WO2019131881A1

WO2019131881A1 - Self-adhesive dental composite resin

Info

Publication number: WO2019131881A1
Application number: PCT/JP2018/048143
Authority: WO
Inventors: 周明石原; 雄輝大山; 康雄平田; 誉也小柳
Original assignee: クラレノリタケデンタル株式会社
Priority date: 2017-12-27
Filing date: 2018-12-27
Publication date: 2019-07-04
Also published as: JP7183185B2; JPWO2019131881A1

Abstract

The present invention provides a self-adhesive dental composite resin that is dischargeable, permits filling a cavity directly, has excellent mechanical strength after polymerization and curing by visible light irradiation, and resists sagging when used in the oral cavity. The present invention pertains to a self-adhesive dental composite resin that contains (a) an acidic-group-containing (meth)acrylic polymerizable monomer, (b) an acidic-group-free polyfunctional (meth)acrylic polymerizable monomer, (c) a photopolymerization initiator, (d) a filler having an isoelectric point of 6.0 or higher, and (e) a filler having an isoelectric point of less than 6.0, the filler (e) being treated by a surface treatment agent and having an average particle size of 0.001-50.0 μm, the surface treatment agent containing (A) a silane coupling agent of general formula (1) and (B) an organosilazane of general formula (2), and the filler (d) content being 0.1-15 parts by mass per 100 total parts by mass of polymerizable monomer components.

Description

Self-adhesive dental composite resin

The present invention relates to a self-adhesive dental composite resin. More specifically, the present invention relates to a self-adhesive dental composite resin which has a high surface hardness, a good dischargeability from a container, an appropriately suppressed flowability of a paste, and a resistance to dripping when applied to the oral cavity.

In the treatment of dental caries and associated defects, restoration with a dental adhesive and a dental composite resin has been generally performed. In the case of repair treatment, work is performed in the following procedure. First, a cavity is formed by scraping a carious portion, and then a dental adhesive is applied to the cavity, and then the site to which the adhesive is applied is irradiated with visible light to be cured. Next, the dental composite resin is filled on the cured adhesive layer, and the final filled dental composite resin is irradiated with visible light to be cured.

In the above-mentioned restoration method, although two materials of dental adhesive and dental composite resin are used, a self-adhesive dental composite resin in which dental composite resin is made to be adhesive has recently been developed, and dental It has begun to be put to practical use as a material which omits the use of adhesive and reduces the operation steps of repair treatment.

The self-adhesive dental composite resin comprises teeth, in addition to the components of the conventional dental composite resin of a multifunctional polymerizable monomer and filler for imparting mechanical strength, and a polymerization initiator for improving the hardenability In order to impart adhesiveness to the quality, polymerizable monomers having an acidic group conventionally used in dental adhesives are contained as components (for example, Patent Documents 1 and 2).

As a polymerizable monomer mixed in a dental composite resin, (meth) acrylate is generally used. For example, in Patent Documents 1 and 2, imparting of self-adhesiveness and adhesion strength to tooth substance are made. In order to improve the stability, a polymerizable monomer having an acidic group such as a phosphoric acid group or a carboxy group is blended.

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

JP 2008-260752 A JP-A-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 flowability of the paste is increased. The problem was that the paste would drip when

In addition, when the self-adhesive dental composite resin is directly filled into the cavity, it may not be possible to push it out of a container such as a syringe containing the self-adhesive dental composite resin. Self-adhesive dental composite resin is compatible with having the dischargeability that can be filled directly into the cavity from the storage container such as a syringe, while providing the sagging property that the paste does not drip when applied to the oral cavity. It was difficult.

Therefore, the present invention includes visible light as well as conventional dental composite resin, by including a multifunctional polymerizable monomer, a filler, and a polymerization initiator, and containing a specific surface-treated filler. While having sufficient mechanical strength after polymerization and curing by irradiation, the flowability of the paste is appropriately suppressed, it is difficult to sag even when applied to the oral cavity, and it has self-ejecting property that can be directly filled from the storage container into the 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-Based Polymerizable Monomer (a), Acidic-Group-Free Multifunctional (Meth) Acrylic-Based Polymerizable Monomer (b), Photopolymerization Initiator (c), etc. It is 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 less than 6.0,
The filler (e) is treated with a surface treatment agent, and the average particle diameter is 0.001 to 50.0 μm, and the surface treatment agent has the following general formula (1):
_{^{_{_{CH 2 = C (R 1)}}}} -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(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- optionally having a substituent) C ₃ alkyl group, p is an integer of 1 to 13, q is 2 or 3.)
Silane coupling agent (A) represented by the following general formula (2)
R ⁴ R ⁵ R ⁶ -Si-NH-Si-R ⁷ R ⁸ R ⁹ (2)
(Wherein, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group which may have a substituent, R ⁴ , R ⁵ and R 6 ^At least one of ^{6 is} a C ₁ to C ₃ alkyl group which may have a substituent, and R ⁷ , R ⁸ and R ⁹ each independently have a hydrogen atom or a substituent Or C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a C ₁ -C ₃ alkyl group which may have a substituent.
Containing an organosilazane (B) represented by
A self-adhesive dental composite resin comprising 0.1 to 15 parts by mass of the filler (d) based on 100 parts by mass of a total amount of polymerizable monomer components.
[2] The self-adhesive dental composite resin of the above-mentioned [1], wherein the average particle diameter of the filler (d) is 0.001 to 0.5 μm.
[3] R ² is an unsubstituted hydrolyzable group, R ³ is an unsubstituted C ₁ to C ₃ alkyl group, and R ⁴ , R ⁵ and R ⁶ are each independently hydrogen An atom or unsubstituted C ₁ to C ₃ alkyl group, at least one of R ⁴ , R ⁵ , and R ⁶ is an unsubstituted C ₁ to C ₃ alkyl group, R ⁷ , R ⁸ and R ⁹ is 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 The self-adhesive dental composite resin of [1] or [2] above.
[4] The silane coupling agent (A) is selected from 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and The self-adhesive dental composite resin according to any one of the above [1] to [3], which is one or more selected from the group consisting of 6-methacryloyloxyhexyl trimethoxysilane.
[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 the above [1] to [4], which is one or more selected from the group consisting of 3-pentamethyldisilazane.
[6] 1 to 40 parts by mass of the acidic group-containing (meth) acrylic polymerizable monomer (a) in the total amount of 100 parts by mass of the polymerizable monomer component, and a polyfunctional group not containing the acidic group The photopolymerization initiator (c) is contained in an amount of 30 to 95 parts by mass of the (meth) acrylic polymerizable monomer (b) and 0.001 to 100 parts by mass of the total amount of the polymerizable monomer components. The self-adhesive dental composite according to any one of the above [1] to [5], which contains 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 according to any one of the above [1] to [6], further comprising a polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton.
[8] The content of the multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton is 0.5 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component 7] Self-adhesive dental composite resin.
[9] The self-adhesive dental composite resin according to any one of the above [1] to [8], further comprising a hydrophilic monofunctional polymerizable monomer (g).
[10] The hydrophilic monofunctional polymerizable monomer (g) is a hydrophilic monofunctional (meth) acrylate type polymerizable monomer and a hydrophilic monofunctional (meth) acrylamide type polymerizable monomer The self-adhesive dental composite resin of the above-mentioned [9], which is one or more selected from the group consisting of monomers.
[11] The above-mentioned [9] or [9], wherein the content of the hydrophilic monofunctional polymerizable monomer (g) is 1 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component. 10] Self-adhesive dental composite resin.
[12] The self-adhesive dental material according to any one of the above [1] to [11], wherein the filler (e) is treated with a surface treatment agent, and the average particle diameter is 0.03 to 20.0 μm. Composite resin.
[13] The self-adhesive dental composite resin according to any one of the above [1] to [12], which is a one-material type.

According to the present invention, while having sufficient mechanical strength after polymerization and curing by visible light irradiation, the flowability of the paste is appropriately suppressed, it is difficult to droop even when applied to the oral cavity, and from the storage container to the cavity A self-adhesive dental composite resin is provided that has direct-to-fill exhalation properties. Moreover, since it has the characteristics that surface hardness is high, it is excellent in abrasion resistance and abradability, and pigment deposition can be suppressed, it can be used suitably for dental composite resin. Furthermore, the self-adhesive dental composite resin of the present invention also has an effect that the change in paste properties is small during long-term storage.

FIG. 1 is an explanatory view of a reaction mechanism in the case where the organosilazane (B) according to one embodiment of the present invention is 1,1,1,3,3,3-hexamethyldisilazane. FIG. 2: is explanatory drawing regarding the dispersion state of the filler (e) in a paste, a filler (d), and a filler (e).

The self-adhesive dental composite resin of the present invention comprises an acidic group-containing (meth) acrylic polymerizable monomer (a), a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, 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 the average particle diameter is 0.001 to 50.0 μm, and the surface treatment agent has the following general formula (1):
_{^{_{_{CH 2 = C (R 1)}}}} -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(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- optionally having a substituent) C ₃ alkyl group, p is an integer of 1 to 13, q is 2 or 3.)
Silane coupling agent (A) represented by the following general formula (2)
R ⁴ R ⁵ R ⁶ -Si-NH-Si-R ⁷ R ⁸ R ⁹ (2)
(Wherein, R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a C ₁ to C ₃ alkyl group which may have a substituent, R ⁴ , R ⁵ and R 6 ^At least one of ^{6 is} a C ₁ to C ₃ alkyl group which may have a substituent, and R ⁷ , R ⁸ and R ⁹ each independently have a hydrogen atom or a substituent Or C ₁ -C ₃ alkyl group, and at least one of R ⁷ , R ⁸ and R ⁹ is a C ₁ -C ₃ alkyl group which may have a substituent.
And the filler (d) is contained in an amount of 0.1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer component.

In addition, in this specification, the description of "(meth) acryl" is used by the meaning which includes both methacryl and an acryl. In the present specification, the upper limit value and the lower limit value of numerical ranges (the content of each component, the value calculated from each component, each physical property, the numerical value of the symbol of the formula, etc.) can be combined as appropriate.

