JP2015196686A - High-toughness teeth-bondable silane coupling agent and dental composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which various acidic monomers proposed for conventional dental primers, dental adhesives etc. to solve the problem of teeth bondability degradation caused by hydrolysis are not satisfactory, because their durability and toughness of teeth bonding are inferior and their low refractive indices also cause inferior transparency when combined with a filler having a high refractive index having an x-ray contrast property.SOLUTION: A high-toughness teeth-bondable silane coupling agent is disclosed in which functional groups such as an acidic group and an aldehyde group can be introduced into a silicon atom via a thiourethane bond, a thioester bond and a thioether bond so as to impart to an inorganic filler very high bonding toughness, durability and reactivity for teeth. The use of the silane coupling agent of the present invention can significantly improve bonding performance of a dental primer, a dental adhesive, a dental cement, a dental resin cement, a dental resin modified cement and a dental composite resin.

Description

The present invention relates to a high-toughness tooth-adhesive silane coupling agent, a dental inorganic filler surface-treated with the high-toughness tooth-adhesive silane coupling agent, the high-toughness tooth-adhesive silane coupling agent, and A dental inorganic filler surface-treated with a radically polymerizable silane coupling agent, the high-toughness dental adhesive silane coupling agent alone, or a dental inorganic filler condensed and granulated in the presence of a metal alkoxide, and The present invention relates to a dental adhesive composition comprising a dental inorganic filler condensed and granulated with a radically polymerizable silane coupling agent alone or in the presence of a metal alkoxide in the presence of the high toughness dental adhesive silane coupling agent. More specifically, the present invention includes a dental primer, a dental adhesive, a dental glass ionomer cement, a dental dental material that contains the above-described dental inorganic filler and can exhibit strong adhesiveness and durability with the tooth. The present invention relates to a resin cement, a dental resin modified cement, and a self-adhesive dental composite resin.

In the dental field, a curable composition called a composite resin is used daily in clinical practice. The composite resin is filled in a defect site such as a tooth, and external energy such as light irradiation is applied to cure by radical polymerization and preservation and restoration are performed. At this time, it is common to use a dental primer and a dental adhesive in advance to strengthen the adhesion between the tooth and the composite resin. In recent years, self-adhesive composite resins that do not require dental primers and dental adhesives have been developed. (Patent Documents 1 to 5) However, these inventions are characterized by containing an acidic group-containing polymerizable unsaturated monomer (acidic monomer) that has been used conventionally, and are a carboxyl group or a phosphate group. There are few descriptions on the active efforts related to the connecting group for connecting to the radical polymerizable group via the carbon chain. In other words, there are few descriptions regarding active efforts to increase adhesion toughness or to suppress hydrolysis. Furthermore, in these patent documents, only an acidic monomer is used as a compound for tooth adhesion, and a concept for achieving both strong adhesion and durability with the tooth is not shown. Therefore, it can be said that there is no inventive step compared to the prior art.

Generally for dental primer, dental adhesive, dental cement, dental resin cement, dental resin modified cement and self-adhesive dentistry, such as methyl methacrylate, triethylene glycol dimethacrylate, urethane dimethacrylate, etc. (Meth) acrylic acid derivative monomers are used. In free radical polymerization (hereinafter referred to as radical polymerization) of polymerizable monomers such as (meth) acrylic acid derivative monomers and acidic monomers having adhesiveness to teeth (hereinafter referred to as radical polymerization), the carbon-carbon double bond is cleaved to become a single bond. As a result, a polymer is formed and cured. Here, adhesion to a dentin (enamel containing a lot of hydroxyapatite, dentin containing an organic substance such as collagen fiber) is one of important issues. When this adhesion is insufficient or the adhesion durability is low, a gap is formed between the restoration material such as the composite resin and the tooth, and the dental caries progresses to secondary caries. As a result, treatment such as tooth extraction is performed, resulting in a great disadvantage for the patient.

Dental materials containing acidic monomers capable of chemical bonding with hydroxyapatite or collagen fibers are used for adhesion to these teeth. For example, acidic monomers including aldehyde, β diketone, β ketoester, carboxylic acid, carboxylic anhydride, phosphoric acid, phosphonic acid and the like are used.

  For dental adhesive compositions, conventional one-component self-etching primers and one-component one-step bonding materials that contain an acidic monomer such as a (meth) acrylate monomer having an acidic group in the molecule have been proposed. Although it has been commercialized, the adhesiveness decreases due to hydrolysis of ester bonds such as (meth) acrylate monomers in strong acidic solutions and hydrolysis at the adhesive interface between the adhesive and the tooth. There's a problem. Recently, many techniques relating to (meth) acrylamide monomers having an acidic group have been disclosed in order to solve anxiety factors for adhesion.

  Non-Patent Document 1 reports that a phosphonic acid group-containing monomer having no ester bond prevents adhesion deterioration due to hydrolysis.

  Patent Document 6 and Non-Patent Document 2 report that a self-etching primer containing N-methacryloyl-ω-aminoalkylphosphonic acid and N-methacryloylglycine improves deterioration of adhesion performance due to hydrolysis. However, N-methacryloyl-ω-aminoalkylphosphonic acid, such as N-methacryloylaminoethylphosphonic acid, is excellent in hydrolytic stability with an aqueous primer, but has a great disadvantage that it does not dissolve in a hydrophobic resin.

  In recent years, many adhesive monomers have been reported which advocate so-called hydrolysis stability. Such adhesive monomers are reported by patent documents 7-11.

  Among these, since the compounds disclosed in Patent Documents 7, 8 and 11 have a phosphate group in the molecule, the C—O—P bond may be hydrolyzed.

The compounds disclosed in Patent Document 9 and Patent Document 10 can be expected to be hydrolytically stable, but have poor solubility in water and hydrophobic resins.

  As described above, various acidic monomers have been proposed in order to solve the problem of deterioration of the adhesive performance due to hydrolysis in water-based self-etching primers, one-part dental one-step bonding materials, and composite resins. Not enough.

Patent Document 12 discloses a silane coupling agent containing an acidic group, an aldehyde group, or the like instead of the acidic monomer described above. However, although the hydrolytic property is certainly reduced in the patent, it cannot be said that sufficient mechanical strength has been reached. Further, since the connecting group of the compound is an ether, thioether, amide, ester and urethane group, it can be said that the invention is inferior in toughness and durability.

JP-A-2005-320284 JP2009-227676 JP2011-42609 JP2012-171885 JP 2014-9219 A JP 2003-89613 A JP 2006-176511 A JP 2006-176522 A JP 2006-199695 A JP 2006-514114 A JP 2006-520344 A JP 2009-167186 A

Macro Molecule Chemistry Physics Volume 200, 1062-1067 (1999) Journal of Dental Research, Volume 86, Special Issue, Presentation No. # 2661

As described above, various acidic monomers have been proposed in order to solve the problem that the dental adhesion performance decreases due to hydrolysis in conventional dental primers and dental adhesives, etc., but the toughness of dental adhesion and It is not enough because it is inferior in durability. Furthermore, since the refractive index is low, the transparency when combined with a filler having a high refractive index such as X-ray contrast is poor. In addition, polyacrylic acid used in dental glass ionomer cements and dental resin modified cements is chelated with teeth while showing cross-linking and hardening by reaction with alkaline earth metals such as fluoroaluminosilicate glasses. However, the polyacrylic acid concentration exceeding 40 wt% has a limit in content because gelation occurs. That is, there was a limit to the content of acidic groups.

As a result of intensive studies by the inventors, by introducing functional groups such as acidic groups and aldehyde groups into silicon atoms via thiourethane bonds, thioester bonds and thioether bonds, extremely high adhesive toughness to teeth, We have discovered a high-tough dentin adhesive silane coupling agent that can impart durability and reactivity to inorganic fillers. Further, the dental inorganic filler surface-treated with the high toughness tooth adhesive silane coupling agent and radical polymerizable silane coupling agent of the present invention, the high toughness tooth adhesive silane coupling agent of the present invention alone or metal A dental adhesive composition containing a dental inorganic filler condensed and granulated with a radically polymerizable silane coupling agent in the presence of an alkoxide has both dental adhesiveness and covalent bond (radical polymerizable) properties. On the other hand, it was discovered that it had very high adhesive toughness and durability, and the present invention was completed. In addition, dental treatment that can react with fluoroaluminosilicate powder (glass ionomer cement powder) in the presence of water instead of polyacrylic acid by surface treatment of inorganic filler with only high-toughness tooth-bonding silane coupling agent Inorganic filler was developed. As a result, acidic groups such as carboxyl groups, which have been difficult with the prior art, can be contained in a high proportion of the dental glass ionomer cement powder. Since these acidic groups are also bonded to the inorganic powder through a thiourethane bond, a thioester bond, and a thioether bond, the toughness of the cured product is increased as compared with polyacrylic acid. The dental inorganic filler surface-treated with the high toughness tooth adhesive silane coupling agent and radical polymerizable silane coupling agent of the present invention, the high toughness tooth adhesive silane coupling agent of the present invention alone or a metal alkoxide Dental primer and dental adhesive containing a dental inorganic filler condensed and granulated with a radically polymerizable silane coupling agent in the presence of ionic bonds to the tooth of functional groups such as acidic groups and aldehyde groups It showed remarkable improvement in adhesion strength, durability and high refractive index due to the synergistic effect of covalent bond to radical polymerizable monomer. These inorganic fillers can be regarded as adhesive inorganic fine particles having high toughness. As described above, by using the high-toughness tooth-bonding silane coupling agent according to the present invention, dental primer, dental adhesive, dental cement, dental resin cement, dental resin modified cement, and self-adhesion The present invention was completed by discovering that it is possible to improve the adhesion performance of the composite dental resin.

As described above, the high-toughness tooth-adhesive silane coupling agent in which a functional group such as an acid group or an aldehyde group according to the present invention is introduced into a silicon atom via a thiourethane bond, a thioester bond, and a thioether bond, Inorganic fillers surface-treated with both tough dentin adhesive silane coupling agent and radical polymerizable group silane coupling solve the conventional problems, greatly maintain the adhesion performance, and improve the caries of patients. In order to ensure treatment and preservation of teeth, it is highly valuable to greatly contribute to dentistry.

以下に代表的な化合物の化学構造を記載する。

[Chemical Formula 1] shows the molecular structure of the high-toughness tooth-adhesive silane coupling agent having a functional group such as an acid group or an aldehyde group of the present invention. The structure shown in [Chemical Formula 1] will be described in more detail. A represents —COOH, —P (O) (OH) ₂ , —S (O) ₂ OH, —O—P (O) (OH) ₂ , — A CHO, —NH—C (O) —CHO, —C (O) —CHO group, which may contain a —C (O) —O—C (O) — group only when R ¹ is aromatic; ¹ is a C _{2 to} C ₆₀ linear or branched alkylene group, an at least trivalent aromatic group, and Z is —C (O) —O—, —C (O) —S—, —NH -C (O)-, -NH-C (O) -NH-, -NH-C (O) -S-, -NH-C (O) -O-, -S- group, D represents Represents a C _{2 to} C ₆₀ divalent to tetravalent linear or branched alkylene group, —C (O) —O—, —C (O) —S—, —NH—C (O) —, -NH-C (O) -NH-, -S-, -NH- (O) —S—, —NH—C (O) —O— groups may be included and / or have a trivalent triazine molecular skeleton or a divalent barbituric acid molecular skeleton, E is —NH— C (O) —S—, —NH—C (O) —NH—, —C (O) —S— group, wherein R ³ is a C _{1 to} C ₆₀ straight chain or branched alkylene group. , —S—, —NH—, —NR ⁴ — (R ⁴ represents an alkylene group), —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) — R ² represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one or more halogen atoms are present in Si. Join. R ⁴ represents a C _{1 to} C ₆ linear or branched alkyl group. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, n is 0 to 3, a is 1 to 2, and R1 is aromatic only when a is 2. Represents.

