle diameters.
pH:
4 parts by mass of the sample is dispersed in 100 parts by mass of distilled water at room temperature 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 conforms to ISO 787-9:1981 except that a 4% by weight aqueous dispersion is used.
Apparent specific gravity:
It is measured according to the method according to ISO 787-11:1981, and the tapped density (also called tamped density) is calculated by the following formula.

Further, it is preferable that the fumed silica is treated with the surface treatment agent described above for the filler (i), then heat-treated, and then structurally modified. Here, to structurally modify means to increase the apparent specific gravity without significantly changing the BET specific surface area, average primary particle size, and pH.

Means for structural modification are not particularly limited as long as the apparent specific gravity can be increased without significantly changing the BET specific surface area, average primary particle size, and pH. It can be structurally modified by first spraying with water, then with a surface treatment agent, optionally further mixing, and then heat treatment.

The water used may be acidified (pH 1-7) with an acid (eg hydrochloric acid), and if several surface treatment agents are used, these surface treatment agents may be used simultaneously. They may also be used separately one at a time or as a mixture. One or more surface treatment agents may be dissolved in a suitable solvent such as water, ethanol, isopropyl alcohol. Mixing may be continued for an additional 5-30 minutes after spraying is complete.

Furthermore, the mixture is heat-treated at a temperature of 20-400° C. for 0.1-6 hours, the heat treatment being carried out under a protective gas, for example a nitrogen atmosphere.

Structurally modified fumed silica has a high apparent specific gravity. Dental compositions containing modified fumed silica (self-adhesive dental composite resins) exhibit significantly increased viscosity compared to dental compositions containing structurally unmodified fumed silica. can be suppressed. That is, the structurally modified fumed silica can be blended in a larger amount than the structurally unmodified fumed silica, and the effect of imparting leveling properties to the paste can be greatly improved. can.

The apparent specific gravity of the structurally modified fumed silica is preferably 100 to 300 g/L, more preferably 110 to 290 g/L, and even more preferably 120 to 280 g/L, from the above viewpoints. Fumed silica can use a commercial item. In particular, commercial products of structurally modified fumed silica include, for example, AEROSIL (registered trademark) R7200 (surface treatment agent: silane compound containing methacryloyloxysilyl group, 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 (registered trademark) R8200 (surface treatment agent: 1,1,1,3,3,3-hexamethyl Disilazane, 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 (surface treatment agent : dimethyldichlorosilane, BET specific surface area: 170 m ² /g, average primary particle size: 12 nm, pH: 4.0, apparent specific gravity: 200 g/L, manufactured by EVONIK INDUSTRIES) and the like.

The total content of fillers (filler (d), filler (e) and filler (i)) contained in the self-adhesive dental composite resin of the present invention is 50% with respect to the entire self-adhesive dental composite resin. 0% by mass or more is preferable, 55.0% by mass or more is more preferable, and 59.0% by mass or more is even more preferable. The total content of fillers is preferably 90.0% by mass or less, more preferably 85.0% by mass or less, and even more preferably 80.0% by mass or less, relative 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 the filler (d) and the filler (e), the preferred content is the sum of the filler (d) and the filler (e) It is good also as content.

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

In other embodiments, a polymerization accelerator (h) is used together with a photoinitiator (c) and/or a chemical polymerization initiator. Examples of the polymerization accelerator (h) include amines, sulfinic acid and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfurous acid. salts, hydrogen sulfites, thiourea compounds, and the like.

The amines are divided into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methylethanolamine; ; N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2-(dimethylamino)ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono tertiary aliphatic amines such as methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine and tributylamine; Among these, tertiary aliphatic amines are preferred from the viewpoint of curability and storage stability of the self-adhesive dental composite resin, and among these, N-methyldiethanolamine and triethanolamine are more preferred.

Examples of the aromatic amine include N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline, N,N-bis(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-t-butylaniline, N,N-dimethyl-3,5-di-t-butylaniline, 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)benzoate methyl acid, 4-(N,N-dimethylamino)propyl benzoate, 4-(N,N-dimethylamino)n-butoxyethyl benzoate, 2-(N,N-dimethylamino)benzoate 2-(methacryloyl oxy)ethyl, 4-(N,N-dimethylamino)benzophenone, 4-(N,N-dimethylamino)butyl benzoate and the like. Among these, N,N-bis(2-hydroxyethyl)-p-toluidine and 4-(N,N-dimethylamino)benzoic acid are used from the viewpoint of imparting excellent curability to self-adhesive dental composite resins. 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, hydrogensulfites, and thiourea compounds can include those described in International Publication No. 2008/087977.