The self-adhesive dental composite resin of the present invention has sufficient mechanical strength after polymerization and curing by visible light irradiation, the flowability of the paste is appropriately suppressed, and it is difficult to sag even when applied in the oral cavity, The reason why the change in paste properties is small during long-term storage is not clear, but is estimated 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 groups (R ¹ is a hydrogen atom or a methyl group, 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) Have. Since the C ₁ to C ₃ alkyl groups repel each other due to their hydrophobicity, the filler (e) is a repulsion between C ₁ to C ₃ alkyl groups in the self-adhesive dental composite resin. It is hard to aggregate by force, and it maintains separated and non-bonded state. Further, 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 and the polymerizable group It is considered that polymerization is possible, bonding 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 alkyl ~ C ₃ is given by deammoniation organosilazane (B). In the treatment with only a general silane coupling agent (A) known as the prior art, a silanol group (-SiOH) formed by hydrolysis of the alkoxy group of the silane coupling agent (A) and a filler (e) The silanol groups (—SiOH) on the surface of the 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 material (hereinafter, this remaining silanol group Is called “residual silanol group”. On the other hand, in the present invention, as shown in FIG. 1, the residual silanol group (-SiOH) on the surface of the filler (e) or the residual silanol group (-SiOH) derived from the silane coupling agent (A) and the organosilazane The residual silanol group (-SiOH) can be hydrophobized by the deammonia reaction with (B). The residual silanol group (-SiOH) on the surface of the filler (e) or the residual silanol group (-SiOH) derived from the silane coupling agent (A) on the surface of the filler (e) is as small as possible by the treatment (deammoniating reaction) with this organosilazane (B). It is considered possible. Therefore, in the same one material, a proton generated from the acidic group-containing (meth) acrylic polymerizable monomer (a), which is an essential component from the viewpoint of imparting adhesiveness to a self-adhesive dental composite resin It is less likely that hydroxyl groups (-OH) or the like contained in (H ⁺ ) or other polymerizable monomers cause strong interactions with silanol groups (-SiOH) due to hydrogen bonds, and the filler (e ) Is considered to be highly dispersed, and this highly dispersed state provides the paste with high fluidity. While the high fluidity of the paste has the advantage of being easy to pour into the cavity, the paste does not intend to treat the gingiva or dentin other than the filling point until it is filled with the cavity and hardened with a visible light irradiator There was a problem of flowing to the place.

It became clear that the said subject can be solved without impairing the characteristic obtained by the mixing | blending of a filler (e) by containing a filler (d) whose isoelectric point is 6.0 or more. The detailed reason is not clear, but is estimated as follows. The filler (e) has an isoelectric point of less than 6.0, is considered to be negatively charged in a paste having a pH equal to or higher than the isoelectric point of the filler (e), and is dispersed by its zeta potential. On the other hand, in the paste having a pH equal to or higher than the isoelectric point of the filler (e), the filler (d) has a charge opposite to that of the filler (e), ie, positively charged, and the fillers (d) also disperse It is thought that As shown in FIG. 2, when the filler (d) and the filler (e) are simultaneously present in the paste, the filler (d) and the filler (e) form and maintain electrostatically weak association state, As a result, the flowability of the paste is appropriately suppressed, the dripping property of the paste is improved, the change of the paste property is small during long-term storage, and the dischargeability can be directly filled from the storage container into the cavity it is conceivable that. Moreover, as an unexpected effect, it was found that the surface hardness is improved by the blending of the filler (d). Although the detailed reason is not clear, the filler (d) and the filler (e) form an electrostatic association state, and the packing density per unit volume of paste is improved by being in a close packing state. As a result, it is possible that the surface hardness 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 more used in the present invention will be described. In the present invention, the isoelectric point of the filler indicates the pH when the zeta potential of the particles in the aqueous dispersion is 0 mV. The zeta potential refers to a value measured by laser Doppler velocimetry. Generally, when the particles are charged, the particles move towards the electrode when an electric field is applied to the aqueous dispersion. The moving speed of the particles is proportional to the charge amount of the particles. 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 acid or alkali is added to the aqueous dispersion to track the zeta potential while changing the pH continuously, and the obtained measurement data is obtained by plotting the X axis as the pH and the Y axis as the zeta potential. By drawing a line in consideration of the above plot, the pH at which the zeta potential becomes 0 mV can be calculated, and the pH becomes the isoelectric point of the particles.

As the filler (d) in the present invention, as long as the isoelectric point is 6.0 or more, conventionally known materials can be used without any limitation, but metals such as alumina, zirconia, titania, zinc oxide and nickel oxide Composite metal oxides such as oxides, alumina-zirconia, alumina-titania, zirconia-titania and the like can be mentioned. Among them, alumina, zirconia and titania are more preferable, alumina and zirconia are more preferable, and alumina is most preferable. One of these may be used alone, or two or more may be used in combination.

The average particle size of the filler (d) is preferably 0.001 to 0.5 μm, more preferably 0.003 to 0.4 μm, and still more preferably 0.005 to 0.3 μm. Within these ranges, the dischargeability from the container is excellent, the flowability is appropriate, the liquid is less likely to sag, and during storage over a long period of time, the change in paste properties is small and the surface hardness is also excellent. In the present specification, the average particle size of the filler means the average particle size (average primary particle size) of the primary particles of the filler.

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

The content of the filler (d) is at least 0.1 parts by mass with respect to 100 parts by mass of the polymerizable monomer component from the viewpoint of being excellent in appropriate fluidity, sag and surface hardness. It is necessary and preferably 0.2 parts by mass or more, and more preferably 0.3 parts by mass or more from the viewpoint of paste properties such as appropriate fluidity and sag of the self-adhesive dental composite resin. Also, from the viewpoint of not impairing the operability of the paste, such as the adhesive strength of the self-adhesive dental composite resin and the dischargeability from the container, the amount is 15 parts by mass or less based on 100 parts by mass of the total polymerizable monomer component. It is necessary that the amount is 10 parts by mass or less, more preferably 8 parts by mass or less. 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 component. 0.3 to 8 parts by mass is more preferable.

The filler (d) is preferably treated with a surface treatment agent. The 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 using two or more kinds of organic metal compounds, it may be a surface treatment layer of a mixture of two or more kinds of organic metal compounds, or as a surface treatment layer of a multilayer structure in which two or more kinds of organic metal compound layers are laminated. Good.

Examples of the organosilicon compounds include compounds represented by (W) _n SiY _4-n (wherein W is a C ₁ to C ₁₂ substituted or unsubstituted hydrocarbon group, and Y is C an alkoxy group having _{1 ~} C _4, a hydroxyl group, a halogen atom or a hydrogen atom, n is respectively when there are a plurality of .W and Y is 0, 1, 2 or 3, may be the same or different ).

Specifically, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, and vinyltrimethylsilane. 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- Tacryloyloxypropylmethyldimethoxysilane, γ-methacroyloxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrit Methoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, vinyltrichlorosilane, trimethyl Lomosilane, diethylsilane, vinyltriacetoxysilane, ω- (meth) acryloyloxyalkyltrimethoxysilane (number of carbons between (meth) acryloyloxy group and silicon atom: 3 to 12, eg, 3-methacryloyloxypropyl tri) Methoxysilane, etc.), ω- (Meth) acryloyloxyalkyltriethoxysilane (the carbon number between (meth) acryloyloxy group and silicon atom: 3 to 12, eg, 3-methacryloyloxypropyltriethoxysilane, etc.), etc. Can be mentioned.

Among them, a coupling agent having a functional group copolymerizable with the polymerizable monomer component, such as ω- (meth) acryloyloxyalkyltrimethoxysilane (a carbon between a (meth) acryloyloxy group and a silicon atom Number: 3 to 12), ω- (meth) acryloyloxyalkyltriethoxysilane (number of carbons 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, tetra (2-ethylhexyl) titanate and the like.

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

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

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

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 on the surface thereof — (CH ₂ ) _p —OOC—C (R ¹ ) = CH ₂ and a C ₁ to C ₃ alkyl group. The C ₁ -C ₃ alkyl groups repel each other due to their hydrophobicity. Accordingly, the filler (e) of the present invention is difficult to be aggregated even in the self-adhesive dental composite resin due to the repulsive force of the C ₁ to C ₃ alkyl groups, and is not easily aggregated 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 diameter of 0.001 to 50.0 μm, and the surface treatment agent has a general formula (1) As long as it contains the silane coupling agent (A) represented by 1.) and the organosilazane (B) represented by the general formula (2), the known filler used for the dental composite resin is not limited. used. As the filler (e) before being treated with the surface treatment agent, various kinds of glasses [oxides such as heavy metals, boron, aluminum and the like in the range which contains silica as a main component and has an isoelectric point less than 6.0] contains. For example, glass powder of a 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, fluoroaluminosilicate glass, etc., composite oxides such as silica-titania and silica-zirconia, calcium fluoride having a core-shell structure surface-coated with silica, silica Fluoride-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium fluoride, silica surface-coated core-shell structure calcium phosphate, silica surface-coated core-shell structure sulfuric acid Barrio , Zirconium dioxide core-shell structure having a surface coated with silica, titanium dioxide coated core-shell structure of the surface with silica, hydroxyapatite coated core-shell structure of the surface silica and the like. Among these, various glasses such as various silicas, complex oxides such as silica-titania and silica-zirconia, and silicas, from the viewpoint of being able to react efficiently with the silane coupling agent (A) or organosilazane (B) -Coated core-shell structure calcium fluoride, silica surface-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium-fluoride, silica surface-coated core-shell structure calcium phosphate , Barium sulfate of core-shell structure coated with silica, zirconium dioxide of core-shell structure coated with silica, titanium dioxide of core-shell structure coated with silica, core-shell structure of silica coated surface Hydroxyapatite Siri Ytterbium fluoride of core-shell structure coated surface in, yttrium fluoride of the core-shell structure coated with silica are preferred. One of these may be used alone, or two or more may be used in combination.

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 can be obtained, no stickiness occurs in the paste, no problem occurs in operability, and the abrasion resistance or lubricity durability of the cured product is excellent.

In addition, since the filler (e) used in the present invention is hard to aggregate, it can be easily washed with water. For this reason, the filler (e) used in the present invention is an acid-base reaction with an acidic group-containing (meth) acrylic polymerizable monomer (a), and a content of an ionic impurity such as an alkali metal to be chelated. Can be reduced.