The chemical structures of typical compounds are described below.

The inorganic filler to be treated with the high-toughness tooth-adhesive silane coupling agent of the present invention is not particularly limited regardless of their chemical composition. Specific examples include silicon dioxide, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass ceramic, alumino Examples thereof include silicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, and strontium calcium fluoroaluminosilicate glass. In particular, fluoroaluminosilicate barium glass, fluoroaluminosilicate strontium glass, fluoroaluminosilicate glass, and the like used for dental glass ionomer cement, resin-reinforced glass ionomer cement, and resin cement can be suitably used. The fluoroaluminosilicate glass mentioned here has silicon oxide and aluminum oxide as a basic skeleton, and contains an alkali metal for introducing non-crosslinkable oxygen. Furthermore, it has an alkaline earth metal containing strontium and fluorine as a modification / coordination ion. In addition, it is a glass composition in which a lanthanoid series element is incorporated into a skeleton in order to impart further radiopacity. This lanthanoid series element is incorporated into the glass composition as a modified / coordinating ion depending on the glass composition range. These inorganic fillers can be used alone or in admixture of two or more. The high-toughness tooth-adhesive silane coupling agent in the present invention may be used alone or in combination. Further, it may be used in combination with a radical polymerizable silane coupling agent. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler before the surface treatment, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . As content in the dental composition in this invention of the inorganic filler processed with the high-toughness tooth | gear adhesive silane coupling agent of this invention, Preferably it exists in the range of 5-90 weight%. If it is 5% by weight or less, the adhesive strength is low, which is not preferable. On the other hand, if it is 90% by weight or more, the viscosity of the prepared paste is too high, so that clinical operability is poor and not preferable. Furthermore, it is preferable that the average particle diameter of the said inorganic filler is 0.001-100 micrometers, More preferably, it is 0.001-10 micrometers. Furthermore, the shape of the inorganic filler may be either spherical or indefinite.

[Chemical Formula 2] shows the molecular structure of a silane coupling agent having a radical polymerizable group used in the surface treatment of an inorganic filler together with the high-toughness tooth-adhesive silane coupling agent of the present invention. The structure shown in [Chemical Formula 2] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —C (O) —NH—, —NH—C (O) —NH—. , —NH—C (O) —S—, —NH—C (O) —O— group, Z represents a C _{1 to} C ₃₀ linear or branched alkylene group, and Y represents — NH—C (O) —O— group, R ² is a C _{7 to} C ₃₀ linear or branched alkylene group, —S—, —NH—, —NR ⁴ — (R ⁴ is alkylene) Group), —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, —O— group, and R ³ represents C _{1 to} C alkyl of ₆ straight or branched chain Represents a group, R ¹ is linear or branched alkyl group of C ₁ -C _16, at least one or more halogen atoms when n represents a phenyl group or a halogen atom 0 are bound to Si. In addition, a is 1-6 and n is 0-3.

These silane coupling agents having a radical polymerizable group may be used alone or in combination. Moreover, the ratio in the case of using both the high toughness tooth adhesive adhesive silane coupling agent of this invention and the silane coupling agent which has a radically polymerizable group for surface treatment has the preferable range of 1: 10-10: 1. When the ratio of the silane coupling agent having a radical polymerizable group is higher than 1:10, the effect of the high-toughness adhesive adhesive silane coupling agent is reduced, and the silane coupling agent having a radical polymerizable group is higher than 10: 1. This is because the effect of the silane coupling agent having a radical polymerizable group is diminished when the ratio is low. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . Further, the surface treatment with the high-toughness tooth-adhesive silane coupling agent of the present invention and the silane coupling agent having a radical polymerizable group may be performed separately or simultaneously. The chemical structure of a silane coupling agent having a typical radical polymerizable group is described below.

このラジカル重合性基を有するシランカップリング剤は１種または複数の組み合わせで用いても良い。また本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤とを共に表面処理に使用する場合の比率は１：１０〜１０：１の範囲が好ましい。１：１０よりラジカル重合性基を有するシランカップリング剤の比率が高い場合には高靭性歯質接着性シランカップリング剤の効果が薄れ、１０：１よりラジカル重合性基を有するシランカップリング剤の比率が低い場合には、ラジカル重合性基を有するシランカップリング剤の効果が薄れるためである。また、処理濃度に関しては無機充填剤のシラノール基密度（ｍｏｌ／ｇ）にもよるが、一般的にはシラノール基密度の等倍から１０倍が好ましい。等倍より低い処理では十分にシランカップリング剤を導入出来ず、また、１０倍を超えた場合にはシランカップリング剤のみの縮合物が生成し、機械的強度に影響を与えるために好ましくない。さらに、本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤による表面処理は別々に行っても、同時に行っても良い。以下に代表的なラジカル重合性基を有するシランカップリング剤の化学構造を記載する。

[Chemical Formula 3] shows the molecular structure of the silane coupling agent having a radical polymerizable group used when the inorganic filler is surface-treated with the high-toughness tooth-adhesive silane coupling agent of the present invention. The structure shown in [Chemical Formula 3] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄₋ group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —C (O) —NH—, —NH—C (O) —NH—. , —NH—C (O) —S—, —NH—C (O) —O— group, Z represents a C _{1 to} C ₃₀ linear or branched alkylene group, and Y represents — NH-, -S-, -NH-C (O) -S-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH ( OH) —CH ₂ —S—, —CH (OH) —CH ₂ —O— group, wherein R ² is a C _{7 to} C ₃₀ linear or branched alkylene group, —S—, — NH—, —NR ⁴ — (R ⁴ represents an alkylene group) , —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, —O— group, and R ³ is a straight chain of C _{1 to} C ₆ . Or a branched alkyl group, and R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one or more halogen atoms are bonded to Si. . In addition, a is 1-6 and n is 0-3.

These silane coupling agents having a radical polymerizable group may be used alone or in combination. Moreover, the ratio in the case of using both the high toughness tooth adhesive adhesive silane coupling agent of this invention and the silane coupling agent which has a radically polymerizable group for surface treatment has the preferable range of 1: 10-10: 1. When the ratio of the silane coupling agent having a radical polymerizable group is higher than 1:10, the effect of the high-toughness adhesive adhesive silane coupling agent is reduced, and the silane coupling agent having a radical polymerizable group is higher than 10: 1. This is because the effect of the silane coupling agent having a radical polymerizable group is diminished when the ratio is low. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . Further, the surface treatment with the high-toughness tooth-adhesive silane coupling agent of the present invention and the silane coupling agent having a radical polymerizable group may be performed separately or simultaneously. The chemical structure of a silane coupling agent having a typical radical polymerizable group is described below.

このラジカル重合性基を有するシランカップリング剤は１種または複数の組み合わせで用いても良い。また本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤とを共に表面処理に使用する場合の比率は１：１０〜１０：１の範囲が好ましい。１：１０よりラジカル重合性基を有するシランカップリング剤の比率が高い場合には高靭性歯質接着性シランカップリング剤の効果が薄れ、１０：１よりラジカル重合性基を有するシランカップリング剤の比率が低い場合には、ラジカル重合性基を有するシランカップリング剤の効果が薄れるためである。また、処理濃度に関しては無機充填剤のシラノール基密度（ｍｏｌ／ｇ）にもよるが、一般的にはシラノール基密度の等倍から１０倍が好ましい。等倍より低い処理では十分にシランカップリング剤を導入出来ず、また、１０倍を超えた場合にはシランカップリング剤のみの縮合物が生成し、機械的強度に影響を与えるために好ましくない。さらに、本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤による表面処理は別々に行っても、同時に行っても良い。以下に代表的なラジカル重合性基を有するシランカップリング剤の化学構造を記載する。

[Chemical Formula 4] shows the molecular structure of the silane coupling agent having a radical polymerizable group used when the inorganic filler is surface-treated together with the high-toughness tooth-adhesive silane coupling agent of the present invention. The structure shown in [Chemical Formula 4] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H _4- group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —C (O) —NH—, —NH—C (O) —NH—. , —NH—C (O) —S—, —NH—C (O) —O— group, wherein Z is a C _{1 to} C ₆₀ linear or branched alkylene group, —CH (OH) A —CH ₂ —S—, —CH (OH) —CH ₂ —O— group, wherein D represents a C ₂ -C ₆₀ divalent to tetravalent linear or branched alkylene group; C (O) -O-, -C (O) -S-, -NH-C (O)-, -NH-C (O) -NH-, -S-, -NH-C (O) -S -, -NH-C (O) -O-, and / or Has a trivalent triazine molecule skeleton or a divalent barbituric acid molecule skeleton, E ^{is, -NH -, - NR 4 -} (R 4 represents an alkylene group), - O -, - S -, - NH—C (O) —S—, —NH—C (O) —NH—, —C (O) —S—, —NH—C (O) —O—, —C (O) —O— groups R ² represents a C _{1 to} C ₆₀ linear or branched alkylene group, and —S—, —NH—, —CH ₂ —C ₆ H ₄ —C ₆ H ₄ represents a phenylene group. , —C (O) —O—, —O— group, wherein R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group or a halogen atom, and at least 1 when n is 0 The above halogen atoms are bonded to Si, and R ³ represents a C _{1 to} C ₆ linear or branched alkyl group. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, n is 0 to 3, and a is 1 to 6.

These silane coupling agents having a radical polymerizable group may be used alone or in combination. Moreover, the ratio in the case of using both the high toughness tooth adhesive adhesive silane coupling agent of this invention and the silane coupling agent which has a radically polymerizable group for surface treatment has the preferable range of 1: 10-10: 1. When the ratio of the silane coupling agent having a radical polymerizable group is higher than 1:10, the effect of the high-toughness adhesive adhesive silane coupling agent is reduced, and the silane coupling agent having a radical polymerizable group is higher than 10: 1. This is because the effect of the silane coupling agent having a radical polymerizable group is diminished when the ratio is low. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . Further, the surface treatment with the high-toughness tooth-adhesive silane coupling agent of the present invention and the silane coupling agent having a radical polymerizable group may be performed separately or simultaneously. The chemical structure of a silane coupling agent having a typical radical polymerizable group is described below.