The polymerization accelerator (h) may be blended alone or in combination of two or more. The content of the polymerization accelerator (h) is not particularly limited, but from the viewpoint of the curability of the obtained self-adhesive dental composite resin, the content is 0.00 per 100 parts by mass of the total amount of the polymerizable monomer components. 001 to 30 parts by weight is preferred, 0.01 to 10 parts by weight is more preferred, and 0.1 to 5 parts by weight is most preferred. The content of the polymerization accelerator (h) 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 monomer components. If the content of the polymerization accelerator (h) is less than 0.001 parts by mass with respect to the total amount of 100 parts by mass of the polymerizable monomer components, the polymerization may not proceed sufficiently, resulting in a decrease in adhesiveness. be. On the other hand, when the content of the polymerization accelerator (h) exceeds 30 parts by mass with respect to the total amount of 100 parts by mass of the polymerizable monomer components, sufficient adhesion may be obtained depending on the polymerization performance of the polymerization initiator itself. Moreover, the polymerization accelerator (h) may precipitate from the self-adhesive dental composite resin.

The self-adhesive dental composite resin of the present invention may further contain a fluoride ion releasing substance (k). By blending the fluoride ion-releasing material (k), a self-adhesive dental composite resin can be obtained that can impart acid resistance to tooth substance. Examples of such fluoride ion-releasing substances include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, and ytterbium fluoride. The fluoride ion-releasing substance (k) may be used alone or in combination of two or more.

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 ( A meth)acrylic polymerizable monomer (a), a polyfunctional (meth)acrylic polymerizable monomer containing no acidic group (b), and a polyfunctional (meth)acrylamide polymerizable monomer having an amide proton A self-adhesive dental composite resin containing (f) and containing a filler (d) and a filler (e) as the filler; or a polymerizable monomer, a photopolymerization initiator (c), and a filler containing, the polymerizable monomer is an acidic group-containing (meth)acrylic polymerizable monomer (a), a polyfunctional (meth)acrylic polymerizable monomer containing no acidic group (b), and A self-adhesive dental composite resin containing a hydrophilic monofunctional polymerizable monomer (g) and containing a filler (d) and a filler (e) as the filler is exemplified.

In another preferred embodiment, a polymerizable monomer, a photopolymerization initiator (c), and a filler are contained, and the polymerizable monomer is an acidic group-containing (meth)acrylic polymerizable Monomer (a), polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group, polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons, and hydrophilic A self-adhesive dental composite resin containing a monofunctional polymerizable monomer (g) having a molecular weight and containing a filler (d) and a filler (e) as the filler.

Furthermore, another preferred embodiment contains 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, and polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons, and hydrophilic containing a monofunctional polymerizable monomer (g), wherein the polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group is an aliphatic compound-based bifunctional polymerizable monomer wherein the polyfunctional (meth)acrylamide polymerizable monomer (f) having the amide proton contains a polyfunctional (meth)acrylamide polymerizable monomer (f3) represented by the general formula (5) , the hydrophilic monofunctional polymerizable monomer (g) contains a hydrophilic monofunctional (meth)acrylate polymerizable monomer, and as the filler, a filler (d) and a filler (e) A self-adhesive dental composite resin containing

Furthermore, another preferred embodiment contains a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer is an acidic group-containing (meth)acrylic polymerizable Monomer (a), polyfunctional (meth)acrylic polymerizable monomer (b) containing no acidic group, polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons, and hydrophilic 1 to 1 of an acidic group-containing (meth)acrylic polymerizable monomer (a) in 100 parts by mass of the total amount of the polymerizable monomer components. 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 (f) having an amide proton. 0.5 to 30 parts by mass, containing 1 to 30 parts by mass of a hydrophilic monofunctional polymerizable monomer (g), and as the filler, a filler (d) and a filler (e), self Adhesive dental composite resins are included.

In any of the preferred embodiments described above, the content of each component can be appropriately changed based on the above description, the type of compound can be appropriately selected, and any component (e.g., polymerization accelerator (h), chemical polymerization initiator, polymerization inhibitor, etc.) may be added or removed.

In addition, the self-adhesive dental composite resin of the present invention may contain a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, a thickener, a coloring agent, an antibacterial agent, a fragrance, etc. within a range that does not impair the effects of the present invention. May be blended.