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

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

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

As a method of surface treatment of the filler (e), a method of bonding the silane coupling agent (A) represented by the general formula (1) to the surface of the filler (e) by a dehydration polycondensation reaction, and a general formula (2) The method is not particularly limited as long as it is a method of bonding the organosilazane (B) represented by (IV) to the surface of the filler (e) by a deammonia reaction. For example, a method of spraying a solution obtained by diluting each surface treatment agent with a solvent while stirring the filler (e) in a mixing tank, heating and drying in the tank for a fixed time while continuing the stirring; filler (e) and surface treatment The agent is stirred and mixed in a solvent and then heated and dried. The solvent is not particularly limited, and examples thereof include alcohol 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 the general formula (1), R ¹ is a hydrogen atom or a methyl group. R ² is a hydrolyzable group which may have a substituent. R ³ is a C ₁ to C ₃ alkyl group which may have a substituent. p is an integer of 1 to 13, preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. q is 2 or 3, preferably 3.

The hydrolyzable group which may have a substituent of R ² is not particularly limited, and examples of the hydrolyzable group include, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n- A C ₁ to C ₆ linear or branched alkoxy group such as butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, isohexyloxy group; A chlorine atom or an isocyanate group is mentioned. Considering hydrolyzability, the alkoxy group as a hydrolyzable group is a C ₁ to C ₄ linear alkoxy group, which is any of a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group. Is more preferable, and a C ₁ to C ₃ linear alkoxy group is more preferable. The hydrolyzable group of R ² 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, R ³ Is preferably a substituted 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 a straight-chain or branched alkoxy group having ~ C _4, p is 2 to 8, more preferable q is 3, R ¹ is a methyl group, C ₁ ~ of R ² is unsubstituted More preferably, it is a C ₃ linear or branched alkoxy group, p is 2 to 6 and q is 3.

Examples of the C ₁ to C ₃ alkyl group which may have a substituent of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include, for example, methyl group, ethyl group, n And -propyl and isopropyl. The alkyl group of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ may be each independently unsubstituted. The alkyl group of ^{^{^{^{R 4, R 5, R 6}}}} , R 7, R 8 and ^{R 9,} methyl group, ethyl group, and more preferably methyl group. R ^4, ^{R 5,} and at least one of ^{R 6} is an alkyl group ~ _{C 3} _C 1 may have a substituent group, these two are good _C 1 ~ optionally having substituent may be an alkyl group of C _3, all three may be an alkyl group _~ C ₃ C ₁ may have a substituent group. At least one of R ⁷ , R ⁸ and R ⁹ is an optionally substituted C ₁ to C ₃ alkyl group, and two of these may be substituted C ₁ to C _It may be ₃ alkyl groups, or all 3 may be C ₁ to C ₃ alkyl groups which may have a substituent.

Examples of the substituent of the hydrolyzable group of R ² and the alkyl group of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ include, for example, a halogen atom (a fluorine atom, a chlorine atom, bromine atom, iodine atom), a carboxy group, hydroxy group, amino group, C 1 _~ C ₆ alkyl mono- or di-substituted amino group, acyl, 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 to 5. The number of substituents of the alkyl group of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ is one, two or three.

Specific examples of the silane coupling agent (A) represented by the 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) acryloyloxy Ndecyltrimethoxysilane, 11- (meth) acryloyloxyundecyldichloromethylsilane, 11- (meth) acryloyloxyundecyltrichlorosilane, 11- (meth) acryloyloxyundecyldimethoxymethylsilane, 12- (meth) acryloyloxy Examples include oxydodecyltrimethoxysilane, 13- (meth) acryloyloxytridecyltrimethoxysilane and the like. One of these may be used alone, or two or more of these may be used in combination as appropriate. Among these, when the alkylene group represented by-(CH ₂ ) _p- is moderately long, it is well compatible with the polymerizable monomer in the self-adhesive dental composite resin, and as a self-adhesive dental composite resin From the point that the content of the filler (e) contained can be sufficiently increased, and if the alkylene group represented by-(CH ₂ ) _p- is appropriately short, the hydrophobicity will not be too strong and the adhesion strength will increase. 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and 6-methacryloyloxyhexyltrimethoxysilane are preferred, Methacryloyloxypropyl trimethoxysilane is more preferred .

As organosilazane (B) represented by General formula (2), the hydroxyl group which exists on the surface of a filler (e), and the hydroxyl group derived from the silane coupling agent (A) represented by General formula (1) Any one may be used as long as it bonds by a deammonia reaction, but it is preferable to use one having a small molecular weight. 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., and 1,1,3,3-tetramethyl Disilazane, 1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3-pentamethyldisilazane and the like are preferable.

The treatment amount of the filler (e) with the silane coupling agent (A) represented by the general formula (1) is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the filler (e) before surface treatment 1 to 10 parts by mass is more preferable, and 2 to 8 parts by mass is particularly preferable. If the amount is less than 0.5 parts by mass, a sufficient polymerizable group can not be provided on the surface of the filler (e), and the mechanical strength may be reduced.

The molar ratio of the silane coupling agent (A) to the organosilazane (B) in the surface treatment of the filler (e) is: silane coupling agent (A): organosilazane (B) = 1: 1 to 1:20 Is preferable, and 1: 2 to 1:10 is more preferable. If the amount of organosilazane (B) is smaller than that of the silane coupling agent (A), aggregation may proceed in the paste and the transparency during the storage period may not be ensured, and the silane represented by formula (1) If the organosilazane (B) represented by the general formula (2) exceeds 20 moles relative to 1 mole of the coupling agent (A), the hydrophobicity may be so strong that sufficient adhesive strength may not be obtained. is there.

In addition, in surface treatment, in order to suppress superposition | polymerization of the silane coupling agent (A) represented by General formula (1), you may add a polymerization inhibitor. As the polymerization inhibitor, known ones such as 3,5-dibutyl-4-hydroxytoluene (BHT) and p-methoxyphenol (methquinone) 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 preferred. 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. It means that it is less than 0.1% by mass, more preferably.

Furthermore, what solidified the filler (e) after surface treatment as a filler (e) is preferable. Solidification is a step of precipitating the surface-treated filler (e) with a mineral acid, and washing the precipitate with water and / or dehydrating (eg, drying) to obtain a solid of the filler (e). As described above, the conventional filler surface-treated only with the silane coupling agent (A) represented by the general formula (1) is very susceptible to aggregation, so once solidified it is highly dispersed again Have difficulty. However, since the filler (e) of the present invention is difficult to aggregate, it is difficult to aggregate even if it is solidified, and it is easy to redisperse even if it is aggregated. As described above, by washing the filler (e) with water, it is possible to easily produce the filler (e) containing few ionic impurities such as alkali metals. By using the filler (e) containing few ionic impurities, it is possible to maintain the repulsive force between the above-mentioned alkyl groups for a longer time, maintain the high transparency of the paste for a longer time, and to carry out the acidic group-containing (meth) acrylic polymerization. (H ⁺ ) generated from the anionic monomer (a) or hydroxyl groups (-OH) contained in other polymerizable monomers or the like, or interaction with very small residual silanol groups and ionic impurities Possibilities can be further reduced, and changes in the transparency and properties of the paste can be further suppressed. In the washing step, washing is preferably repeated until the electric conductivity of the extracted water of the filler (e) (for example, water soaked with the filler (e) for 24 hours at 121 ° C.) becomes 50 μS / cm or less. .

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

Washing with the mineral acid aqueous solution can also be performed multiple times. It is preferable to stir after washing | cleaning by mineral acid aqueous solution immersing a filler (e) in mineral acid aqueous solution. In addition, in the immersed state, it may be left for about 1 to 24 hours, or for about 72 hours. Stirring may or may not be continued upon standing. When washing in a mineral acid aqueous solution, heating can also be performed at or above normal temperature. 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 a mass basis). For example, it is ion exchange water, distilled water, pure water or the like. The washing with water may be carried out by dispersing and suspending the filler (e) in the same manner as washing with an aqueous solution of mineral acid, followed by filtration, and water is continuously passed through the collected filler (e). May be The end time of washing with water may be judged by the electric conductivity of the above-mentioned extracted water, or it may be a time when the alkali metal concentration in the waste water after washing the filler (e) becomes 1 ppm or less. The point may be when the alkali metal concentration of the extracted water is 5 ppm or less. In addition, when wash | cleaning with water, it can also heat above normal temperature.

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

As a method of dewatering the filler (e) other than drying, an aqueous organic solvent having a boiling point higher than that of water is added to the water-containing filler (e), and then a mixed material soluble in the aqueous organic solvent is mixed And a method of removing water can be used. As an 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) is a polymerizable monomer because it has sufficient mechanical strength after polymerization and curing by visible light irradiation and is excellent in property stability of the paste during storage over a long period before polymerization and curing. 25 parts by mass or more is preferable, 50 parts by mass or more is more preferable, and 100 parts by mass or more is more preferable from the viewpoint that the self-adhesive dental composite resin has higher mechanical strength with respect to 100 parts by mass of the total amount of components . Also, from the viewpoint of not impairing the adhesive strength and consistency of the self-adhesive dental composite resin, such as paste strength, 400 parts by mass or less is preferable and 100 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 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 100 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer. More preferable. The filler (d) and the filler (e) form an electrostatic association state, and the mass ratio of the filler (d) to the filler (e) is excellent because the paste is more excellent in properties such as sag, surface hardness, and dischargeability. The filler (d): filler (e) is preferably 0.05 to 15: 100, more preferably 0.1 to 10: 100, and still more preferably 0.5 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 the self-adhesive dental composite resin of the present invention to exhibit adhesiveness. The acidic group-containing (meth) acrylic polymerizable monomer (a) has an action of decalcifying dentin. The acidic group-containing (meth) acrylic polymerizable monomer (a) has at least one acidic group such as phosphoric acid group, phosphonic acid group, pyrophosphoric acid group, carboxylic acid group and sulfonic acid group, and acryloyl group It is a polymerizable monomer having at least one polymerizable group such as a group, a methacryloyl group, an acrylamide group and a methacrylamide group. From the viewpoint of adhesion to 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 preferred to be monofunctional. Specific examples include the following.