このラジカル重合性基を有するシランカップリング剤は１種または複数の組み合わせで用いても良い。また本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤とを共に表面処理に使用する場合の比率は１：１０〜１０：１の範囲が好ましい。１：１０よりラジカル重合性基を有するシランカップリング剤の比率が高い場合には高靭性歯質接着性シランカップリング剤の効果が薄れ、１０：１よりラジカル重合性基を有するシランカップリング剤の比率が低い場合には、ラジカル重合性基を有するシランカップリング剤の効果が薄れるためである。また、処理濃度に関しては無機充填剤のシラノール基密度（ｍｏｌ／ｇ）にもよるが、一般的にはシラノール基密度の等倍から１０倍が好ましい。等倍より低い処理では十分にシランカップリング剤を導入出来ず、また、１０倍を超えた場合にはシランカップリング剤のみの縮合物が生成し、機械的強度に影響を与えるために好ましくない。さらに、本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤による表面処理は別々に行っても、同時に行っても良い。以下に代表的なラジカル重合性基を有するシランカップリング剤の化学構造を記載する。

[Chemical Formula 5] shows the molecular structure of a silane coupling agent having a radical polymerizable group used when the inorganic filler is surface-treated with the high-toughness tooth-adhesive silane coupling agent of the present invention. The structure shown in [Chemical Formula 5] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —NH—C (O) —, —NH—C (O) —NH—. , —NH—C (O) —S—, —NH—C (O) —O— group, Z represents a C _{1 to} C ₆₀ linear or branched alkylene group, and R ² represents C 1 _{1 to} C _{6 represents} a linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group, or a halogen atom, and when n is 0, at least one or more A halogen atom is bonded to Si. In addition, a is 1-6 and n is 0-3.

These silane coupling agents having a radical polymerizable group may be used alone or in combination. Moreover, the ratio in the case of using both the high toughness tooth adhesive adhesive silane coupling agent of this invention and the silane coupling agent which has a radically polymerizable group for surface treatment has the preferable range of 1: 10-10: 1. When the ratio of the silane coupling agent having a radical polymerizable group is higher than 1:10, the effect of the high-toughness adhesive adhesive silane coupling agent is reduced, and the silane coupling agent having a radical polymerizable group is higher than 10: 1. This is because the effect of the silane coupling agent having a radical polymerizable group is diminished when the ratio is low. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . Further, the surface treatment with the high-toughness tooth-adhesive silane coupling agent of the present invention and the silane coupling agent having a radical polymerizable group may be performed separately or simultaneously. The chemical structure of a silane coupling agent having a typical radical polymerizable group is described below.

このラジカル重合性基を有するシランカップリング剤は１種または複数の組み合わせで用いても良い。また本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤とを共に表面処理に使用する場合の比率は１：１０〜１０：１の範囲が好ましい。１：１０よりラジカル重合性基を有するシランカップリング剤の比率が高い場合には高靭性歯質接着性シランカップリング剤の効果が薄れ、１０：１よりラジカル重合性基を有するシランカップリング剤の比率が低い場合には、ラジカル重合性基を有するシランカップリング剤の効果が薄れるためである。また、処理濃度に関しては無機充填剤のシラノール基密度（ｍｏｌ／ｇ）にもよるが、一般的にはシラノール基密度の等倍から１０倍が好ましい。等倍より低い処理では十分にシランカップリング剤を導入出来ず、また、１０倍を超えた場合にはシランカップリング剤のみの縮合物が生成し、機械的強度に影響を与えるために好ましくない。さらに、本発明の高靭性歯質接着性シランカップリング剤とラジカル重合性基を有するシランカップリング剤による表面処理は別々に行っても、同時に行っても良い。以下に代表的なラジカル重合性基を有するシランカップリング剤の化学構造を記載する。

[Chemical formula 6] shows the molecular structure of the silane coupling agent having a radical polymerizable group used when the inorganic filler is surface-treated with the high-toughness tooth-adhesive silane coupling agent of the present invention. The structure shown in [Chemical Formula 6] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ — group (C ₆ H ₄ represents a phenylene group), R ² represents a C _{1 to} C ₆ linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, phenyl group Alternatively, it represents a halogen atom, and when n is 0, at least one or more halogen atoms are bonded to Si. In addition, n is 0-3.

These silane coupling agents having a radical polymerizable group may be used alone or in combination. Moreover, the ratio in the case of using both the high toughness tooth adhesive adhesive silane coupling agent of this invention and the silane coupling agent which has a radically polymerizable group for surface treatment has the preferable range of 1: 10-10: 1. When the ratio of the silane coupling agent having a radical polymerizable group is higher than 1:10, the effect of the high-toughness adhesive adhesive silane coupling agent is reduced, and the silane coupling agent having a radical polymerizable group is higher than 10: 1. This is because the effect of the silane coupling agent having a radical polymerizable group is diminished when the ratio is low. Further, the treatment concentration depends on the silanol group density (mol / g) of the inorganic filler, but generally it is preferably from 1 to 10 times the silanol group density. If the treatment is lower than 1X, the silane coupling agent cannot be sufficiently introduced, and if it exceeds 10 times, a condensate of only the silane coupling agent is formed, which affects the mechanical strength. . Further, the surface treatment with the high-toughness tooth-adhesive silane coupling agent of the present invention and the silane coupling agent having a radical polymerizable group may be performed separately or simultaneously. The chemical structure of a silane coupling agent having a typical radical polymerizable group is described below.

As the radical polymerizable monomer contained in the dental composition of the present invention, those used in the dental field can be used without any limitation, but it is preferable that the molecular skeleton has a urethane bond. This is because the urethane bond (—NH—C (O) —O—) effectively forms a hydrogen bond with the acidic group. For example, when a carboxyl group (-C (O) OH) is considered as an acidic group, NH of the urethane group and C (O) of the carboxyl group effectively form a hydrogen bond, and similarly, C (O) of the urethane group. This is because hydrogen bonds are effectively formed with the OH of the carboxyl group. The radical polymerizable monomer used in the dental composition of the present invention is, for example, 7,7,9- synthesized by urethane reaction of 2,2,4-trimethylhexamethylene diisocyanate and 2-hydroxyethyl methacrylate (HEMA). Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl dimethacrylate (UDMA), HEMA and HEA with 2,4-toluylene diisocyanate, hydrogenated diphenylmethane diisocyanate Radical polymerizable monomers synthesized by urethane reaction with naphthalene diisocyanate or hexamethylene diisocyanate, aliphatic and / or aromatic diisocyanates and glycerol (meth) acrylate or 3-methacrylol-2-hydro Urethane diacrylates and obtained by reaction of a propyl ester, 1,3-bis (2-isocyanate, 2-propyl) urethane reaction products of a compound having a benzene and hydroxy group. More specifically, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 2,7, 7,9,15-pentamethyl-4,13-18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 2,8,10,10,15-pentamethyl-4,13 , 18-trioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 2,7,7,9,15-pentamethyl-4,13-dioxo-3,14-dioxa-5 12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 2,2 ′-(cyclohexane-1,2-diylbis (methylene)) bis ( Zandiyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2-((2-(((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) cyclohexyl) ) Methylcarbamoyloxy) propyl methacrylate, 2,2 '-(cyclohexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methyl acrylate), 2,2 ′-(bicyclo [4.1.0] heptane-3,4-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2 , 1-Diyl) diacrylate, 2-((4-(((1- (acryloyloxy) propane 2-yloxy) carbonylamino) methyl) bicyclo [4.1.0] heptan-3-yl) methylcarbamoyloxy) propyl methacrylate, 2,2 ′-(bicyclo [4.1.0] heptane-3,4 -Diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methyl acrylate), 7,7,9-trimethyl-4,13-dioxo -3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 7,7,9-trimethyl-4,13,18-trioxo-3,14,17-trioxa-5,12 Diazaicos-19-enyl methacrylate, 8,10,10-trimethyl-4,13,18-trioxo3,14,17-trioxa -5,12-diazaicos-19-enyl methacrylate, 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate) ), 4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 4,13,18-trioxo-3,14,17-trioxa-5,12- Diazaicos-19-enyl methacrylate, 4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 2- (1- (2-((2 -(Acryloyloxy) ethoxy) carbonylamino) -4,4-dimethylcyclohexyl) ethylcarbamoyloxy) ethyl methacrylate 2- (1- (2-((2- (acryloyloxy) ethoxy) carbonylamino) ethyl) -5,5-dimethylcyclohexylcarbamoyloxy) ethyl methacrylate, 2- (2-(((1- (methacrylic Leuoxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2-methylacrylate), 2- (2-(((1 -(Methacryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-trimethylcyclohexylcarbamoyloxy) propane-1,3-diyldiacrylate, 2- (2-(((1- (Acryloyloxy) propan-2-yloxy) carbonylamino) methyl) -2,5,5-to Methylcyclohexylcarbamoyloxy) propane-1,3-diylbis (2-methylacrylate), 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa- 4,11-diazahenicos-20-enyl) pentane-1,5-diyl diacrylate, 3- (15- (2- (acryloyloxy) ethyl) -3,12,19-trioxo-2,13,18-trioxa- 4,11-diazahenicos-20-enyl) pentane-1,5-diylbis (2-methyl acrylate), 2,2 ′-(cyclhexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) ) Bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((2-(((2- (a Acryloyloxy) ethoxy) carbonylamino) methyl) cyclohexyl) methylcarbamoyloxy) ethyl methacrylate, 2,2 ′-(cyclhexane-1,2-diylbis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) Bis (ethane-2,1-diyl) bis (2-methyl acrylate), 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1 , 16-diyl diacrylate, 2,15-bis (cyclohexyloxymethyl) -4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diylbis (2-methyl acrylate), 2,15-bis (cyclohexyloxymethyl) -4,13,18- Lioxo-3,14,17-trioxa-5,12-diazaicos-19-enyl methacrylate, 1,18-bis (cyclohexyloxy) -5,14-dioxo-4,15-dioxa-6,13-diazaoctadecane -2,17-diyl diacrylate, 1- (cyclohexyloxy) -17- (cyclohexyloxymethyl) -5,14,19-trioxo-4,15,18-trioxa-6,13-diazahenicos-20-ene- 2-yl methacrylate, 1,18-bis (cyclohexyloxy) -5,14-dioxo-4,15-dioxa-6,13-diazaoctadecane-2,17-diylbis (2-methyl acrylate), 7,7 , 9-Trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexade 1,16-diylbis (2-methyl acrylate), 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazahexadecane-1,16-diyl diacrylate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 ′ -(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2- (3-(((2- (acryloyloxy) ) Ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 2,2 '-(1,3-phenylenebis (methylene)) bi (Methylazanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(1,3-phenylenebis (methylene)) bis (methyl Azandiyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((3-(((((2- (acryloyloxy) ethoxy) carbonyl) (methyl) amino) methyl ) Benzyl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) Bis (2-methyl acrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (Oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2- (3-(((2- (acryloyloxy) ethoxy) carbonylamino) methyl) benzylcarbamoyloxy) propyl methacrylate, 2 -(3-(((1- (acryloyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) ethyl methacrylate, 4,4 '-(1,3-phenylenebis (methylene)) bis (azanediyl) ) Bisoxomethylene) bis (oxy) bis (4,1-phenylene) bis (2-methylacrylate), 4,4 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bisoxomethylene) bis (Oxy) bis (4,1-phenylene) diacrylate, 4- (3-(( (4- (Acryloxy) phenoxy) carbonylamino) methyl) benzylcarbamoyloxy) phenyl methacrylate, 4,4 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) Bis (butane-4,1-diyl) bis (2-methyl acrylate), 4,4 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane) -4,1-diyl) diacrylate, 4- (3-(((4- (acryloyloxy) butoxy) carbonylamino) methyl) benzylcarbamoyloxy) butyl methacrylate, 2,2 '-(1,3-phenylenebis (Methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- Phenoxypropane-2,1-diyl) bis (2-methylacrylate), 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- Phenoxypropane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3-phenoxypropan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3-phenoxypropyl Methacrylate, 2-2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) bis (2 -Methyl acrylate), 2-2 '-(1,3-phenylenebis (methylene)) bis (azanediyl) Bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (phenylamino) propane- 2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylamino) propyl methacrylate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis ( Oxy) bis (3- (phenylthio) propane-2,1-diyl) bis (2-methylacrylate), 2,2 ′-(1,3phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (Oxy) bis (3- (phenylthio) propane-2,1-diyl) diacrylate, 2- (3- ( (1- (acryloxy) -3- (phenylthio) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (phenylthio) propyl methacrylate, 2,2 ′-(1,3-phenylenebis ( Methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) bis (2-methyl acrylate), 2,2 ′-(1,3- Phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (benzyloxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) ) -3- (Benzyloxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamo Iroxy) -3- (benzyloxy) propyl methacrylate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) ) Propane-2,1-diyl) dibenzoate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propane- 2,1-diyl) dibenzoate, 2,2 ′-(1,3-phenylenebis (methylene)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane- 2,1-diyl) bis (2-methylacrylate), 2,2 '-(1,3-phenylenebis (methylene)) bis Azandiyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (3-(((1- (acryloyloxy) -3- (2 -Phenylacetoxy) propan-2-yloxy) carbonylamino) methyl) benzylcarbamoyloxy) -3- (2-phenylacetoxy) propyl methacrylate 2,2 '-(2,2'-(1,3-phenylene) bis (Propane-2.2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(2,2 ′ -(1,3-phenylene) bis (propane-2.2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis ( Tan-2,1-diyl) diacrylate, 2- (2- (3- (2-((2- (acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy ) Ethyl methacrylate, 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (methylazanediyl) bis (oxomethylene) bis (oxy) bis ( Ethane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (methylazanediyl) Bis (oxomethylene) bis (oxy) bis (ethane-2,1-diyl) diacrylate, 2-((2- (3- (2-(((2- (acryloyloxy) ethoxy) carbonyl) ) (Methyl) amino) propan-2-yl) phenyl) propan-2-yl) (methyl) carbamoyloxy) ethyl methacrylate, 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane) -2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) bis (2-methylacrylate), 2,2 '-(2,2'- (1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (propane-2,1-diyl) diacrylate, 2- (2- ( 3- (2-((2- (acryloyloxy) ethoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) propyl methacrylate 2- (2- (3- (2-((1- (acryloyloxy) propan-2-yloxy) carbonylamino) propan-2-ylcarbamoyloxy) ethyl methacrylate, 4,4 ′-(2,2′- (1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (4,1-phenylene) bis (2-methylacrylate), 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (4,1-phenylene) diacrylate, 4- (2- (3- (2-((4- (acryloyloxy) phenoxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyl B) Phenyl methacrylate, 4,4 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (butane) -4,1-diyl) bis (2-methacrylate), 4,4 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxo Methylene) bis (oxy) bis (butane-4,1-diyl) diacrylate, 4- (2- (3- (2-((4-acryloyloxy) butoxy) carbonylamino) propan-2-yl) phenyl) propane -2-ylcarbamoyloxy) butyl methacrylate, 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis Oxomethylene) bis (oxy) bis (3-phenoxypropane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2) , 2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3-phenoxypropane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (Acryloyloxy) -3-phenoxypropan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3-phenoxypropyl methacrylate, 2,2 ′-(2,2′- (1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (fluoro Enylamino) propane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) Bis (oxomethylene) bis (oxy) bis (3- (phenylamino) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- ( Phenylamino) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (phenylamino) propyl methacrylate, 2,2 ′-(2,2′- (1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (phenylthio) Lopan-2,1-diyl) bis (2-methyl acrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (Oxomethylene) bis (oxy) bis (3- (phenylthio) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (phenylthio)) Propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (phenylthio) propyl methacrylate, 2-2 '-(2,2'-(1,3 -Phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (3- (benzyloxy) propane-2,1-diyl) bis ( -Methyl acrylate), 2-2 '-(2,2'-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (3- (benzyloxy) Propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- (acryloyloxy) -3- (benzyloxy) propan-2-yloxy) carbonylamino) propan-2-yl) ) Phenyl) propan-2-ylcarbamoyloxy) -3- (benzyloxy) propyl methacrylate, 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl) ) Bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (methacryloyloxy) propane-2,1-diyl) dibenzoate, 2,2 ′-( 2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (acryloyloxy) propane-2,1-diyl ) Dibenzoate, 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl)) bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-Phenylacetoxy) propane-2,1-diyl) bis (2-methacrylate), 2,2 ′-(2,2 ′-(1,3-phenylene) bis (propane-2,2-diyl))) Bis (azanediyl) bis (oxomethylene) bis (oxy) bis (3- (2-phenylacetoxy) propane-2,1-diyl) diacrylate, 2- (2- (3- (2-((1- ( Ak Leuoxy) -3- (2-phenylacetoxy) propan-2-yloxy) carbonylamino) propan-2-yl) phenyl) propan-2-ylcarbamoyloxy) -3- (2-phenylacetoxy) propyl methacrylate, polyethylene Examples include glycol dimethacrylate and polyethylene glycol diacrylate.