The self-adhesive dental composite resin of the present invention may be preferably of a one-component type or a divided package type. Among them, one material type is more preferable from the viewpoint of simplicity of operation. The self-adhesive dental composite resin of the present invention preferably has a surface hardness (Vickers hardness) of 25 to 55 Hv, more preferably 30 to 50 Hv, and more preferably 35 to 45 Hv. More preferred.

The present invention includes various combinations of the above configurations within the technical scope of the present invention as long as the effects of the present invention are exhibited.

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The abbreviations and abbreviations used below are as follows. Commercially available compounds were used for the compounds used in the following examples and comparative examples, except when synthesis methods were specifically described.

[Acidic 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 number of added moles of ethoxy groups of 2.6)
TEGDMA: triethylene glycol dimethacrylate

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

[Filler (d)]
ALU-C: Commercial product (trade name: AEROXIDE (registered trademark) Alu C, BET specific surface area: 100 m ² /g, average primary particle size: 13 nm, pH: 5.0, apparent specific gravity: 50 g/L, EVONIK INDUSTRIES company) was used as it was. The isoelectric point was 9.0.
ST-ALU-C: commercial product (trade name: AEROXIDE (registered trademark) Alu C, BET specific surface area: 100 m ² /g, average primary particle size: 13 nm, pH: 5.0, apparent specific gravity: 50 g/L, EVONIK INDUSTRIES) was surface-treated with 10-methacryloyloxydecyldihydrogen phosphate and 11-methacryloyloxyundecyltrimethoxysilane. The isoelectric point was 9.0.

ＭＡＥＡ：Ｎ－メタクリロイルオキシエチルアクリルアミド（下記式で表される非対称型の多官能（メタ）アクリルアミド重合性単量体）

[Polyfunctional (meth)acrylamide polymerizable monomer having amide protons (f)]
TAC4: N,N',N'',N'''-tetraacryloyltriethylenetetramine (compound (f1-5) represented by the following formula)

MAEA: N-methacryloyloxyethylacrylamide (asymmetric polyfunctional (meth)acrylamide polymerizable monomer represented by the following formula)

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

[Filler (e)]
Fillers (e-1) and (e-2) described later in Production Examples were used.

[Filler (i)]
R 7200:
Commercial product (trade name: AEROSIL (registered trademark) R 7200, surface treatment agent: silane compound containing methacryloyloxysilyl group, 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.
R711:
Commercial product (trade name: AEROSIL (registered trademark) R 711, surface treatment agent: silane compound containing methacryloyloxysilyl group, BET specific surface area: 150 m ² /g, average primary particle size: 12 nm, pH: 4.5, apparent Specific gravity: 50 g/L, manufactured by EVONIK INDUSTRIES) was used as it was.
SiO ₂ coated YBF: silica-coated ytterbium fluoride:
A commercially available product (SG-YBF100WSCMP10, average particle size 110 nm, spherical particles, manufactured by Sukgyung AT) was used as it was.

[Polymerization accelerator (h)]
DABE: 4-(N,N-dimethylamino) ethyl benzoate [others]
BHT: 3,5-dibutyl-4-hydroxytoluene (stabilizer (polymerization inhibitor))

(Production example 1)
Production of Filler (e-1) As silica particles, SNOWTEX OL (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 50 nm, dispersed in water, solid content concentration 20%), which is a kind of colloidal silica, was prepared. Isopropanol was prepared as alcohol. 3-Methacryloyloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared as a silane coupling agent (A). As the organosilazane (B), 1,1,1,3,3,3-hexamethyldisilazane (HMDS, manufactured by Shin-Etsu Chemical Co., Ltd., HMDS-1) was prepared. 60 parts by mass of isopropanol was added to 100 parts by mass of slurry in which silica particles were dispersed in water at a concentration of 20% by mass, and the mixture was mixed at room temperature (about 25°C) to obtain a dispersion in which silica particles were dispersed in a liquid medium. Obtained. 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 Kagaku Co., Ltd.) were added to this dispersion. , 40° C. for 72 hours. Through this step, the hydroxyl groups present on the surfaces of the silica particles were surface-treated with the silane coupling agent (A). At this time, 3-methacryloyloxypropyltrimethoxysilane was added so that the required amount of hydroxyl groups (part) remained without surface treatment. Next, 0.78 parts by mass of 1,1,1,3,3,3-hexamethyldisilazane was added to this mixture and left at 40° C. for 72 hours. This step surface-treated the silica particles to obtain a silica particle material. As the surface treatment progressed, the hydrophobic silica particles became unable to exist stably in water and isopropanol, aggregated and precipitated. The molar ratio of 3-methacryloyloxypropyltrimethoxysilane and hexamethyldisilazane as the surface treatment agent was 2:5. 2.6 parts by mass of a 35% hydrochloric acid aqueous solution 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 filter paper (5A manufactured by Advantech). The filtration residue (solid content) was washed with pure water and then vacuum-dried at 100° C. to obtain a filler (e-1) (average particle size: 50 nm). The isoelectric point was 1.8.