Examples of the phosphoric acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acryloyloxyethyl hydrogen phosphate, 3- (meth) acryloyl oxypropyl hydrogen phosphate, 4- (meth) acryloyloxy Butyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyl oxyhexyl dihydrophosphate, 7- (meth) acryloyloxyheptyl dihydrophosphate, 8- (meth) acryloyloxyoctyl dihydro Gen phosphate, 9- (meth) acryloyl oxynonyl dihydrophosphate, 10- (meth) acryloyl oxydecyl dihydrophosphate, 11- (meth) a 2- (meth) acryloyloxy dodecyl dihydrophosphate, 16- (meth) acryloyl oxyhexadecyl dihydrophosphate, 20- (meth) acryloyl oxyeicosyl dihydrophosphate, 2- ( Meta) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyl oxyethyl 2-bromoethyl hydrogen phosphate, 2- (meth) acryloyl oxyethyl- (4-methoxyphenyl) hydrogen phosphate, 2- (meth) ) Phosphoric acid group-containing monofunctional (meth) acrylate compounds such as acryloyloxypropyl- (4-methoxyphenyl) hydrogen phosphate, acid chlorides thereof, alkali Metal salts, ammonium salts and amine salts; bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis [4- (meth) acryloyloxybutyl] hydrogen phosphate, bis [6- (meth) acryloyloxyhexyl Hydrogen phosphate, bis [8- (meth) acryloyloxyoctyl] hydrogen phosphate, bis [9- (meth) acryloyl oxynonyl] hydrogen phosphate, bis [10- (meth) acryloyl oxydecyl] hydrogen phosphate, Examples thereof include phosphoric acid group-containing difunctional (meth) acrylate compounds such as 1,3-di (meth) acryloyloxypropyl hydrogenogen phosphate, acid chlorides thereof, alkali metal salts, ammonium salts, amine salts and the like.

Examples of the phosphonic acid group-containing (meth) acrylic polymerizable monomer include 2- (meth) acryloyloxyethyl phenyl phosphonate, 5- (meth) acryloyl oxypentyl 3-phosphonopropionate, 6- ( Meta) acryloyloxyhexyl 3-phosphonopropionate, 10- (meth) acryloyloxydecyl-3-phosphonopropionate, 6- (meth) acryloyloxyhexyl phosphonoacetate, 10- (meth) acryloyloxy And decyl phosphono acetate, acid chlorides, alkali metal salts, ammonium salts, and amine salts of these.

As the pyrophosphate group-containing (meth) acrylic polymerizable monomer, for example, bis [2- (meth) acryloyloxyethyl] pyrophosphate, bis [4- (meth) acryloyloxybutyl] pyrophosphate, bis pyrophosphate [6- (Meth) acryloyloxyhexyl], bis [8- (meth) acryloyloxyoctyl] pyrophosphate, bis [10- (meth) acryloyloxydecyl] pyrophosphate, acid chlorides thereof, alkali metal salts, ammonium And salts and amine salts.

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

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

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

The acidic group-containing (meth) acrylic polymerizable monomer (a) may be used singly 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 effects of the present invention are exhibited, but the total content of the polymerizable monomer component is higher in terms of higher adhesive strength. In 100 parts by mass, the range of 1 to 40 parts by mass is preferable, the range of 2 to 20 parts by mass is more preferable, the range of 3 to 20 parts by mass is more preferable, and the range of 4 to 20 parts by mass is most preferable. In the present specification, the content of a certain polymerizable monomer in 100 parts by mass of the total amount of the polymerizable monomer component refers to the case where 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 the respective polymerizable monomer components does not exceed 100 parts by mass.

Then, the polyfunctional (meth) acrylic-type polymerizable monomer (b) which does not contain the acidic group used by this invention is demonstrated. The polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group has no acidic group in the molecule and 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-based difunctional polymerizable monomers, aliphatic compound-based difunctional polymerizable monomers, trifunctional or higher polymerizable monomers, and the like.

Examples of the aromatic compound-based difunctional polymerizable monomer include, for example, 2,2-bis ((meth) acryloyloxyphenyl) propane and 2,2-bis [4- (3- (meth) acryloyloxy- 2-Hydroxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane (average of ethoxy groups) With an addition number of moles of 2.6), 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) acrylic acid Iyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth)) Acryloyloxyethoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxy Phenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxy) Difunctional (meta) such as isopropoxyphenyl) propane Acrylate compounds, and the like.

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

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

Among the above-mentioned polyfunctional (meth) acrylic polymerizable monomers (b) not containing an acidic group, in view of mechanical strength or handleability, bifunctional polymerizable monomers of aromatic compound type, and fats Preferably, a difunctional polymerizable monomer of a group compound type is used. As a bifunctional polymerizable monomer based on an aromatic compound, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (generally called “Bis-GMA”), and 2, 2-Bis (4-methacryloyloxypolyethoxyphenyl) propane (having an average addition mole number of ethoxy groups of 2.6, commonly called "D-2.6E") is preferred. Examples of aliphatic compound difunctional polymerizable monomers include glycerol di (meth) acrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate (generally called “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 called "UDMA") is preferred.

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

The polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group may be used alone or in combination of two or more. The content of the polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group is not particularly limited as long as the effects of the present invention are exhibited, but the dental composition (self-adhesive dental composite resin) 30 to 95 parts by mass in 100 parts by mass of the polymerizable monomer component in the self-adhesive dental composite resin from the viewpoint of having high permeability to the tooth material and excellent adhesion and having sufficient strength The range of 40 to 90 parts by mass is more preferable, the range of 50 to 85 parts by mass is more preferable, and the range of 60 to 80 parts by mass is most preferable.

The self-adhesive dental composite resin of the present invention may further contain a multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton as a polymerizable monomer component. The multifunctional (meth) acrylamide polymerizable monomer (f) having at least one or more amide protons has high hydrophilicity since it has at least one or more amide protons, and penetrates into the collagen layer of dentin And because it has multiple polymerizable groups in the molecule, together with the other components of the self-adhesive dental composite resin, it exhibits a very high degree of hardenability, resulting in higher adhesion to dentin. can get.

As a polyfunctional (meth) acrylamide polymerizable monomer (f), a table with a multifunctional (meth) acrylamide polymerizable monomer (f1) represented by the following general formula (3), and the following general formula (4) Examples thereof include polyfunctional (meth) acrylamide polymerizable monomers (f2) and polyfunctional (meth) acrylamide polymerizable monomers (f3) represented by the following general formula (5).

(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, and X ¹ and X ² are each independently a substitution A C ₁ to C ₈ linear or branched alkylene group which may have a group))

(Wherein, R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a methyl group, t is 2 or 3, and X ³ and X ⁴ each independently have a substituent) (C ₁ to C ₈ linear or branched alkylene group)

(Wherein, Z is a C ₁ to C ₈ linear or branched aliphatic group or aromatic group which may have a substituent, and the aliphatic group is —O—, —S, ^{-, - CO -, - CO} -O -, - O-CO -, - NR 15 -, - CONR 15 -, - NR 15 -CO -, - CO-O-NR 15 -, - O-CONR R ¹⁵ may be interrupted by at least one bonding group selected from the group consisting of ¹⁵ — and —NR ¹⁵ —CO—NR ¹⁵ — R ¹⁵ may be a hydrogen atom or a C ₁ optionally having a substituent. It represents a linear or branched chain aliphatic group of ~ C _8.)

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms from the viewpoint of adhesion to dentin and polymerization curing. s is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. It is preferable that t is three.

Examples of the C ₁ to C ₈ linear or branched alkylene group which may have a substituent of X ¹ , X ² , X ³ and X ⁴ include, for example, a methylene group, a methyl methylene 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, 1,2,2-trimethylethylene, 1-ethyltrimethylene, 2-ethyltrimethylene, 3-ethyltrime Tylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1- Methyltetramethylene, 2-methyltetramethylene, 3-methyltetramethylene, 4-methyltetramethylene, pentamethylene, 1-butylethylene, 2-butylethylene, 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 Group, 3-methyl-pentamethylene group, 4-methyl-pentamethylene group, 5-methyl-pentamethylene group, hexamethylene group and the like.

As a substituent of X ¹ , X ² , X ³ and X ⁴ , for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a carboxy group, a hydroxy group, an amino group, C ₁ to C ₈ Alkyl group mono- or di-substituted amino group, acyl group, acyloxy group, amide group, C ₂ -C ₈ alkoxycarbonyl group, C ₁ -C ₈ alkoxy group, C ₁ -C ₈ alkylthio group, C ₁ -C ₈ alkyl groups and the like are preferable, and halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), C ₁ to C ₈ alkyl groups and the like are more preferable. 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 Groups, 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 to C ₄ alkyl group. The number of substituents is not particularly limited, and may be about 1 to 8, preferably one, two or three.

The C ₁ to C ₈ aliphatic group which may have a substituent represented by Z is a saturated aliphatic group (alkylene group, cycloalkylene group (eg, 1,4-cyclohexylene group etc.)) Or unsaturated aliphatic group (an alkenylene group, an alkynylene group) may be any, and a saturated aliphatic group (alkylene group) is preferable from the viewpoint of easy availability or production and chemical stability. Z is preferably a linear or branched C ₁ to C ₄ aliphatic group which may have a substituent, from the viewpoint of adhesiveness to dentin and polymerization curing property, and Z has a substituent It is more preferable that it is a linear or branched C ₂ -C ₄ aliphatic group which may be substituted. Examples of the C ₁ to C ₈ alkylene group include the same as X ¹ , X ² , X ³ and X ⁴ .

As an aromatic group which may have a substituent represented by Z, an aryl group and an aromatic heterocyclic group are mentioned, for example. As the aromatic group, an aryl group is preferable to an aromatic heterocyclic group. The heterocycle of the aromatic heterocycle group is generally unsaturated. The aromatic heterocycle is preferably a 5- or 6-membered ring. As an aryl group, a phenyl group is preferable, for example. As the aromatic heterocyclic group, for example, furan group, thiophene group, pyrrole group, oxazole group, isoxazole group, thiazole group, isothiazole group, imidazole group, pyrazole group, frazane group, triazole group, pyran group, pyridine Groups, pyridazine groups, pyrimidine groups, pyrazine groups, and 1,3,5-triazine groups. Among the above-mentioned aromatic groups, a phenyl group is particularly preferred.

The aliphatic group in R ¹⁵ may be any of a saturated aliphatic group (alkyl group) and an unsaturated aliphatic group (alkenyl group, alkynyl group), and is easy to obtain or manufacture and has chemical stability. From the point of view, saturated aliphatic groups (alkyl groups) are preferred. Examples of the alkyl group include C ₁ to C ₈ alkyl groups similar to those described as the substituents for X ¹ , X ² , X ³ , and X ⁴ . R ¹⁵ is more preferably a hydrogen atom or a linear or branched C ₁ to C ₄ alkyl group which may have a substituent, and a hydrogen atom or a linear or branched group which may have a substituent More preferred are C ₁ -C ₃ alkyl groups in the chain.