As the polymerization initiator contained in the dental composition of the present invention, a polymerization initiator used in the industry can be selected and used, and it is preferable to use a polymerization initiator used for dental use. Specifically, among the polymerization initiators included in the dental composition of the present invention, the photopolymerization initiator includes (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or thioxanthones. Quaternary ammonium salts, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds and the like can be mentioned. Moreover, those ratios are preferably 0.5 wt% to 5 wt% with respect to the radical polymerizable monomer. If the concentration is lower than 0.5 wt%, the unpolymerized radical polymerizable monomer increases, so that the mechanical strength decreases. Further, when the concentration is higher than 5 wt%, the degree of polymerization is lowered and the mechanical strength is lowered.

Specific examples of acylphosphine oxides used as photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenyl. Phosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6 -Dimethylphenyl) phosphonate and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, and the like (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentyl phosphine oxide.

Specific examples of thioxanthones or quaternary ammonium salts of thioxanthones used as photopolymerization initiators include, for example, thioxanthone, 2-chlorothioxanthen-9-one, 2-hydroxy-3- (9-oxy -9H-thioxanthen-4-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (1-methyl-9-oxy-9H-thioxanthen-4-yloxy) -N , N, N-trimethyl-propanaminium chloride, 2-hydroxy-3- (9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-propanaminium chloride, 2-hydroxy- 3- (3,4-Dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N Trimethyl-1-propaneaminium chloride, 2-hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2-hydroxy -3- (1,3,4-trimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride and the like.

Specific examples of the α-diketone used as the photopolymerization initiator include, for example, diacetyl, dibenzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4, 4'-oxybenzyl, acenaphthenequinone, etc. are mentioned.

Specific examples of the coumarin compound used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, 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-benzoyl-8-methoxycoumarin, 3,5-carbonylbis (7-methoxycoumarin), 3-benzoyl-6-bromocoumarin, 3,3 ′ -Carbonylbiscoumarin, 3-benzoyl-7-dimethylaminocoumarin, 3 Benzoylbenzo [f] coumarin, 3-carboxycoumarin, 3-carboxy-7-methoxycoumarin, 3-ethoxycarbonyl-6-methoxycoumarin, 3-ethoxycarbonyl-8-methoxycoumarin, 3-acetylbenzo [f] coumarin, 7-methoxy-3- (p-nitrobenzoyl) coumarin, 3- (p-nitrobenzoyl) coumarin, 3-benzoyl-8-methoxycoumarin, 3-benzoyl-6-nitrocoumarin-3-benzoyl-7-diethylaminocoumarin , 7-dimethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 7-diethylamino-3- (4-diethylamino) coumarin, 7-methoxy-3- ( 4-methoxybenzoyl) coumarin, 3- ( -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-benzoimidazoloyl)- 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 , 3,6,7-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one, 10- (2-benzothiazoyl ) -2,3,6,7-tetrahydro-1,1,7,7-tetramethyl 1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolidin-11-one Such compounds.

Among the coumarin compounds, 3,3′-carbonylbis (7-diethylaminocoumarin) and 3,3′-carbonylbis (7-dibutylaminocoumarin) are particularly preferable.

Specific examples of anthraquinones used as a photopolymerization initiator include, for example, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethyl. Anthraquinone, 1-hydroxyanthraquinone, etc. are mentioned.

Specific examples of benzoin alkyl ethers used as photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Specific examples of α-aminoketones used as photopolymerization initiators include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

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

Of the polymerization initiators contained in the dental composition of the present invention, an organic peroxide is preferably used as the chemical polymerization initiator. The organic peroxide used for said chemical polymerization initiator is not specifically limited, A well-known thing can be used. Typical organic peroxides include ketone peroxide, hydroperoxide, diacyl peroxide, dialkyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and the like.

Specific examples of the ketone peroxide used as the chemical polymerization initiator include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.

Specific examples of hydroperoxides used as chemical polymerization initiators include, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydro Examples thereof include peroxide and 1,1,3,3-tetramethylbutyl hydroperoxide.

Specific examples of the diacyl peroxide used as the chemical polymerization initiator include, for example, acetyl peroxide, isobutyryl peroxide, benzoyl peroxide, decanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 2 , 4-dichlorobenzoyl peroxide and lauroyl peroxide.

Specific examples of dialkyl peroxides used as chemical polymerization initiators include, for example, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (T-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like. .

Specific examples of peroxyketals used as chemical polymerization initiators include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl). Peroxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane and 4,4-bis (t-butylperoxy) valeric acid-n -Butyl ester etc. are mentioned.

Specific examples of peroxyesters used as chemical polymerization initiators include, for example, α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2 , 4-Trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate Di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-tilperoxyacetate, t-butylperoxybenzoate and t-butylperoxymaleate Rick acid etc. are mentioned.

Specific examples of peroxydicarbonates used as chemical polymerization initiators include, for example, di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxide. Examples thereof include oxydicarbonate, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

Among organic peroxides, diacyl peroxide is preferably used from the overall balance of safety, storage stability and radical generating ability, and benzoyl peroxide is particularly preferably used.

Specific examples of the polymerization accelerator include amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiol compounds, and the like. Is mentioned.

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

Specific examples of aromatic amines include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, N, N. -Bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl) ) -3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-to Idin, N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethyl Aminobenzoic acid methyl ester, N, N-dimethylaminobenzoic acid-n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid-2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone , 4-dimethylaminobutyl benzoate and the like. Among these, N, N-di (2-hydroxyethyl) -p-toluidine, 4-N, N-dimethylaminobenzoic acid ethyl ester, N, N- from the viewpoint of imparting excellent curability to the composition. Examples thereof include dimethylaminobenzoic acid-n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone.

Specific examples of sulfinic acid and salts thereof used as polymerization accelerators include, for example, p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluene. Calcium sulfinate, benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate 2,4,6-trimethylbenzenesulfinate potassium, 2,4,6-trimethylbenzenesulfinate lithium, 2,4,6-trimethylbenzenesulfinate calcium, 2,4,6-triethyl Benzenesulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, 2,4,6-triethylbenzenesulfinate Calcium, 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfin Lithium acid salt, calcium 2,4,6-triisopropylbenzenesulfinate, and the like, sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate Masui.

Specific examples of the borate compound used as the polymerization accelerator include a borate compound having one aryl group in one molecule. For example, trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p -Fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron, trialkyl [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl ) Phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m-butylphenyl) boron, trialkyl (p- Butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron , Trialkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl A quinolinium salt, a butyl quinolinium salt, etc. are mentioned.