(Production example 2)
Production of Filler (e-2) All processes for synthesizing filler (e-1) except that the amount of 1,1,1,3,3,3-hexamethyldisilazane used was changed to 2.8 parts by mass. Filler (e-2) (average particle size 50 nm) was produced in the same manner. The molar ratio of 3-methacryloyloxypropyltrimethoxysilane and hexamethyldisilazane used as surface treatment agents was 2:18. The isoelectric point was 1.8.

(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, 0.75 mol) were placed in a 1 L four-necked flask. 03 mmol) and 250 mL of dichloromethane were added, 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 lower over 2 hours. After dropping, the mixture was stirred at room temperature for 24 hours. The reaction mixture was filtered, the insoluble matter was washed with dichloromethane, and the filtrate was 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 (volume ratio)). After 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 it was confirmed from the position and integral value of the signal that the obtained white solid was the desired compound. 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 Hydroxyethylacrylamide (Kohjin Film & Chemicals Co., Ltd., 172.7 g, 1.5 mol), triethylamine (167 g, 1.65 mol), p-methoxyphenol (38 mg, 0.3 mmol) were placed in a 10 L four-necked flask. , and 1500 mL of anhydrous tetrahydrofuran were 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 lower over 2 hours. After dropping, the mixture was stirred at room temperature for 24 hours. The reaction solution was filtered, and the insoluble matter was washed with ethyl acetate. The filtrate was concentrated under reduced pressure and the residue was dissolved in ethyl acetate. After removing a small amount of insoluble matter by filtration through celite, the filtrate was washed with a mixture of saturated saline and purified water (volume ratio 1:1). The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure at 35°C or lower. 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 and integral value of the signal that the pale yellow liquid obtained 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 to 21 and Comparative Examples 1 to 5)
Using the materials of each of the production examples described above, among the components listed in Tables 1 to 3, the components other than filler (d), filler (e) and filler (i) (all powders) were added at room temperature ( After mixing at about 25 ° C.) to form a uniform liquid component, the obtained liquid component and the powder components of the filler (d), the filler (e) and the filler (i) were kneaded. 21 self-adhesive dental composite resins and Comparative Examples 1-5 dental composite resins (pastes) were prepared. Then, these pastes were used to evaluate surface hardness, sagging, tensile adhesive strength to dentin, flexural strength, and ejection properties 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.

[surface hardness]
An appropriate amount of the dental composite resin paste prepared in each example and comparative example was placed on a slide glass, and the top and bottom surfaces were pressed against the slide glass using a 1 mm gauge (manufactured by Mitutoyo Co., Ltd.). A visible light irradiator for polymerization (trade name: Pencure 2000, manufactured by Morita Co., Ltd.) was used to irradiate and cure for 10 seconds to prepare a disc having a diameter of 10 mm and a thickness of 1 mm. The clean smooth surface was polished with #1500 abrasive paper under dry conditions, and finally mirror-polished with diamond paste. The sample prepared here was measured for Vickers hardness (Hv) by applying a load of 200 g for 10 seconds using a microhardness tester (HM-221, manufactured by Mitutoyo Co., Ltd.) (n = 5). value was calculated. The surface hardness (Vickers hardness) of the cured product is preferably 25 to 55 Hv, more preferably 30 to 50 Hv, even more preferably 35 to 45 Hv.

[Sagging]
The sagging, which is an index of paste fluidity, was evaluated as follows. After vacuum defoaming, the dental composite resin paste prepared in each of Examples and Comparative Examples was filled in a syringe made of polyolefin resin. Next, a needle tip with a needle thickness of 20G (gauge) was attached to the syringe. After that, in a 37 ° C. environment, 20 mg was dispensed on a kneaded Japanese paper, and the distance (mm) that the paste moved 1 minute after tilting the kneaded paper vertically was measured (n = 5), and the average value was calculated. and the sagging property of the dental composite resin immediately after preparation.
Separately from the above, the dental composite resin paste was vacuum degassed, filled into a syringe made of polyolefin resin, and then allowed to stand in a thermostat kept at 60 ° C. for 4 weeks. The value measured by the above method was taken as the sagging property of the dental composite resin after 4 weeks at 60°C. The difference between the sagging property immediately after preparation and the sagging property after 4 weeks at 60° C. is preferably 2.5 mm or less, more preferably 2.3 mm or less, and even more preferably 2.2 mm or less.