The aliphatic groups of Z may be interrupted by at least one linking group as described 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 one, two or three. And more preferably one or two. In the above formula (5), it is preferable that the aliphatic group of Z is not interrupted by the continuous bonding group. That is, it is preferable that the bonding groups are not adjacent to each other. As a bonding group, -O-, -S-, -CO-, -CO-O-, -O-CO-, -NH-, -CO-NH-, -NH-CO-, -CO-O- More preferably, at least one linking group selected from the group consisting of NH-, -O-CO-NH- and -NH-CO-NH-, -O-, -S-, -CO-, -NH-, More preferred is at least one linking group selected from the group consisting of -CO-NH- and -NH-CO-.

Although it does not specifically limit as a specific example of the polyfunctional (meth) acrylamide polymerizable monomer (f1) represented by said Formula (3), What is shown below is mentioned.

Among them, the compound (f1-1), the compound (f1-3), the compound (f1-5) and the compound (f1-7) are preferable from the viewpoints of the adhesiveness to the tooth substance and the polymerization curing property, and the compound (f1-) 1) The compound (f1-5) is more preferable, and the compound (f1-5) is most preferable from the viewpoint of hydrophilicity involved in penetration of dentin into the collagen layer.

Although it does not specifically limit as a specific example of the polyfunctional (meth) acrylamide polymerizable monomer (f2) represented by said Formula (4), What is shown below is mentioned.

Among them, the compound (f2-1), the compound (f2-3), the compound (f2-5) and the compound (f2-7) are preferable from the viewpoint of adhesion to dentin and polymerization curing property, and the compound (f2-2) is preferable. 1) The compound (f2-3) is more preferable, and the compound (f2-1) is most preferable from the viewpoint of the hydrophilicity involved in the penetration of dentin into the collagen layer.

Specific Examples of the Multifunctional (Meth) Acrylamide Polymerizable Monomer (f3) Represented by the Above Formula (5) (Hereinafter, Also Referred to as Asymmetric Multifunctional (Meth) Acrylamide Polymerizable Monomer (f3)) Although it does not specifically limit as this, The thing shown below is mentioned.

Among them, N-methacryloyloxyethyl acrylamide, N-methacryloyloxypropyl acrylamide, N-methacryloyloxybutyl acrylamide, N- (1-ethyl- (2-methacryloyloxy), from the viewpoint of adhesion to teeth and polymerization curing. Ethyl) acrylamide, N- (2- (2-methacryloyloxyethoxy) ethyl) acrylamide is more preferable, and N-methacryloyloxyethyl acrylamide, N- from the viewpoint of hydrophilicity involved in penetration of dentin into collagen layer. Most preferred is methacryloyloxypropyl acrylamide.

As the polyfunctional (meth) acrylamide polymerizable monomer (f) having at least one or more amide protons, one type may be used alone, or two or more types may be used in combination. For example, a group comprising a polyfunctional (meth) acrylamide polymerizable monomer (f3), 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 effects of the present invention are exhibited, but the content is 0.5 to 5 parts by mass in 100 parts by mass of the polymerizable monomer component. The range of 30 parts by mass is preferable, the range of 2 to 25 parts by mass is more preferable, the range of 2.5 to 28 parts by mass is more preferable, and the range of 3 to 20 parts by mass is most preferable.

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) has a solubility in water at 25 ° C. of 5% by mass or more and is monofunctional polymerizable other than the above (a), the above (b) and the above (f) It means a monomer, the one having the same solubility of 10% by mass or more is preferable, and the one having the same solubility of 15% by mass or more is more preferable. 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 or more hydrophilic groups such as a hydroxyl group, an oxymethylene group, an oxyethylene group, an oxyproprene group, and an amide group. As a hydrophilic monofunctional polymerizable monomer (g), 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl Hydrophilic monofunctional (meth) acrylate type polymerizable monomer such as (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-trimethylammonium ethyl (meth) acrylic 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) Acry Hydrophilic monofunctional (such as yl morpholine, N-trihydroxymethyl-N-methyl (meth) acrylamide, and a monofunctional (meth) acrylamide type polymerizable monomer represented by the following general formula (6) A meta) acrylamide type | system | group polymerizable monomer is mentioned.

(Wherein, R ¹⁶ and R ¹⁷ are each independently a linear or branched C ₁ to C ₃ alkyl group which may have a substituent, and R ¹⁸ is a hydrogen atom or a methyl group. is there.)

Examples of the substituent in R ¹⁶ and R ¹⁷ include the same as the substituents in X ¹ , X ² , X ³ and X ⁴ . Examples of the C ₁ to C ₃ alkyl group for R ¹⁶ and R ¹⁷ include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.

Among these hydrophilic monofunctional polymerizable monomers (g), 2-hydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate and diacetone (meth ) Monofunctional (meth) acrylamide-based polymerizable monomers represented by acrylamide and general formula (6) are preferable, and monofunctional (meth) acrylamide-based polymerizable monomers represented by 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 type polymerizable monomers represented by the general formula (6), N, N-dimethyl acrylamide and N, N-diethyl acrylamide 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 effects of the present invention are exhibited, but from the viewpoint of showing a sufficient adhesive strength improvement effect and mechanical strength, self The total amount of 100 parts by mass of the polymerizable monomer component in the adhesive dental composite resin 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 in the range of 5 to 25 parts by mass More preferably, the range of 7 to 20 parts by mass is particularly preferable.

The self-adhesive dental composite resin of the present invention has an acidic group-containing (meth) acrylic polymer within a range that does not impair the effects of the present invention for the purpose of improving adhesion, handleability, mechanical strength, etc. Monomer (a), Multifunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, Multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton, hydrophilic A polymerizable monomer (j) other than the monofunctional polymerizable monomer (g) may be blended. Examples of the polymerizable monomer (j) include hydrophilic polyfunctional (meth) acrylate type polymerizable monomers (j1) and / or symmetrical (meth) acrylamide compounds (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 not limited to (a), (b), and (f). It means a functional polymerizable monomer, preferably having a solubility of 10% by mass or more, and more preferably one having a solubility of 15% by mass or more. As a hydrophilic polyfunctional (meth) acrylate type polymerizable monomer (j1), for example, pentaerythritol di (meth) acrylate, erythritol di (meth) acrylate, mannitol di (meth) acrylate, xylitol di (meth) Acrylate, sorbitol di (meth) acrylate and the like. Examples of the symmetrical (meth) acrylamide compound (j2) include N, N'-ethylenebisacrylamide, N, N'-diethyl-1,3-propylenebisacrylamide and the like. As the polymerizable monomer (j), one type may be used alone, or two or more types may be used in combination.

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 with respect to the entire self-adhesive dental composite resin, and 44.5 mass. Less than% is more preferable, and less than 40.0% by mass is more preferable. Moreover, 9.0 mass% or more is preferable with respect to the whole self-adhesive dental composite resin, as for content of the sum total of a polymerizable monomer, 14.0 mass% or more is more preferable, and 19.0 mass%. The above is more preferable.

The photopolymerization initiator (c) in the present invention is a component that accelerates the polymerization and curing of the self-adhesive dental composite resin. The photopolymerization initiator (c) can be selected from known photopolymerization initiators, and among them, the photopolymerization initiator used for dental use is preferably used. The photopolymerization initiator (c) may be used alone or in combination of two or more.

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

Among these photopolymerization initiators (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 is excellent in photo-curing properties in the visible and near-ultraviolet regions and exhibits sufficient photo-curing properties using any light source of halogen lamp, light emitting diode (LED) and xenon lamp. can get.

Examples of the acyl phosphine oxides include 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, 2,6-dimethoxy benzoyl diphenyl phosphine oxide, 2,6-dichloro benzoyl diphenyl phosphine oxide, 2,4,6-trimethyl benzoyl Examples thereof include methoxyphenyl phosphine oxide, 2,4,6-trimethyl benzoyl ethoxy phenyl phosphine oxide, 2,3,5,6- tetramethyl benzoyl diphenyl phosphine oxide, benzoyl di- (2,6-dimethylphenyl) phosphonate and the like. Among these, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide is preferable.

Examples of the bisacyl phosphine oxides include bis (2,6-dichlorobenzoyl) phenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenyl phosphine oxide, and bis (2,6-dichloro). Benzoyl) -4-propylphenyl phosphine oxide, bis (2,6-dichlorobenzoyl) -1-naphthyl phosphine oxide, bis (2,6-dimethoxybenzoyl) phenyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4,4-trimethylpentyl phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,5-dimethylphenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) phenyl phosphine oxide, bis (2,5,5 6-trime Rubenzoiru) -2,4,4-trimethyl pentyl phosphine oxide and the like. Among these, bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide is preferable.

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

Examples of the coumarin compounds include 3,3′-carbonylbis (7-diethylaminocoumarin), 3- (4-methoxybenzoyl) coumarin, 3-thienoyl coumarin, 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-carboxy coumarin, 3-carboxy 7-Methoxycoumarin, 3-Ethoxycarbonyl-6-methoxycoumarin, 3-Ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 3-benzoyl-6-nitrocoumarin, 3-benzoyl-7-diethylamino Coumarin, 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-benzothiazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazoyl) -7- (diethylamino) coumarin, 3- (2-benzothiazoyl) -7- (dioctylamino) ) Coumarin, 3-acetyl-7- (dimethylamino) coumarin, 3,3'-carbonylbis (7-dibutylaminocoumarin), 3 , 3'-Carbonyl-7-diethylaminocoumarin-7'-bis (butoxyethyl) aminocoumarin, 10- [3- [4- (dimethylamino) phenyl] -1-oxo-2-propenyl] -2,3, 6,7-Tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-one, 10- (2-benzothiazoyl) Japanese Patent Application Laid-Open No. 9 of 2,3-6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-one, etc. The compounds described in JP-A-3109 and JP-A-10-245525 can be mentioned. Among them, 3,3'-carbonylbis (7-diethylaminocoumarin) and 3,3'-carbonylbis (7-dibutylaminocoumarin) are preferable.