Specific examples of the borate compound having two aryl groups in one molecule include, for example, dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, and dialkyldi (3,5 -Bistrifluoromethyl) phenyl boron, dialkyldi [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron , Dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi ( p-octyloxyph Nyl) boron and dialkyldi (m-octyloxyphenyl) boron (wherein the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group and the like), lithium Salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium Examples include salt.

Furthermore, specific examples of the borate compound having three aryl groups in one molecule include, for example, monoalkyltriphenyl boron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron. , Monoalkyltri (3,5-bistrifluoromethyl) phenyl boron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] Boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri ( p-butyloxyphenyl) boron, monoalkyltri (m-butyloxypheny) 1) Boron, monoalkyltri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (wherein the alkyl group is selected from n-butyl group, n-octyl group, n-dodecyl group, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethyl A quinolinium salt, a butyl quinolinium salt, etc. are mentioned.

Further specific examples of the borate compound having four aryl groups in one molecule include, for example, tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5- Bistrifluoromethyl) phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron , Tetrakis (m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis ( p-octyloxyphenyl) boron, tetrakis m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) tri Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutyl of phenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron Examples include ammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, and butylquinolinium salt.

Among these aryl borate compounds, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule from the viewpoint of storage stability. These aryl borate compounds may be used alone or in combination of two or more.

Specific examples of the babituric acid derivative used as a polymerization accelerator include, for example, barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5 -Butyl barbituric acid, 5-ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethyl barbituric acid, 1,3-dimethyl-5-ethyl barbituric acid 1,3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, , 3-Dimethyl-5-cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1- Chlohexyl-1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methyl Barbituric acid, 1-ethyl-5-isobutylbarbituric acid, 1,3-diethyl-5-butylbarbituric acid, 1-cyclohexyl-5-methylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-cyclohexyl-5-octylbarbituric acid, 1-cyclohexyl-5-hexylbarbituric acid, 5-butyl-1-cyclohexylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and These salts (especially alkali metals or alkaline earth metals are preferred) Gerare, the salts of these barbituric acids include sodium 5-butyl barbituric acid, etc. 1,3,5-trimethyl barbituric acid sodium and 1-cyclohexyl-5-ethyl barbituric sodium tool acid.

Specific examples of particularly suitable barbituric acid derivatives include, for example, 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5 -Phenyl barbituric acid and sodium salts of these barbituric acids.

Specific examples of the triazine compound used as the polymerization accelerator include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trick (Romethyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s- Triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Styryl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (O-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-trimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-biphenylyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- [2- {N, N-bis (2-hydroxyethyl) amino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- {N-hydroxyethyl-N-ethylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N-hydroxyethyl-N-methylamino} ethoxy ] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- {N, N-diallylamino} ethoxy] -4,6-bis (trichloromethyl) -s-triazine, and the like.

Among the triazine compounds exemplified above, 2,4,6-tris (trichloromethyl) -s-triazine is particularly preferable from the viewpoint of polymerization activity, and 2-phenyl-4 is preferable from the viewpoint of storage stability. , 6-Bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, and 2- (4-biphenylyl) -4,6-bis ( Trichloromethyl) -s-triazine. You may use the said triazine compound 1 type or in mixture of 2 or more types.

Specific examples of the copper compound used as the polymerization accelerator include acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like.

Specific examples of tin compounds used as polymerization accelerators include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. Can be mentioned. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

The vanadium compound used as a polymerization accelerator is preferably an IV and / or V vanadium compound. Specific examples of IV and / or V valent vanadium compounds include, for example, divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), Oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammon metavanadate (V), etc. Is mentioned.

Specific examples of halogen compounds used as polymerization accelerators include, for example, dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide. Etc.

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

Specific examples of the thiol compound used as the polymerization accelerator include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

Furthermore, in order to give adhesiveness as needed, you may add the radically polymerizable monomer which has the conventional acidic group to the dental adhesive composition of this invention. Specific examples of the radical polymerizable monomer having an acidic group include 4- [2- (N-methacryloylaminoethylamino)]-trimeritec acid, 4- [3- (N-methacryloylaminopropylamino)]. Trimerite acid, 4- [3- (N-methacryloylamino-iso-propylamino)]-Trimerite acid, 4- [4- (N-methacryloylaminobutylhexylamino)]-Trimerite acid, 4- [ 4- (N-methacryloylamino-iso-butylhexylamino)]-trimeritec acid, 4- [5- (N-methacryloylaminopentylamino)]-trimeritec acid, 4- [5- (N-methacryloylamino-) iso-pentylamino)]-trimeritec acid, -[6- (N-methacryloylaminohexylamino)]-trimeritec acid, 4- [6- (N-methacryloylamino-iso-hexylamino)]-trimeritec acid, 4- [10- (N-methacryloylamino) Decylamino)]-trimeritec acid, 4- [10- (N-methacryloylamino-iso-decylamino)]-trimeritec acid, 4- [2- (N-methacryloylaminoethylamino)]-trimeritec acid anhydride , 4- [3- (N-methacryloylaminopropylamino)]-trimeritec acid anhydride, 4- [3- (N-methacryloylamino-iso-propylamino)]-trimeritec acid anhydride, 4- [4 -(N-methacryloyl Minobutylhexylamino)]-trimeritec acid anhydride, 4- [4- (N-methacryloylamino-iso-butylhexylamino)]-trimeritec acid anhydride, 4- [5- (N-methacryloylaminopentylamino) ] -Trimeritec acid anhydride, 4- [5- (N-methacryloylamino-iso-pentylamino)]-trimeritec acid anhydride, 4- [6- (N-methacryloylaminohexylamino)]-trimeritec acid Anhydride, 4- [6- (N-methacryloylamino-iso-hexylamino)]-trimeritec acid Anhydride, 4- [10- (N-methacryloylaminodecylamino)]-trimeritecide acid Hydride, 4- [10- (N-methacryloylamino-iso-decylamino)]-trimeritec acid anhydride, 4- [2- (N-methacryloylaminoethylamino)]-trimeritec acid, 4- [4- (N-methacryloylaminobutylhexylamino)]-trimeritec acid, 4- [6- (N-methacryloylaminohexylamino)]-trimeritec acid, 4- [10- (N-methacryloylaminodecylamino)]-trime Litec acid, 4- [2- (N-methacryloylaminoethylamino)]-trimeritec acid anhydride, 4- [4- (N-methacryloylaminobutylhexylamino)]-trimellitec acid anhydride, 4- [ 6- (N-methacrylo Ruaminohexylamino)]-trimeritec acid anhydride, 4- [10- (N-methacryloylaminodecylamino)]-trimeritec acid anhydride, 3- (meth) acryloxypropyl-3-phosphonopropionate 3- (meth) acryloxypropyl phosphonoacetate, 4- (meth) acryloxybutyl-3-phosphonopropionate, 4- (meth) acryloxybutylphosphonoacetate, 5- (meth) acryloxypentyl -3-phosphonopropionate, 5- (meth) acryloxypentylphosphonoacetate, 6- (meth) acryloxyhexyl-3-phosphonopropionate, 6- (meth) acryloxyhexylphosphonoacetate, Bis [2- (meth) acryloxyethyl] hydro Phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydrogen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl Dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, dipentaerythritol pentamethacrylate, N- (meth) acryloyl-ω-aminopropylphosphonic acid, N- (meth) acryloyl 1-amino-1 -Benzylphosphonic acid, N-methacryloyl 1-methyl-1-aminophosphonic acid, N-methacryloyl 1-ethyl-1-aminophosphonic acid, N-methacrylic acid Royl 1-butyl-1-aminophosphonic acid, 5- (N-methacryloyl) pentyl-1-aminomethylphosphonic acid, 6- (N-methacryloyl) hexyl-1-aminomethylphosphonic acid, 10- (N -Methacryloyl) decyl-1-aminomethylphosphonic acid, 6- (N-methacryloyl) hexyl-1-aminopropyl phonic acid, 6- (N-methacryloyl) hexyl-2-aminopropyl phonic acid, 10- ( N-methacryloyl) decyl-2-aminopropyl phonic acid, methacrylic acid, 4- (meth) acryloxyethyl trimellitic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) acryloyloxyb Ruoxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid, 2 -(Meth) acryloyloxyethylmaleic acid, 5- (meth) acryloylaminopentylcarboxylic acid, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 7- (meth) acryloyloxy-1 , 1-Heptanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxy Rick acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, N- (meth) acryloylalanine, N- (meth) acryloylglycine, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 6-sulfohexyl (meth) acrylate, 10-sulfodecyl (meth) acrylate, 2- (meth) acrylamido-2-methylpropane sulfonic acid, 6- (meth) acryloxyhexyl-3-phosphonoacetate, 6- ( (Meth) acryloxyhexyl-3-phosphonopropionate, 10- (meth) acryloxydecyl hydrogen phosphate, N- (meth) acryloyl 1-amino-1-benzylphosphonic acid, N-methacryloyl 1-methyl- 1-A Noho Suho Nick acid, 4- (meth) acryloxy ethyl trimellitate Tech acid, 4- (meth) acryloyloxyethyl trimellitate Tech acid anhydride and the like.

High-toughness tooth-adhesive silane coupling agent, method for producing dental inorganic filler surface-treated with high-toughness tooth-adhesive silane coupling agent, and method for preparing a dental composition containing them The physical characteristics will be described in detail, but the present invention is not limited to these descriptions.