[Tensile bond strength to dentin]
The lip surface of the bovine mandibular anterior tooth was polished with #80 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water to obtain a sample to be bonded in which the flat surface of the dentin was exposed. The obtained sample to be adhered was further polished with #1000 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. After finishing the polishing, the water on the surface was dried by air blowing. An adhesive tape having a thickness of about 150 μm and having a round hole with a diameter of 3 mm was adhered 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). Then, a slide glass was placed on the release film and pressed to smooth the surface on which the paste was applied. Subsequently, the paste is irradiated with light for 10 seconds using a visible light irradiation device for dental polymerization (trade name: Pencure 2000, manufactured by Morita Co., Ltd.) through the release film to obtain a cured product. rice field.

A commercially available dental resin cement (trade name: Panavia (registered trademark) 21, manufactured by Kuraray Noritake Dental Co., Ltd.) was applied to the surface of the cured dental composite resin obtained, and a stainless steel cylindrical rod (diameter 7 mm) was applied. , length 2.5 cm) was adhered to one end surface (circular cross section) to prepare an adhesion test sample. After adhesion, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. A total of 5 test samples for the adhesion test were prepared and allowed to stand in a constant temperature chamber maintained at 37° C. for 24 hours.

The tensile bond strength of the test sample for the bond test was measured with a precision universal tester (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value was taken as the tensile bond strength (MPa). A tensile bond strength of 9.5 MPa or more was considered acceptable.

[Bending strength]
After vacuum degassing the prepared dental composite resin paste of each example and comparative example, it was filled in a stainless steel mold (dimensions 2 mm × 2 mm × 25 mm), and the upper and lower sides were pressed with slide glass. A light irradiator (trade name: Pencure 2000, manufactured by Morita Co., Ltd.) was used to irradiate both sides of the slide glass with light for 10 seconds per point, 5 points on each side, to obtain a cured product. Five cured products were produced for each of the examples and comparative examples, and after removing the cured products from the mold, they were stored in distilled water at 37° C. for 24 hours. Using a precision universal testing machine (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation), the cured product after storage is used as a test sample, under the conditions of a fulcrum distance of 20 mm and a crosshead speed of 1 mm / min. The bending strength was measured, and the average value of the measured values of each sample was calculated as the bending strength (MPa). A bending strength of 100 MPa or more was considered acceptable.

[Ejectability]
After vacuum defoaming of the paste prepared in each example and comparative example, 1.5 ml was filled in a syringe, a needle tip was attached to the tip of the syringe, and the plunger was pushed to eject the paste from the tip of the needle tip. . The ejection force at this time (the force required to extrude the paste from the syringe) was measured using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name "AG-I 100 kN") (n = 5), and the average value was calculated. The syringe was set vertically, and the crosshead equipped with the jig for the compressive strength test was lowered at 4 mm/min to discharge the paste while applying a load, and the maximum load at that time was taken as the discharge force. The ejection force was measured at 25°C. When the ejection force is less than 36N, the ink can be easily ejected and the ejection property is good. That is, the ejection property of the paste was evaluated according to the following evaluation criteria.
⊚: 10 N or less ○: More than 10 N to less than 36 N ×: 36 N or more Note that the pastes of ⊚ or ∘ have ejection properties that allow operators to operate without stress.

As shown in Tables 1 and 2, the self-adhesive dental composite resins (Examples 1 to 21) according to the present invention exhibited good results in terms of surface hardness, ejection property, and paste dripping property. . Also, the difference in the sagging property immediately after preparation and the sagging property after 4 weeks at 60° C. was 2.3 mm or less, showing almost no change. Furthermore, all of them exhibited a tensile bond strength of 9.9 MPa or more to dentin, and a bending strength of 101.5 MPa or more.

As shown in Table 3, the dental composite resins of Comparative Examples 1, 2, and 5, which did not contain the filler (d) having an isoelectric point of 6.0 or higher, had low surface hardness and high sagging. Furthermore, the sagging property changed remarkably after storage for 4 weeks at 60°C. Moreover, in Comparative Examples 3 and 4, in which a large amount of the filler (d) was blended, there was no problem with surface hardness and sagging, but discharge from the container was poor.