Specific examples of water-soluble acyl phosphine oxides, quaternary ammonium salts of thioxanthones or thioxanthones, ketals, anthraquinones, benzoin alkyl ether compounds, and α-amino ketone compounds are disclosed in WO 2008/087977. And those described in

The content of the photopolymerization initiator (c) is not particularly limited, but from the viewpoint of the curability and the like of the resulting self-adhesive dental composite resin, it is 0 with respect to 100 parts by mass in total of the polymerizable monomer component. .001 to 20 parts by mass is preferable, 0.05 to 10 parts by mass is more preferable, and 0.10 to 5 parts by mass is more preferable. When content of a photoinitiator (c) is less than 0.001 mass part with respect to 100 mass parts of total amounts of a polymerizable monomer component, superposition | polymerization does not fully advance but causes the fall of adhesive strength. Since there is a possibility, 0.05 mass part or more is more preferred, and 0.10 mass part or more is still more preferred. On the other hand, when the content of the photopolymerization initiator (c) exceeds 20 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer components, sufficient when the polymerization performance of the photopolymerization initiator itself is low Adhesive strength may not be obtained, and there is a possibility that precipitation from the self-adhesive dental composite resin may occur, so 10 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monomer component Is more preferable, and 5 parts by mass or less is more preferable.

The self-adhesive dental composite resin of the present invention may further contain a chemical polymerization initiator. An organic peroxide is preferably used as a chemical polymerization initiator. 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, peroxy esters, peroxy dicarbonates, and the like. As specific examples of these organic peroxides, those described in WO 2008/087977 can be mentioned. The chemical polymerization initiators may be used alone or in combination of two or more.

In the self-adhesive dental composite resin of the present invention, the filler (i) which is not the filler (d) and is not the filler (e) affects the appropriate dischargeability, fluidity, sag and surface hardness. You may include in the range which is not. The filler (i) is a filler that has an isoelectric point of less than 6.0, and is not treated with a surface treatment agent that contains both the silane coupling agent (A) and the organosilazane (B), The component is intended to impart radiopacity to a self-adhesive dental composite resin, or to improve the strength or paste operability as a matrix.

As used herein, "radiopaque" refers to the ability of the solidified 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 the condition of the teeth.

As the filler (i), known fillers used in dental composite resins are used without any limitation, as long as they do not correspond to the filler (d) and the filler (e). As the filler, for example, liquid phase synthetic amorphous silica, fumed silica, fused silica, quartz, soda lime silica glass, E glass, C glass, borosilicate glass (pyrex glass), etc. Powders of various compositions; dental glass powders such as barium glass, strontium borosilicate glass, lanthanum glass ceramics, fluoroaluminosilicate glass, etc., composite oxides such as silica-titania and silica-zirconia, and surfaces coated with silica Core-shell structure calcium fluoride, silica surface-coated core-shell structure ytterbium fluoride, silica surface-coated core-shell structure yttrium-fluoride, silica surface-coated core-shell structure calcium phosphate, silica surface The Core-shell structure barium sulfate, silica surface-coated core-shell structure zirconium dioxide, silica surface-coated core-shell structure titanium dioxide, silica surface-coated core-shell structure hydroxyapatite Be One of these may be used alone, or two or more may be used in combination. Among these, those having a silica surface are preferable in that they can be treated with the silane coupling agent (A) and form an electrostatically weak association state with the filler (d) having an isoelectric point of 6.0 or more. Thus, fumed silica, ytterbium fluoride having a core-shell structure surface-coated with silica, and yttrium fluoride having a core-shell structure coated with silica are preferable.

The average particle diameter of the filler (i) is preferably 0.001 to 50.0 μm, more preferably 0.005 to 20.0 μm, and 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 can be obtained, no stickiness occurs in the paste, no problem occurs in operability, and the abrasion resistance and lubricity durability of the cured product are excellent.

The average particle size of the filler (i) can be measured in the same manner as the method of measuring the average particle size of the filler (d) or the filler (e) described above.

The filler (i) is preferably treated with a surface treatment agent. Examples of 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, and the silane coupling agent (A) and The surface treatment agent which contains the said organosilazane (B) together is remove | excluded. When using two or more kinds of organic metal compounds, it may be a surface treatment layer of a mixture of two or more kinds of organic metal compounds, or as a surface treatment layer of a multilayer structure in which two or more kinds of organic metal compound layers are laminated. Good.

Examples of the organosilicon compounds include the compounds represented by (W) _n SiY _4-n mentioned as the surface treatment agent for the filler (d) (in the formula, the symbols have the same meanings as described above).

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, and specifically, it can be used as a powder of amorphous or spherical particles . The use of the indeterminate filler (i) is particularly excellent in mechanical strength and abrasion resistance, and the use of the spherical filler (i) is particularly excellent in polishing lubricity and lubricity durability. The filler (i) in the present invention may be a commercially available product.

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

In the self-adhesive dental composite resin of the present invention, the above-mentioned fumed silica can be suitably used as a filler (i) for the purpose of providing leveling to a paste. The above-mentioned fumed silica is a silica which is produced dry 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. And may be blended for the purpose of adjusting the leveling properties of the paste. In addition, the leveling property of a paste is a characteristic in which the corner of the paste taken out of the container disappears by its own weight.

The BET specific surface area (specific surface area according to 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 the leveling property of the paste. 100 m ² / g or more is more preferable. Moreover, in the viewpoint which does not impair the leveling property of a self-adhesive dental composite resin, 400 m < ² > / g or less is preferable, 350 m < ² > / g or less is more preferable, 250 m < ² > / g or less is more preferable. Therefore, from the point of view, BET specific surface area of the fumed silica is preferably 25 ~ 400m ² / g, more preferably 50 ~ 350m ² / g, more preferably 100 ~ 250m ² / g.

The average primary particle diameter of the fumed silica is preferably 5 nm or more, more preferably 7 nm or more, and still more preferably 10 nm or more from the viewpoint of not deteriorating the leveling property of the paste. Moreover, in the viewpoint which provides the leveling property of a paste, 50 nm or less is preferable, 30 nm or less is more preferable, and 20 nm or less is more preferable. Therefore, from the above viewpoint, the average primary particle diameter of fumed silica is preferably 5 to 50 nm, more preferably 7 to 30 nm, and still more preferably 10 to 30 nm.

The pH of the fumed silica is preferably 3.0 or more, more preferably 3.5 or more, and 4.0 or more, from the viewpoint of not affecting the other components in the self-adhesive dental composite resin of the present invention. Is more preferred. Further, in view of suppressing the reaction with the acidic group-containing (meth) acrylic polymerizable monomer (a), 10.0 or less is preferable, 9.0 or less is more preferable, and 8.0 or less is more preferable. 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 still 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 still more preferably 120 g / L or more, from the viewpoint of suppressing an increase in viscosity when compounded. Further, from the viewpoint of a higher effect of imparting fluidity to the paste by the bearing effect, the amount is preferably 300 g / L or less, more preferably 290 g / L or less, and still more preferably 280 g / L or less. Therefore, from the above viewpoint, the apparent specific gravity of the fumed silica (d) is preferably 20 to 300 g / L, more preferably 50 to 290 g / L, and still more preferably 120 to 280 g / L.

That is, from the viewpoint of obtaining higher paste leveling properties, 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, BET It is more preferable that the specific surface area is 100 to 250 m ² / g and the apparent specific gravity is 120 to 280 g / L, and the BET specific surface area is 100 to 250 m ² / g, and the pH is 4.0 to 8.0. More preferably having 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 diameter of 7 to 30 nm, and a pH of 4.0 to 8 Particularly preferred are those having an apparent specific gravity of 120 to 280 g / L.

In addition, the measuring method of the said chemical property of fumed silica is as follows.
BET specific surface area (m ² / g):
Specific surface area measuring device (trade name: BELSORP-mini-II, fixed volume gas adsorption method (nitrogen adsorption and desorption measurement), Microtrac Bell, according to the BET method described in JIS Z 8830: 2013 or ISO 9277: 2010 (Manufactured by KK).
Average Primary Particle Size (nm):
Taking a picture of a sample with a scanning electron microscope (S-4000, manufactured by Hitachi, Ltd.) and measuring the particle diameter of particles (200 or more) observed in the unit field of the picture, image analysis type particle size distribution measurement It is determined 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 and shortest lengths of the particles, and the average primary particle diameter is calculated from the number of particles and the particle diameter thereof.
pH:
4 parts by mass of a sample is dispersed at normal temperature with respect to 100 parts by mass of distilled water to obtain a 4% by mass aqueous dispersion. Next, the pH in the 4% by mass aqueous dispersion is measured with a bench-top pH meter (F71, manufactured by Horiba, Ltd.). The above method conforms to ISO 787-9: 1981 except that a 4% by mass aqueous dispersion is used.
Apparent specific gravity:
The measurement is performed according to the method according to ISO 787-11: 1981, and is calculated by the following equation as Tapped density (also referred to as Tamped density).

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

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

The water used may be acidified (pH 1 to 7) with an acid (for example hydrochloric acid), and in the case of using several surface treatments, these surface treatments may be used simultaneously. It may also be used separately once or as a mixture. One or more surface treatment agents may be dissolved in a suitable solvent such as water, ethanol, isopropyl alcohol. Mixing may be continued for an additional 5 to 30 minutes after spraying is complete.

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

The structurally modified fumed silica has a high apparent specific gravity, so when structurally modified fumed silica and the polymerizable monomer are respectively incorporated in the same amount, the structural modification is made. The dental composition containing self-adhesive fumed silica (self-adhesive dental composite resin) has a significantly increased viscosity compared to the dental composition containing non-structurally modified fumed silica Can be reduced. That is, the structurally modified fumed silica can be compounded in a larger amount than the structurally unmodified fumed silica, and the effect of imparting leveling to the paste can be significantly improved. it 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 still more preferably 120 to 280 g / L from the viewpoint described above. As the fumed silica, commercially available products can be used. In particular, commercially available products of structurally modified fumed silica include, for example, AEROSIL (registered trademark) R7200 (surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m ² / g, average primary) Particle size: 12 nm, pH: 4.5, apparent specific gravity: 230 g / L, manufactured by EVONIK INDUSTRIES), AEROSIL (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 diameter: 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 content of the total of the 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 mass% or more is preferable, 55.0 mass% or more is more preferable, 59.0 mass% or more is more preferable. Moreover, 90.0 mass% or less is preferable with respect to the whole self-adhesive dental composite resin, as for content of the sum total of a filler, 85.0 mass% or less is more preferable, and 80.0 mass% or less is more preferable. . 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 preferable content is the total 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 another embodiment, a polymerization accelerator (h) is used together with a photopolymerization initiator (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, bisulfites, thiourea compounds and the like can be mentioned.