(Synthesis Example 1) Synthesis 1 of a high-toughness dental adhesive silane coupling agent having an acidic group
In a four-necked flask (200 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, a solution obtained by dissolving 10.0 g (0.10 mol) of dihydrofuran-2,5-dione in 50 mL of tetrahydrofuran was added. It was slowly added dropwise so that the temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and dihydrofuran-2,5-dione peaks disappear and new peak: 4,4-diethoxy-11,22-dimethyl-9,13,20,24-tetraoxo-3,14,19-trioxa -10,23-dithia-8-aza-4-silaheptacosane-27-euic acid (molecular weight 641.9) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 2) Synthesis 2 of a high-toughness tooth-adhesive silane coupling agent having an acidic group
In a four-necked flask (200 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C. When the temperature became constant, dihydro-2H-pyran-2,6 (3H) -dione: 11.4 g (0.10 mol) of 50 mL of tetrahydrofuran The solution dissolved in was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and dihydrofuran-2,5-dione peaks disappear and new peak: 4,4-diethoxy-11,22-dimethyl-9,13,20,24-tetraoxo-3,14,19-trioxa -10,23-dithia-8-aza-4-silaoctacosane-28-euic acid (molecular weight 655.9) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 3) Synthesis 3 of a high-toughness dental adhesive silane coupling agent having an acidic group
In a four-necked flask (200 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid: 19.2 g (0. 10 mol) in tetrahydrofuran (50 mL) was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid peaks disappeared and new peaks: 4- (21,21-diethoxy-3,14-dimethyl-5,12 , 16-trioxo-6,11,22-trioxa-2,15-dithia-17-aza-21-silatetracosanoyl) isophthalic acid (molecular weight 733.9). Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 4) Synthesis 4 of high-toughness dental adhesive silane coupling agent having an acidic group
Butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin in a four-necked flask (500 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C. When the temperature became constant, 10.1 g (0.10 mol) of triethylamine and 150 mL of chloroform were added and sufficiently stirred to make uniform. Next, a solution prepared by dissolving 21.1 g (0.10 mol) of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride in 150 mL of chloroform was slowly added so that the internal temperature did not exceed 50 ° C. It was dripped. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, triethylamine hydrochloride was removed by filtration, and HPLC and FT-IR measurements were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride peaks disappeared and a new peak: 4-((3-((1,3-dioxo-1,3-dihydro Isobenzofuran-5-carbonyl) thio) butanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight) 715.9) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 5) Synthesis 5 of high-toughness tooth adhesive silane coupling agent having an acidic group
In a four-necked flask (200 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Then, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when it became constant temperature, 2,2-dimethoxy-1,2-diphenylethane-1-one: 33.2 mg (corresponding to 500 ppm) was added. Stirred uniformly. Next, a solution prepared by dissolving 12.2 g (0.10 mol) of allyl phosphonic acid in 50 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and allyl phosphonic acid peaks disappear and new peaks: (4,4-diethoxy-11,22-dimethyl-9,13,20-trioxo-3,14,19-trioxa-10,23- Dithia-8-aza-4-silahexacosane-26-yl) phosphonic acid (molecular weight 663.9) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 6) Synthesis 6 of a high-toughness dental adhesive silane coupling agent having an acidic group
A (2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl) tris (three, four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser was used. Ethane-2,1-diyl) tris (3-mercaptobutanoate): 56.8 g (0.10 mol) and dibutyltin (IV) dilaurate: 81.5 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw material (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris (ethane-2,1-diyl) tris (3-mercaptobutano Ate) and triethoxy (3-isocyanatopropyl) silane peaks disappeared and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10- Thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis ( 3-mercaptobutanoate) (molecular weight 815.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, a solution of dihydrofuran-2,5-dione: 20.0 g (0.20 mol) dissolved in 100 mL of tetrahydrofuran was added. It was slowly added dropwise so that the temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2 , 4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3-mercaptobutanoate) and dihydrofuran-2,5-dione The peak disappears and a new peak: 4,4 ′-(((((5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8- Aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl)) bis (oxy)) Bis (4-oxobutane-4,2-diyl )) Bis (sulfanediyl)) bis (4-oxobutanoic acid) (molecular weight 1015.2) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 7) Synthesis 7 of a high-toughness tooth-bonding silane coupling agent having an acidic group 7
A (2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl) tris (three, four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser was used. Ethane-2,1-diyl) tris (3-mercaptobutanoate): 56.8 g (0.10 mol) and dibutyltin (IV) dilaurate: 81.5 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw material (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris (ethane-2,1-diyl) tris (3-mercaptobutano Ate) and triethoxy (3-isocyanatopropyl) silane peaks disappeared and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10- Thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis ( 3-mercaptobutanoate) (molecular weight 815.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, dihydro-2H-pyran-2,6 (3H) -dione: 22.8 g (0.20 mol) was added to 100 mL of tetrahydrofuran. The solution dissolved in was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2 , 4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3-mercaptobutanoate) and dihydro-2H-pyran-2,6 The peak of (3H) -dione disappears and a new peak: 5,5 ′-(((((5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa- 10-thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) ) Bis (oxy)) bis (4-oxobutane) -4,2-diyl)) bis (sulfanediyl)) bis (5-oxopentanoic acid) (molecular weight 1043.3) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 8) Synthesis 8 of high-toughness tooth-adhesive silane coupling agent having an acidic group
A (2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl) tris (three, four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser was used. Ethane-2,1-diyl) tris (3-mercaptobutanoate): 56.8 g (0.10 mol) and dibutyltin (IV) dilaurate: 81.5 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw material (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris (ethane-2,1-diyl) tris (3-mercaptobutano Ate) and triethoxy (3-isocyanatopropyl) silane peaks disappeared and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10- Thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis ( 3-mercaptobutanoate) (molecular weight 815.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid: 38.4 g (0. 20 mol) in 100 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2 , 4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3-mercaptobutanoate) and 1,3-dioxo-1,3 The peak of -dihydroisobenzofuran-5-carboxylic acid disappears and a new peak: 2,2 '-((((((5- (4,4-diethoxy-11-methyl-9,13-dioxo- 3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane- 2,1-diyl)) bi S (oxy)) bis (4-oxobutane-4,2-diyl)) bis (sulfanediyl)) bis (carbonyl)) diterephthalic acid (molecular weight 1199.3) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 9) Synthesis 9 of high-toughness dental adhesive silane coupling agent having an acidic group
In a four-necked flask (500 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris ( Ethane-2,1-diyl) tris (3-mercaptobutanoate): 56.8 g (0.10 mol) and dibutyltin (IV) dilaurate: 81.5 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw material (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris (ethane-2,1-diyl) tris (3-mercaptobutano Ate) and triethoxy (3-isocyanatopropyl) silane peaks disappeared and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10- Thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis ( 3-mercaptobutanoate) (molecular weight 815.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when it became constant temperature, 20.2 g (0.20 mol) of triethylamine and 150 mL of chloroform were added and sufficiently stirred to homogenize. Then, a solution of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride: 42.1 g (0.20 mol) dissolved in 150 mL of chloroform was slowly added so that the internal temperature did not exceed 50 ° C. It was dripped. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, triethylamine hydrochloride was removed by filtration, and HPLC and FT-IR measurements were performed. As a result of HPLC measurement, (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2 , 4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3-mercaptobutanoate) and 1,3-dioxo-1,3 -The peak of dihydroisobenzofuran-5-carbonyl chloride disappears and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8 -Aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3- ( (1,3-Geo Seo-1,3-dihydro-isobenzofuran-5-carbonyl) confirmed thio) butanoate) (molecular weight 1163.3). Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 10) Synthesis 10 of high-toughness dental adhesive silane coupling agent having an acidic group
A (2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl) tris (three, four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser was used. Ethane-2,1-diyl) tris (3-mercaptobutanoate): 56.8 g (0.10 mol) and dibutyltin (IV) dilaurate: 81.5 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw material (2,4,6-trioxo-1,3,5-triazinan-1,3,5-triyl) tris (ethane-2,1-diyl) tris (3-mercaptobutano Ate) and triethoxy (3-isocyanatopropyl) silane peaks disappeared and a new peak: (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10- Thia-8-aza-4-silahexadecan-16-yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis ( 3-mercaptobutanoate) (molecular weight 815.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 2,2-dimethoxy-1,2-diphenylethane-1-one: 53.0 mg (equivalent to 500 ppm) was added. Thoroughly stirred and homogenized. Thereafter, a solution prepared by dissolving 24.4 g (0.20 mol) of allyl phosphonic acid in 100 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, (5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecan-16-yl) -2 , 4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl) bis (3-mercaptobutanoate) and allyl phosphonic acid peaks disappeared , A new peak: (((((5- (4,4-diethoxy-11-methyl-9,13-dioxo-3,14-dioxa-10-thia-8-aza-4-silahexadecane-16 -Yl) -2,4,6-trioxo-1,3,5-triazinan-1,3-diyl) bis (ethane-2,1-diyl)) bis (oxy)) bis (4-oxobutane-4, 2-Diyl)) Bi (Sulfanediyl)) bis (propane-3,1-diyl)) bis (phosphine phonic acid)
(Molecular weight 1059.2) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 11) Synthesis 11 of a high-toughness dental adhesive silane coupling agent having an acidic group 11
In a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, 2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis ( 3-Mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 79.2 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic After that, a solution obtained by dissolving 30.0 g (0.30 mol) of dihydrofuran-2,5-dione in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the addition, an oil bath was added. The reaction was continued for 5 hours while maintaining the temperature of 2. After completion of the aging, HPLC and FT-IR measurements were performed, and as a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3 , 7-Dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis ( The 3-mercaptobutanoate) and dihydrofuran-2,5-dione peaks disappear and a new peak: 11-(((3-((3-carboxypropano L) thio) butanoyl) oxy) methyl) -11- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -6,16-dimethyl-4,8,14,18-tetraoxo-9,13-dioxa-5,17-dithiahenicosandioic acid (molecular weight 1092.3) was confirmed, and FT-IR measurement was performed. As a result, the disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed, and the chemical structural formula of the compound synthesized in this example is described below.

(Synthesis Example 12) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 12
In a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, 2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis ( 3-mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 792 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic Then, a solution of 34.2 g (0.30 mol) of dihydro-2H-pyran-2,6 (3H) -dione dissolved in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was carried out.After completion of the aging, HPLC and FT-IR measurements were carried out. -5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1 , 3-Diylbis (3-mercaptobutanoate) and dihydro-2H-pyran-2,6 (3H) -dione disappeared and a new peak: 12-(( 3-((4-Carboxybutanoyl) thio) butanoyl) oxy) methyl) -12- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8- Aza-12-silapentadecyl) -7,17-dimethyl-5,9,15,19-tetraoxo-10,14-dioxa-6,18-dithiatricosandioic acid (molecular weight 1134.4) As a result of FT-IR measurement, the disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed, and the chemical structural formula of the compound synthesized in this example is described below.

(Synthesis Example 13) Synthesis 13 of a high-toughness tooth-bonding silane coupling agent having an acidic group
In a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, 2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis ( 3-mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 79.2 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid: A solution of 57.6 g (0.30 mol) dissolved in 150 mL of tetrahydrofuran was adjusted so that the internal temperature did not exceed 50 ° C. After the completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, followed by aging.After completion of the aging, HPLC and FT-IR measurements were performed. 12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-(((3-mercaptobutanoyl) oxy) Methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5 The peak of carboxylic acid disappears and a new peak: 2,2 ′-(8-(((3-((2,4-dicarboxybenzoyl) thio) butanoyl) oxy) methyl) -8- (12, 12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -3,13-dimethyl-5,11-dioxo-6,10 -Dioxa-2,14-dithiapentadecanedioyl) diterephthalic acid (molecular weight 1368.5) was confirmed, and as a result of FT-IR measurement, the disappearance of thiol group absorption in the vicinity of 2575 cm ^-1 was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 14) Synthesis 14 of a high-toughness dental adhesive silane coupling agent having an acidic group
2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (( 3-Mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 79.2 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic After that, 30.3 g (0.30 mol) of triethylamine and 150 mL of chloroform were added, and the mixture was sufficiently stirred and homogenized, and then 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride: 63.2 g ( 0.30 mol) in 150 mL of chloroform was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of ripening, triethylamine hydrochloride was removed by filtration, and HPLC and FT-IR measurements were carried out, and as a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13- Dioxa-6-thia-8-aza-12-silapentadecyl) -2-(((3-mercaptobutanoy The peaks for) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride disappear and new peaks: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-((((3-((1 , 3-Dioxo-1,3-dihydroisobenzofuran-5-carbonyl) thio) butanoyl) oxy) methyl) propane-1,3-diyl bis (3-((1,3-dioxo-1,3-dihydroiso) Benzofuran-5-carbonyl) thio) butanoate) (molecular weight 1314.5) was confirmed, and as a result of FT-IR measurement, absorption of thiol groups in the vicinity of 2575 cm ⁻¹ was observed. Confirmed the loss. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 15) Synthesis 15 of a high-toughness dental adhesive silane coupling agent having an acidic group 15
In a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, 2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis ( 3-Mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 79.2 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic 2,2-dimethoxy-1,2-diphenylethane-1-one: 57.9 mg (equivalent to 500 ppm) was added, and the mixture was sufficiently stirred and homogenized, then allyl phosphonic acid: 36.6 g ( 0.30 mol) in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of the aging, HPLC and FT-IR measurement were performed, and the result of HPLC measurement was 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8. Aza-12-silapentadecyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercap) Butanoate) and allyl phosphonic acid peaks disappeared and a new peak: (10- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza) -12-silapentadecyl) -5,15-dimethyl-7,13-dioxo-10-(((3-((3-phosphonopropyl) thio) butanoyl) oxy) methyl) -8,12-dioxa- 4,16-dithianonadecane-1,19-diyl) bis (phosphonic acid) (molecular weight 1158.3) was confirmed, and as a result of FT-IR measurement, the disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 16) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 16
2-(((3-Mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, 2-((((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis (3-mercaptobutanoate and triethoxy (3-isocyanatopropyl) which are raw materials ) The silane peak disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl ) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0), and as a result of FT-IR measurement, 2280-2250 cm ⁻¹ of isocyanate absorption was confirmed. After confirming the disappearance, the temperature of the oil bath in the four-necked flask was set to 40 ° C., and when the temperature became constant, dihydrofuran-2,5-dione: A solution obtained by dissolving 0.0 g (0.20 mol) in 100 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath. After completion of the aging, HPLC and FT-IR measurement were performed, and as a result of the HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6 -Thia-8-aza-12-silapentadecyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and dihydrofuran-2,5-dione peaks disappear and new Peak: 11- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) 6,11,16-trimethyl-4,8,14,18-tetraoxo-9,13-dioxa-5,17-dithiahenicosandioic acid (molecular weight 874.1) was confirmed, and FT-IR. As a result of the measurement, the disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed, and the chemical structural formula of the compound synthesized in this example is described below.