The self-adhesive dental composite resin of the present invention can be used by first forming a cavity, directly filling the cavity with the self-adhesive dental composite resin, and subjecting it to photocuring in the treatment of tooth defect or caries. .

Claims (13)

Acidic group-containing (meth)acrylic polymerizable monomer (a), polyfunctional (meth)acrylic polymerizable monomer containing no acidic group (b), photopolymerization initiator (c), isoelectric point A self-adhesive dental composite resin containing a filler (d) having an isoelectric point of 6.0 or more and a filler (e) having an isoelectric point of less than 6.0,
In a self-adhesive dental composite resin paste having a pH equal to or higher than the isoelectric point of the filler (e), the filler (e) is negatively charged and the filler (d) is positively charged,
The filler (d) has an average particle size of 0.001 to 0.5 μm,
The filler (e) is treated with a surface treatment agent and has an average particle size of 0.001 to 50.0 μm, and the surface treatment agent is represented by the following general formula (1)
_CH2 =C( ^R1 )-COO-( _CH2 ) _p -Si- ^R2qR3 ( ³ _-q) ( ₁ )
(wherein R ¹ is a hydrogen atom or a methyl group, R ² is a hydrolyzable group which may have a substituent, and R ³ is a C ₁ to a _C3 alkyl group, p is an integer of 1 to 13, and q is 2 or 3.)
A silane coupling agent (A) represented by and 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 optionally substituted C ₁ -C ₃ alkyl group, and R ⁴ , R ⁵ and R at least one of ⁶ is an optionally substituted C ₁ to C ₃ alkyl group, and each of R ⁷ , R ⁸ and R ⁹ independently has a hydrogen atom or a substituent; and at least one _{of R 7 , R 8 and R 9 is a C 1 -C 3 alkyl} ^{group which may} _{have a} substituent.)
containing an organosilazane (B) represented by
Containing 0.1 to 15 parts by mass of the filler (d) with respect to 100 parts by mass of the total amount of the polymerizable monomer components,
The molar ratio of the silane coupling agent (A) and the organosilazane (B) in the surface treatment of the filler (e) is silane coupling agent (A):organosilazane (B)=1:1 to 1:20. ,
A self-adhesive dental composite resin, wherein the mass ratio of filler (d) to filler (e) is filler (d):filler (e) = 0.05:100 to 15:100. 2. The self-adhesive dental composite resin according to claim 1, wherein said filler (d) has an average particle size of 0.003 to 0.4 μm . R ² is an unsubstituted hydrolyzable group, R ³ is an unsubstituted C ₁ -C ₃ alkyl group, R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an a substituted 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 are each independently a hydrogen atom or an unsubstituted C ₁ to C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is an unsubstituted C ₁ to C ₃ alkyl group; A self-adhesive dental composite resin according to claim 1 or 2. 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 3, 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 4, which is one or more selected from the group consisting of methyldisilazane. In the total amount of 100 parts by mass of the polymerizable monomer components, 1 to 40 parts by mass of the acidic group-containing (meth)acrylic polymerizable monomer (a), and the acidic group-free polyfunctional (meth) Contains 30 to 95 parts by mass of 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 polymerizable monomer components. The self-adhesive dental composite resin according to any one of claims 1 to 5, comprising 0.1 to 10 parts by mass of said filler (d) and 25 to 400 parts by mass of said filler (e). The self-adhesive dental composite resin according to any one of claims 1 to 6, further comprising a polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons. 8. The content of the polyfunctional (meth)acrylamide polymerizable monomer (f) having amide protons is 0.5 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer components. self-adhesive dental composite resin. The self-adhesive dental composite resin according to any one of claims 1 to 8, further comprising a hydrophilic monofunctional polymerizable monomer (g). The hydrophilic monofunctional polymerizable monomer (g) is a hydrophilic monofunctional (meth) acrylate polymerizable monomer and a hydrophilic monofunctional (meth) acrylamide polymerizable monomer. 10. The self-adhesive dental composite resin according to claim 9, which is one or more selected from the group consisting of: In the total amount of 100 parts by weight of the polymerizable monomer component, the content of the hydrophilic monofunctional polymerizable monomer (g) is 1 to 30 parts by weight, self according to claim 9 or 10 Adhesive dental composite resin. The self-adhesive dental composite resin according to any one of claims 1 to 11, wherein the filler (e) is treated with a surface treatment agent and has an average particle size of 0.03 to 20.0 µm. . The self-adhesive dental composite resin according to any one of claims 1 to 12, which is a one-component type.

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