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

Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-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-tert-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-toluy , N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-tert-butylaniline, N, N-dimethyl-3,5-di-tert-butylaniline, ethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N -Dimethylamino methyl benzoate, propyl 4- (N, N-dimethylamino) benzoate, n-butoxyethyl 4- (N, N-dimethylamino) benzoate, 4- (N, N-dimethylamino) benzoic acid And 2- (methacryloyloxy) ethyl acid, 4- (N, N-dimethylamino) benzophenone, butyl 4- (N, N-dimethylamino) benzoate and the like. Among these, N, N-bis (2-hydroxyethyl) -p-toluidine and 4- (N, N-dimethylamino) benzoic acid from the viewpoint of being able to impart excellent curability to a self-adhesive dental composite resin. At least one selected from the group consisting of ethyl, n-butoxyethyl 4- (N, N-dimethylamino) benzoate and 4- (N, N-dimethylamino) benzophenone is preferably used.

Sulfinic acids and salts thereof, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, sulfites, bisulfites, and thiourea compounds Examples thereof include those described in WO 2008/087977.

The said polymerization accelerator (h) may be mix | blended individually by 1 type, and may be mix | blended combining 2 or more types. The content of the polymerization accelerator (h) is not particularly limited, but from the viewpoint of the curability and the like of the obtained self-adhesive dental composite resin, 0. 0 to 100 parts by mass of the total of the polymerizable monomer components. The amount is preferably 001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, and most preferably 0.1 to 5 parts by mass. The content of the polymerization accelerator (h) may be 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the polymerizable monomer components. When the content of the polymerization accelerator (h) is less than 0.001 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component, the polymerization may not proceed sufficiently, which may cause a decrease in adhesiveness. is there. On the other hand, when the content of the polymerization accelerator (h) exceeds 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable monomer component, sufficient adhesiveness is obtained depending on the polymerization performance of the polymerization initiator itself. In addition, the polymerization accelerator (h) may be precipitated 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 fluorine ion releasing substance (k), a self-adhesive dental composite resin capable of imparting acid resistance to dentin can be obtained. Examples of the fluorine ion-releasing substance include metal fluorides such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride and ytterbium fluoride. The fluorine ion-releasing substance (k) may be used alone or in combination of two or more.

Preferred embodiments of the self-adhesive dental composite resin of the present invention include a polymerizable monomer, a photopolymerization initiator (c), and a filler, and the polymerizable monomer contains an acidic group ( Meta) acrylic polymerizable monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and polyfunctional (meth) acrylamide polymerizable monomer having an amide proton A self-adhesive dental composite resin containing (f) and containing the filler (d) and the filler (e) as the filler; or a polymerizable monomer, a photopolymerization initiator (c), and a filler And the above-mentioned polymerizable monomer contains an acidic group-containing (meth) acrylic polymerizable monomer (a), a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and Hydrophilic monofunctional polymerizable monomer (g) Contains, as the filler, the filler (d) and self-adhesive dental composite resin containing filler (e) can be mentioned.

Moreover, as another suitable embodiment, it contains a polymerizable monomer, a photoinitiator (c), and a filler, and the said polymerizable monomer is acidic group containing (meth) acrylic-type polymerizable property. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, and polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton, and hydrophilicity And a self-adhesive dental composite resin which contains a basic monofunctional polymerizable monomer (g), and the filler includes a filler (d) and a filler (e).

Furthermore, as another suitable 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), a polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group, and a polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton, and hydrophilicity Of the monofunctional polymerizable monomer (g) and the above-mentioned polyfunctional (meth) acrylic polymerizable monomer (b) containing no acidic group is an aliphatic compound-based bifunctional polymerizable monomer And the polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton and containing the polyfunctional (meth) acrylamide polymerizable monomer (f3) represented by the general formula (5) And said hydrophilic monofunctional polymerizable monomer (g) is hydrophilic monofunctional Meth) contains an acrylate-based polymerizable monomer, as the filler, a filler (d) and a filler (e), include self-adhesive dental composite resin.

Furthermore, as another suitable embodiment, the polymerizable monomer, the photopolymerization initiator (c), and the filler are contained, and the polymerizable monomer is an acidic group-containing (meth) acrylic polymer. Monomer (a), polyfunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, and polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton, and hydrophilicity Acid group-containing (meth) acrylic polymerizable monomer (a) in a total amount of 100 parts by mass of the polymerizable monomer component, which contains the polymerizable monofunctional polymerizable monomer (g) 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 of hydrophilic monofunctional polymerizable monomer (g) It contains ~ 30 parts by weight, as the filler, a filler (d) and a filler (e), include self-adhesive dental composite resin.

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 the compound can be appropriately selected, and any component (for example, polymerization accelerator (h), chemistry A polymerization initiator, a polymerization inhibitor and the like 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 light absorber, a thickener, a coloring agent, an antibacterial agent, a flavoring agent, etc. within the range not impairing the effects of the present invention. You may mix | blend.

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

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

Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to these examples. The abbreviations and abbreviations used below are as follows. As the compounds used in the following Examples and Comparative Examples, commercially available products were used except when the synthesis method was described.

[Acidic Group-Containing (Meth) Acrylic-Based Polymerizable Monomer (a)]
MDP: 10-methacryloyloxydecyl dihydrophosphate 4-META: 4- [2- (methacryloyloxy) ethoxycarbonyl] phthalic anhydride

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

[Photopolymerization initiator (c)]
CQ: dl-camphorquinone BAPO: bis (2,4,6-trimethylbenzoyl) phenyl phosphine 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 diameter: 13 nm, pH: 5.0, apparent specific gravity: 50 g / L, EVONIK INDUSTRIES Company company) was used as it was. The isoelectric point was 9.0.
ST-ALU-C: Commercially available 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, An EVONIK INDUSTRIES Inc. product was surface-treated with 10-methacryloyloxydecyl dihydrophosphate and 11-methacryloyloxyundecyl trimethoxysilane. The isoelectric point was 9.0.

[Multifunctional (meth) acrylamide polymerizable monomer (f) having an amide proton]
TAC 4: N, N ', N'',N'''-tetraacryloyltriethylenetetramine (compound represented by the following formula (f1-5))

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

[Hydrophilic Monofunctional Polymerizable Monomer (g)]
DEAA: N, N-diethylacrylamide HEMA: 2-hydroxyethyl methacrylate

[Filler (e)]
The fillers (e-1) and (e-2) described in the below-mentioned production examples were used.

[Filler (i)]
R 7200:
Commercially available product (trade name: AEROSIL (registered trademark) R 7200, surface treatment agent: methacryloyloxysilyl group-containing silane compound, BET specific surface area: 145 m ² / g, average primary particle size: 12 nm, pH: 4.5, apparent) Specific gravity: 230 g / L (manufactured by EVONIK INDUSTRIES) was used as it was.
R 711:
Commercially available product (trade name: AEROSIL (registered trademark) R 711, surface treatment agent: methacryloyloxysilyl group-containing silane compound, 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-YBF100 WSCMP10, average particle diameter 110 nm, spherical particles, manufactured by Sukkyung AT) was used as it was.

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

(Production Example 1)
Preparation of Filler (e-1) As a silica particle, Snowtex OL (manufactured by Nissan Chemical Industries, Ltd., average particle diameter 50 nm, dispersed in water and having a solid content concentration of 20%), which is a type of colloidal silica, was prepared. Isopropanol was prepared as an alcohol. As a silane coupling agent (A), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was prepared. As organosilazane (B), 1,1,1,3,3,3-hexamethyldisilazane (HMDS, manufactured by Shin-Etsu Chemical Co., Ltd., HMDS-1) was prepared. A dispersion of silica particles dispersed in a liquid medium is obtained by adding 60 parts by mass of isopropanol to 100 parts by mass of a slurry in which silica particles are dispersed in water at a concentration of 20% by mass and mixing at room temperature (about 25.degree. C.). 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 Chemical Co., Inc.) are added to this dispersion. And mixed at 40 ° C. for 72 hours. In this step, hydroxyl groups present on the surface of the silica particles were surface-treated with a silane coupling agent (A). At this time, 3-methacryloyloxypropyltrimethoxysilane was added by calculation so that the necessary amount of hydroxyl groups (partially) remained without surface treatment. Then, 0.78 parts by mass of 1,1,1,3,3,3-hexamethyldisilazane was added to the mixture, and the mixture was left to stand at 40 ° C. for 72 hours. By this process, the silica particles were surface-treated to obtain a silica particle material. With the progress of surface treatment, hydrophobicized silica particles can not be stably present in water and isopropanol, and aggregate and precipitate. The molar ratio of 3-methacryloyloxypropyltrimethoxysilane and hexamethyldisilazane as the surface treatment agent was 2: 5. 2.6 parts by mass of 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 through filter paper (Advantec 5A). The filter residue (solid content) was washed with pure water and then vacuum dried at 100 ° C. to obtain a filler (e-1) (average particle diameter: 50 nm). The isoelectric point was 1.8.

(Production Example 2)
Production of Filler (e-2) A method of 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 The filler (e-2) (average particle diameter 50 nm) was produced in the same manner as in the above. The molar ratio of 3-methacryloyloxypropyltrimethoxysilane and hexamethyldisilazane as the surface treatment agent was 2:18. The isoelectric point was 1.8.