(Synthesis Example 17) Synthesis 17 of a high-toughness dental adhesive silane coupling agent having an acidic group
2-(((3-Mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-(((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, dihydro-2H-pyran-2,6 (3H) -dione: 22.8 g (0.20 mol) was added to 100 mL of tetrahydrofuran. The solution dissolved in was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and dihydro-2H-pyran-2,6 (3H) -dione disappear and a new peak: 12- (12,12-diethoxy-5- Methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -7,12,17-trimethyl-5,9,15,19-tetraoxo-10,14 -Dioxa-6,18-dithiatricosandioic acid (molecular weight 902.2) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 18) Synthesis 18 of high-toughness dental adhesive silane coupling agent having acidic group 18
2-(((3-Mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-(((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid: 38.4 g (0. 20 mol) in 100 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane- The peaks of 1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid disappeared, and a new peak: 4- (8- ( ((3-((2,5-dicarboxybenzoyl) thio) butanoyl) oxy) methyl) -20,20-diethoxy-3,8,13-trimethyl-5,11,15-trioxo-6,10,21 -Trioxa-2,14-dithia-16-aza-20-silatricosanoyl) isophthalic acid (molecular weight 1058) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 19) Synthesis 19 of high-toughness tooth-adhesive silane coupling agent having an acidic group
2-((((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (500 mL volume) equipped with a stirring blade, a thermometer, a dropping funnel and a condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-(((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 20.2 (0.20 mol) of triethylamine and 150 mL of chloroform were added and sufficiently stirred to homogenize. Then, a solution of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride: 42.1 g (0.20 mol) dissolved in 150 mL of chloroform was slowly added so that the internal temperature did not exceed 50 ° C. It was dripped. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, triethylamine hydrochloride was removed by filtration, and HPLC and FT-IR measurements were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride disappeared and a new peak: 2- (12,12- Diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane-1,3-diyl bis (3-((1 , 3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl) thio) butanoate) (molecular weight 1022.2). Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 20) Synthesis 20 of high-toughness dental adhesive silane coupling agent having acidic group 20
2-(((3-Mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-(((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath was set to 40 ° C. in the four-necked flask, and when the temperature became constant, 45.9 mg (corresponding to 500 ppm) of 2,2-dimethoxy-1,2-diphenylethane-1-one was sufficiently added. And homogenized. Next, a solution prepared by dissolving 24.4 g (0.20 mol) of allyl phosphonic acid in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and allylphosphonic acid disappeared and a new peak: 10- (12,12-diethoxy-5-methyl-3,7-dioxo-2, 13-dioxa-6-thia-8-aza-12-silapentadecyl) -5,10,15-trimethyl-7,13-dioxo-8,12-dioxa-4,16-dithianonadecane-1,19-diyl ) Bis (phosphonic acid) (molecular weight 918.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 21) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 21
2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (3-mercaptobutanoate): 44.1 g (0.10 mol) and dibutyltin (IV) dilaurate: 68.8 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-ethylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 688.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, a solution of dihydrofuran-2,5-dione: 20.0 g (0.20 mol) dissolved in 100 mL of tetrahydrofuran was added. It was slowly added dropwise so that the temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and dihydrofuran-2,5-dione disappear and a new peak: 11- (12,12-diethoxy-5-methyl-3,7- Dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -11 ethyl-6,16-dimethyl-4,8,14,18-tetraoxo-9,13-dioxa-5 17-dithiahenicosandioic acid (molecular weight 888.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 22) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 22
2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (3-mercaptobutanoate): 44.1 g (0.10 mol) and dibutyltin (IV) dilaurate: 68.8 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-ethylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 688.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, dihydro-2H-pyran-2,6 (3H) -dione: 22.8 g (0.20 mol) was added to 100 mL of tetrahydrofuran. The solution dissolved in was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and dihydro-2H-pyran-2,6 (3H) -dione disappear and a new peak: 12- (12,12-diethoxy-5- Methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -12-ethyl-7,17-dimethyl-5,9,15,19-tetraoxo-10 , 14-dioxa-6,18-dithiatricosandioic acid (molecular weight 916.2) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 23) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 23
2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (3-mercaptobutanoate): 44.1 g (0.10 mol) and dibutyltin (IV) dilaurate: 68.8 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-ethylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 688.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid: 38.4 g (0. 20 mol) in 100 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane- The peaks of 1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid disappeared, and a new peak: 4- (8- ( ((3-((2,5-dicarboxybenzoyl) thio) butanoyl) oxy) methyl) -20,20-diethoxy-8-ethyl-3,13-dimethyl-5,11,15-trioxo-6,10 , 21-trioxa-2,14-dithia-16-aza-20-silatricosanoyl) isophthalic acid (molecular weight 1072.3). Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 24) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 24
2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (3-mercaptobutanoate): 44.1 g (0.10 mol) and dibutyltin (IV) dilaurate: 68.8 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-ethylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 688.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when the temperature became constant, 20.2 (0.20 mol) of triethylamine and 150 mL of chloroform were added and sufficiently stirred to homogenize. Then, a solution of 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride: 42.1 g (0.20 mol) dissolved in 150 mL of chloroform was slowly added so that the internal temperature did not exceed 50 ° C. It was dripped. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, triethylamine hydrochloride was removed by filtration, and HPLC and FT-IR measurements were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and 1,3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl chloride disappeared and a new peak: 2- (12,12- Diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane-1,3-diyl bis (3-((1 , 3-dioxo-1,3-dihydroisobenzofuran-5-carbonyl) thio) butanoate) (molecular weight 1036.2). Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 25) Synthesis of high-toughness tooth-adhesive silane coupling agent having acidic group 25
2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis in a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser (3-mercaptobutanoate): 44.1 g (0.10 mol) and dibutyltin (IV) dilaurate: 68.8 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-ethyl-2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-ethylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 688.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath in the four-necked flask was set to 40 ° C., and when it became constant temperature, 45.6 mg (corresponding to 500 ppm) of 2,2-dimethoxy-1,2-diphenylethane-1-one was sufficiently added. And homogenized. Next, a solution prepared by dissolving 24.4 g (0.20 mol) of allyl phosphonic acid in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-ethylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and allyl phosphonic acid disappeared and a new peak: (10- (12,12-diethoxy-5-methyl-3,7-dioxo-2) , 13-dioxa-6-thia-8-aza-12-silapentadecyl) -10-ethyl-5,15-dimethyl-7,13-dioxo-8,12-dioxa-4,16-dithianonadecane-1, 19-Diyl) bis (phosphonic acid) (molecular weight 932.1) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 26) Synthesis 1 of a high-toughness dental adhesive silane coupling agent having an aldehyde group
In a four-necked flask (200 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, butane-1,4-diylbis (3-mercaptobutanoate): 29.4 g (0.10 mol), dibutyltin (IV) Dilaurate: 54.1 mg (equivalent to 1000 ppm) was added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of butane-1,4-diylbis (3-mercaptobutanoate) and triethoxy (3-isocyanatopropyl) silane, which are raw materials, disappeared, and a new peak: 4-((3- Mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 541.8) was confirmed. . Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Then, the temperature of the oil bath of the four-necked flask was set to 40 ° C., and when it became constant temperature, 2,2-dimethoxy-1,2-diphenylethane-1-one: 33.2 mg (corresponding to 500 ppm) was added. Stirred uniformly. Next, a solution obtained by dissolving 5.61 g (0.10 mol) of acrylaldehyde in 50 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 4-((3-mercaptobutanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo-3-oxa-10-thia-8-aza-4-silatridecane-13 -Oate and allyl phosphonic acid peaks disappear and new peaks: 4-((3-((3-oxopropyl) thio) butanoyl) oxy) butyl 4,4-diethoxy-11-methyl-9-oxo -3-Oxa-10-thia-8-aza-4-silatridecan-13-oate (molecular weight 597.9) was confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 27) Synthesis 2 of high-toughness tooth-adhesive silane coupling agent having an aldehyde group
2-(((3-Mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diylbis was added to a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser. (3-mercaptobutanoate): 42.7 g (0.10 mol) and dibutyltin (IV) dilaurate: 67.4 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, raw materials 2-(((3-mercaptobutanoyl) oxy) methyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-methylpropane-1,3-diyl bis (3-mercaptobutanoate) (molecular weight 674.0) was confirmed. Further, as a result of FT-IR measurement, disappearance of isocyanate absorption at 2280 to 2250 cm ⁻¹ was confirmed. Thereafter, the temperature of the oil bath was set to 40 ° C. in the four-necked flask, and when the temperature became constant, 45.9 mg (corresponding to 500 ppm) of 2,2-dimethoxy-1,2-diphenylethane-1-one was sufficiently added. And homogenized. Next, a solution obtained by dissolving 11.2 g (0.20 mol) of acrylaldehyde in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. As a result of HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane- The peaks for 1,3-diyl bis (3-mercaptobutanoate) and allylphosphonic acid disappeared and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2, 13-dioxa-6-thia-8-aza-12-silapentadecyl) -2-methylpropane-1,3-diylbis (3-((3-oxopropyl) thio) butanoate) (molecular weight 786.1) confirmed. Further, as a result of FT-IR measurement, disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

(Synthesis Example 28) Synthesis 3 of a high-toughness dental adhesive silane coupling agent having an aldehyde group
In a four-necked flask (300 mL volume) equipped with a stirring blade, thermometer, dropping funnel and condenser, 2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis ( 3-Mercaptobutanoate): 54.5 g (0.10 mol) and dibutyltin (IV) dilaurate: 79.2 mg (equivalent to 1000 ppm) were added and dissolved uniformly. In the dropping funnel, 24.7 g (0.10 mol) of triethoxy (3-isocyanatopropyl) silane was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and triethoxy (3-isocyanatopropyl) silane was added dropwise with stirring so that the internal temperature did not exceed 80 ° C. After completion of the dropwise addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the raw materials (2,2-bis (((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoate) and triethoxy (3-isocyanate) The peak of propyl) silane disappears and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12-silapenta Decyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diylbis (3-mercaptobutanoate) (molecular weight 792.1) was confirmed, and FT-IR measurement was performed. results confirmed the disappearance of the isocyanate absorption at 2280~2250cm ^-1. then, the four-necked flask to set the temperature of the oil bath to 40 ° C., it thermostatic 2,2-dimethoxy-1,2-diphenylethane-1-one: 57.9 mg (equivalent to 500 ppm) was added, and the mixture was sufficiently stirred and homogenized. 30 mol) in 150 mL of tetrahydrofuran was slowly added dropwise so that the internal temperature did not exceed 50 ° C. After completion of the addition, the reaction was continued for 5 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of the measurement, HPLC and FT-IR measurements were carried out, and as a result of the HPLC measurement, 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza -12-silapentadecyl) -2-(((3-mercaptobutanoyl) oxy) methyl) propane-1,3-diyl bis (3-mercaptobutanoe ) And the allyl phosphonic acid peak disappeared and a new peak: 2- (12,12-diethoxy-5-methyl-3,7-dioxo-2,13-dioxa-6-thia-8-aza-12 -Silapentadecyl) -2-(((3-((3-oxopropyl) thio) butanoyl) oxy) methyl) propane-1,3-diyl bis (3-((3-oxopropyl) thio) butanoate ( In addition, as a result of FT-IR measurement, the disappearance of thiol group absorption in the vicinity of 2575 cm ⁻¹ was confirmed, and the chemical structural formula of the compound synthesized in this example is shown below.