(Production Example 3)
Synthesis of TAC 4 In a 1 L four-necked flask, 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. 1). 03 mmol) and 250 mL of dichloromethane were charged, stirred, and cooled to an internal temperature of 2 ° C. 100 mL of a dichloromethane solution of acrylic acid chloride (67.9 g, 0.75 mol) was added dropwise at 5 ° C. or less over 2 hours. After dropping, the mixture was stirred at room temperature for 24 hours. The reaction solution was filtered, the insolubles were washed with dichloromethane, and concentrated at 35 ° C. or less under reduced pressure. The concentrated residue obtained 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 from the position and integration value of the signal, it was confirmed that the obtained white solid was the target 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, 6 H), 3.57 (m, 6 H), 5. 66 (m, 4 H), 6.07 (m, 6 H), 6.56 (M, 2H) (ppm)

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

MS m / z: 184 (M + H) ⁺
¹ H-NMR (270 MHz CDCl ₃ ): δ 1.94 (m, 3 H), 3.62 (m, 2 H), 4.28 (m, 2 H), 5.58 (m, 1 H), 5. 66 ( m, 1 H), 6.08 (s, 1 H), 6. 10 (m, 1 H), 6.1 1 (m, 1 H), 6. 28 (m, 1 H) (ppm)

(Examples 1 to 21 and Comparative Examples 1 to 5)
Among the components described in Tables 1 to 3, the components other than the filler (d), the filler (e) and the filler (i) (all in the form of powder) are After mixing at about 25 ° C. to obtain a uniform liquid component, the obtained liquid component and the powder components of filler (d), filler (e) and filler (i) are kneaded to obtain Example 1 A self-adhesive dental composite resin of ̃21 and a dental composite resin (paste) of Comparative Examples 1 to 5 were prepared. Then, using these pastes, surface hardness, sag, tensile bond strength to dentin, bending strength, and discharge property were evaluated according to the method described later. Tables 1 to 3 show the compounding ratio (parts by mass) of this dental composite resin and the test results.

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

[Sag]
Sagability, which is an indicator of paste fluidity, was evaluated as follows. After vacuum degassing the paste of the dental composite resin prepared in each example and comparative example, it was filled in a syringe made of polyolefin resin. Then, a needle tip having a needle diameter of 20 G (gauge) was attached to the syringe. Thereafter, it is separated on a 20 mg paper sheet under 37.degree. C. environment, and after 1 minute of tilting the paper sheet, measure the distance (mm = 5) that the paste has moved (n = 5), and calculate the average value And the dripping property of the dental composite resin immediately after preparation.
Also, separately from the above, after the paste of the dental composite resin is vacuum defoamed and filled into a syringe made of a polyolefin resin, the dental composite resin is allowed to stand for 4 weeks with a thermostat kept at 60 ° C. The value measured by the above method was taken as the sag of the dental composite resin after 4 weeks at 60 ° C. 2.5 mm or less is preferable, as for the difference between the sag property immediately after preparation and the sag property after 60 degreeC 4 weeks, 2.3 mm or less is more preferable, and 2.2 mm or less is more preferable.

[Tensile bond strength to dentin]
The labial surface of the bovine lower incisor was abraded in flowing water with # 80 silicon carbide paper (manufactured by Nippon Kenshi Co., Ltd.) to obtain a sample to be adhered in which the flat surface of dentin was exposed. The obtained sample to be adhered was further polished under flowing water with # 1000 silicon carbide paper (manufactured by Nippon Ken Paper Co., Ltd.). After completion of the polishing, the surface water was dried by air blowing. On the smooth surface after drying, an adhesive tape having a thickness of about 150 μm having a round hole of 3 mm in diameter was attached to define an adhesive area.

In the said round hole, the paste of the dental composite resin of each prepared Example and comparative example was filled, and it covered with the release film (polyester). Next, a slide glass was placed on the release film and pressed to smooth the coated surface of the paste. Subsequently, the paste is irradiated with light through the release film for 10 seconds using a visible light irradiator for dental polymerization (trade name: Pencure 2000, manufactured by Morita Co., Ltd.) to obtain a cured product. The

Using a commercially available dental resin cement (trade name: Panavia (registered trademark) 21, manufactured by Kurare Noritake Dental Co., Ltd.) on the surface of the cured product of the obtained dental composite resin, a stainless steel cylindrical rod (diameter 7 mm) And one end face (circular cross section) of 2.5 cm in length) was bonded to make an adhesion test sample. After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. Adhesion Test A total of five test samples were prepared and allowed to stand in a thermostat maintained at 37 ° C. for 24 hours.

The tensile bond strength of the adhesion test sample was measured using a precision universal testing machine (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation) with the crosshead speed set at 2 mm / min. The tensile bond strength (MPa) was taken as The tensile bond strength passed 9.5 MPa or more.

[Bending strength]
After vacuum degassing the paste of the prepared dental composite resin of each example and comparative example, it is filled in a stainless steel mold (dimension 2 mm × 2 mm × 25 mm), and the upper and lower sides are pressed with a slide glass, visible for dental polymerization With a light beam irradiator (trade name: Pencure 2000, manufactured by Morita Co., Ltd.), the slide glass was irradiated with light for curing at 1 point 10 seconds, 5 points on each side, to obtain a cured product. For each example and comparative example, five cured products were prepared, and after the cured product was removed from the mold, it was stored in distilled water at 37 ° C. for 24 hours. The cured product after storage is used as a test sample sample under the conditions of a distance between supporting points of 20 mm and a crosshead speed of 1 mm / min using a precision universal testing machine (trade name: AG-I 100 kN, manufactured by Shimadzu Corporation) The bending strength was measured, and the average value of the measured values of each sample was calculated to be the bending strength (MPa). The bending strength passed 100 MPa or more.

[Dischargeability]
After vacuum degassing the paste prepared in each example and comparative example, the syringe was filled with 1.5 ml, and the needle tip was attached to the tip of the syringe, and the paste was discharged from the tip of the needle tip by pushing the plunger. . The discharge force (force required to extrude the paste from the syringe) at this time was measured using a precision universal testing machine (manufactured by Shimadzu Corporation, trade name "AG-I 100 kN") (n = 5), and the average was The value was calculated. The syringe was stood vertically and the crosshead equipped with a jig for 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 36 N, ejection is easy and the ejection performance is good, and when it is 36 N or more, ejection is possible, but the ejection performance is poor. That is, it evaluated as the discharge property of a paste according to the following evaluation criteria.
:: 10 N or less :: 10 N or more to less than 36 N C: 36 N or more Furthermore, the operator can operate without stress.

As shown in Tables 1 and 2, the self-adhesive dental composite resin according to the present invention (Examples 1 to 21) gave good results in all of the surface hardness, the dischargeability and the sagging of the paste. . Further, the difference between the sagging property immediately after preparation and the sagging property at 60 ° C. after 4 weeks was hardly changed to 2.3 mm or less. Furthermore, in each case, a tensile bond strength of 9.9 MPa or more and a strength of 101.5 MPa or more were developed with respect to dentin.

As shown in Table 3, the dental composite resins of Comparative Examples 1, 2 and 5 in which the filler (d) having an isoelectric point of 6.0 or more was not blended had a low surface hardness and a large sag. Furthermore, the sag changed significantly after storage at 60 ° C. for 4 weeks. Moreover, in Comparative Examples 3 and 4 in which a large amount of filler (d) was blended, although there were no problems with surface hardness and sag, the dischargeability 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 self-adhesive dental composite resin therein, and photocuring it for treatment of dental defects and caries. .

Claims

Acidic group-containing (meth) acrylic polymerizable monomer (a), multifunctional (meth) acrylic polymerizable monomer (b) not containing an acidic group, photopolymerization initiator (c), isoelectric point A self-adhesive dental composite resin containing a filler (d) 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 the average particle diameter is 0.001 to 50.0 μm, and the surface treatment agent has the following general formula (1):
CH 2 = C (R 1) -COO- (CH 2) p -Si-R 2 q R 3 (3-q) (1)
(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- optionally having a substituent) C 3 alkyl group, p is an integer of 1 to 13, q is 2 or 3.)
Silane coupling agent (A) represented by the following general formula (2)
R 4 R 5 R 6 -Si-NH-Si-R 7 R 8 R 9 (2)
(Wherein, R 4 , R 5 and R 6 each independently represent a hydrogen atom or a C 1 to C 3 alkyl group which may have a substituent, R 4 , R 5 and R 6 At least one of 6 is a C 1 to C 3 alkyl group which may have a substituent, and R 7 , R 8 and R 9 each independently have a hydrogen atom or a substituent Or C 1 -C 3 alkyl group, and at least one of R 7 , R 8 and R 9 is a C 1 -C 3 alkyl group which may have a substituent.
Containing an organosilazane (B) represented by
A self-adhesive dental composite resin comprising 0.1 to 15 parts by mass of the filler (d) based on 100 parts by mass of a total amount of polymerizable monomer components.
The self-adhesive dental composite resin according to claim 1, wherein the average particle diameter of the filler (d) is 0.001 to 0.5 μm.
R 2 is an unsubstituted hydrolyzable group, R 3 is an unsubstituted C 1 to C 3 alkyl group, and R 4 , R 5 and R 6 are each independently a hydrogen atom or no group A substituted C 1 to C 3 alkyl group, at least one of R 4 , R 5 and R 6 is an unsubstituted C 1 to C 3 alkyl group, 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, The self-adhesive dental composite resin according to claim 1 or 2.
The silane coupling agent (A) is selected from 2-methacryloyloxyethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 4-methacryloyloxybutyltrimethoxysilane, 5-methacryloyloxypentyltrimethoxysilane, and 6-methacryloyloxy The self-adhesive dental composite resin according to any one of claims 1 to 3, which is at least one selected from the group consisting of oxyhexyltrimethoxysilane.
The organosilazane (B) is selected from 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 at least one selected from the group consisting of methyldisilazane.
1 to 40 parts by mass of the acidic group-containing (meth) acrylic polymerizable monomer (a) in 100 parts by mass of the total amount of the polymerizable monomer component, and a polyfunctional (meth) not containing the acidic group It contains 30 to 95 parts by mass of the acrylic polymerizable monomer (b), and 0.001 to 20 parts by mass of the photopolymerization initiator (c) based on 100 parts by mass of the total amount of the polymerizable monomer component The self-adhesive dental composite resin according to any one of claims 1 to 5, containing 0.1 to 10 parts by mass of the filler (d) and 25 to 400 parts by mass of the 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 an amide proton.
8. The method according to claim 7, wherein the content of the polyfunctional (meth) acrylamide polymerizable monomer (f) having an amide proton is 0.5 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component. 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 composed of a hydrophilic monofunctional (meth) acrylate type polymerizable monomer and a hydrophilic monofunctional (meth) acrylamide type polymerizable monomer The self-adhesive dental composite resin according to claim 9, which is at least one selected from the group consisting of
11. The self-contained polymer according to claim 9, wherein the content of said hydrophilic monofunctional polymerizable monomer (g) is 1 to 30 parts by mass in 100 parts by mass of the total amount of the polymerizable monomer component. 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-material type.