Comparative Synthesis Example (Comparative Synthesis Example 1) Comparative Synthesis Example 1 of Silane Coupling Agent Having an Acid Group
Dihydrofuran-2,5-dione: 10.1 g (0.10 mol) and 100 mL of THF were uniformly dissolved in a four-necked flask (200 mL volume) equipped with a stirring blade, a thermometer, a dropping funnel and a condenser. To the dropping funnel, 3- (triethoxysilyl) propan-1-ol: 22.2 g (0.10 mol) was weighed. Next, the four-necked flask was immersed in an oil bath heated to 75 ° C., and 3- (triethoxysilyl) propan-1-ol was added dropwise with stirring. After completion of the dropwise addition, the reaction was continued for 12 hours while maintaining the temperature of the oil bath, and aging was performed. After completion of aging, HPLC and FT-IR measurement were performed. The analytical conditions for HPLC measurement are column ZORBAX-ODS, acetonitrile / distilled water = 7/3, flow rate 0.5 mL / min, multi-scan UV detector, RI detector, and MS detector. FT-IR measurement was performed by the ATR method. As a result of HPLC measurement, the peaks of dihydrofuran-2,5-dione and 3- (triethoxysilyl) propan-1-ol as raw materials disappeared, and a new peak: 4-oxo-4- (3- (tri Ethoxysilyl) propoxy) butanoic acid (molecular weight 322.4) was confirmed. Further, as a result of FT-IR measurement, disappearance of hydroxyl group absorption in the vicinity of 3600 cm ⁻¹ was confirmed. The chemical structural formulas of the compounds synthesized in this example are described below.

Examples 1 to 28 (Preparation of dental inorganic filler by high-toughness tooth-bonding silane coupling agent)
OX-50 (manufactured by Nippon Aerosil Co., Ltd.) in combination with the high-toughness dental adhesive silane coupling agent synthesized in Synthesis Examples 1 to 28 and the radical polymerizable silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.) The surface treatment was performed. A specific surface treatment method is described below. The amount and combination of silane coupling agents listed in Table 1 were dissolved in 150 mL of acetone and added to a 500 mL eggplant flask containing 15.0 g of OX-50. Thereafter, an electromagnetic stirrer was added and the mixture was stirred for 10 minutes and further dispersed for 5 minutes by an ultrasonic disperser of 28 KHz-150 W. After completion of the dispersion, 0.6 g of distilled water was added with stirring, and the flask was immersed in a boiling water bath and refluxed for 5 hours. Then, acetone was distilled off with an evaporator to obtain a dental inorganic filler subjected to surface treatment.

Example 29 (Preparation of a dental inorganic filler with a high-toughness tooth-adhesive silane coupling agent)
To a four-necked flask (2 L volume) equipped with a stirring blade, a thermometer, a dropping funnel, and a cooling tube, 109.2 g (0.10 mol) of the high toughness tooth adhesive silane coupling agent synthesized in Synthesis Example 11 was added. Weighed, added 500 mL of ethanol and stirred well. Under ice-cooling, 400 mL of 1N aqueous sodium hydroxide solution was poured all at once and stirred vigorously. Stirring was stopped after 1 hour. Thereafter, the solution was returned to acidic with 1N hydrogen chloride water, and decantation with distilled water was repeated to remove sodium chloride and excess hydrogen chloride. Thereafter, a white spherical dental inorganic filler was obtained by freeze-drying. The average particle size of the obtained dental inorganic filler was 100 nm.

Comparative Example 1
The surface treatment of OX-50 (manufactured by Nippon Aerosil Co., Ltd.) was performed by combining the silane coupling agent synthesized in Comparative Synthesis Example 1 and the radical polymerizable silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.). A specific surface treatment method is described below. 1.09 g of the silane coupling agent synthesized in Comparative Synthesis Example 1 and KBM503: 0.36 g were dissolved in 150 mL of acetone and added to a 500 mL eggplant flask containing 15.0 g of OX-50. Thereafter, an electromagnetic stirrer was added and the mixture was stirred for 10 minutes and further dispersed for 5 minutes by an ultrasonic disperser of 28 KHz-150 W. After completion of the dispersion, 0.6 g of distilled water was added with stirring, and the flask was immersed in a boiling water bath and refluxed for 5 hours. Then, acetone was distilled off with an evaporator to obtain a dental inorganic filler for comparative examples that had been surface-treated.

Preparation of dental primer (PR1 to PR28) and comparative example dental primer (C-PR1, C-PR2) 2.0 g of dental inorganic filler prepared in Examples 1 to 28, 4.0 g of acetone, distilled water 4.0 g was sufficiently stirred to prepare dental primers (PR1 to PR28). The recipe is listed in Table 2. Similarly, 2.0 g of comparative inorganic dental filler prepared in Comparative Example 1, 4.0 g of acetone, and 4.0 g of distilled water were sufficiently stirred to prepare a comparative dental primer (C-PR1). In addition, 2.0 g of 4-MET (4-methacryloxyethyl trimellitic acid), which is an acidic monomer conventionally used for dental bonding, instead of the dental inorganic filler, 4.0 g of acetone, 4.0 g of distilled water. Was sufficiently stirred and a dental primer for comparative example (C-PR2) was prepared.

Shear bond strength test 1
Using dental primer (PR1 to PR28) prepared in the preparation of dental primer and dental primer for comparative example (C-PR1, C-PR2), enamel or dentin and dental composite in two steps A shear adhesion test with the resin was performed. As for the tooth quality, freshly extracted bovine anterior teeth were used, the roots were deleted, the pulp was removed, and the epoxy resin was embedded. Polished enamel was prepared by polishing the lip enamel of the bovine teeth under water pouring with water resistant polishing paper No. 600. Similarly, the dentin was polished to prepare a polished dentin. The polished tooth surface was dried with compressed air containing no oil, and a double-sided tape with a diameter of 4 mm was attached to define an adhesive surface. Next, the prepared primer was dropped onto the eye plate, applied to the adhesion regulating surface with a microbrush, and treated so as to be rubbed for 10 seconds. Then, weak compressed air without oil was blown for 5 seconds to evaporate volatile components. . A photopolymerizable bonding agent “Fluorobond II” (manufactured by Matsukaze Co., Ltd.) was applied to the surface with a microbrush and spread thinly on the tooth surface. Subsequently, the light was irradiated for 10 seconds with Griplight II (manufactured by Matsukaze Corporation). After that, a Teflon mold having a diameter of 4 mm and a height of 2 mm is fixed to the adhesion regulating face frame, and a photopolymerizable composite resin “Beauty Fill II” (manufactured by Matsukaze) is inserted into the mold, and Griplight II (manufactured by Matsukaze) The composite resin was photocured by irradiation with light for 20 seconds, and then the mold was removed to prepare an adhesion test body. After the adhesion test specimen was immersed in distilled water at 37 ° C. for 24 hours, the test specimen was set on a jig for shear bond strength, and an Instron universal testing machine (Instron 5567, manufactured by Instron) was used. The shear bond strength was measured in min. Furthermore, in addition to “immediately after preparation—adhesion strength” in the case of using a primer immediately after preparation, after thermal cycling (shear bond strength test specimens were immersed in cold water at 4 ° C. for 1 minute and then at warm water at 60 ° C. for 1 minute. The adhesion durability test of measuring the shear bond strength after repeating the immersion 3000 times was also performed.

Table 3 (Results of Shear Adhesion Strength Test 1) shows the results of Shear Adhesion Strength Test 1 using dental primers prepared based on the examples. As is apparent from these results, the shear bond strength using the dental primer (PR1 to 28) prepared according to the present invention is a dental primer having only an acidic monomer conventionally used in dentistry (C -Significantly higher shear bond strength compared to the system treated with PR2). In particular, the effect on the shear bond strength after the thermal cycle was remarkable. That is, the system treated with the dental primer (C-PR2) having only the acidic monomer conventionally used in dentistry showed a significant decrease in shear bond strength. Moreover, the dental primer (C-PR1) using the particle | grains containing the acidic group and radical polymerizable group currently disclosed by patent document 12 also showed the fall of the shear bond strength drastically. These reductions in shear bond strength are presumed to be caused by degradation of the adhesion interface due to hydrolysis. As is apparent from these evaluation results, it has become possible to provide a dental material having a high adhesive strength that could not be achieved by the prior art.

Preparation of dental one-step bonding agent Dental one-step bonding agents were prepared (BD1 to BD28) using the dental inorganic filler prepared in Examples 1 to 28. Similarly, preparation of a comparative dental one-step bonding agent (C-BD1) using the comparative inorganic dental filler prepared in Comparative Example 1, and conventional dental adhesive instead of the dental inorganic filler. A comparative dental one-step bonding agent (C-BD2) using 4-MET (4-methacryloxyethyl trimellitic acid), which is an acidic monomer, was prepared. The formulation table is listed in Table 4.

Shear bond strength test 2
Using a dental one-step bonding agent (BD1 to BD28) and a comparative dental one-step bonding agent (C-BD1, C-BD2), a one-step shear adhesion test between enamel or dentin and a composite resin Carried out. As for the tooth quality, freshly extracted bovine anterior teeth were used, the roots were deleted, the pulp was removed, and the epoxy resin was embedded. Polished enamel was prepared by polishing the lip enamel of the bovine teeth under water pouring with water resistant polishing paper No. 600. Similarly, the dentin was polished to prepare a polished dentin. The polished tooth surface was dried with compressed air containing no oil, and a double-sided tape with a diameter of 4 mm was attached to define an adhesive surface. Next, the prepared dental one-step bonding agent (BD1 to BD28) and comparative dental one-step bonding agent (C-BD1, C-BD2) were each applied with a microbrush and spread thinly on the tooth surface. After drying with compressed air containing no oil, it was irradiated with light with Griplight II (manufactured by Matsukaze Co., Ltd.) for 10 seconds. After that, a Teflon mold having a diameter of 4 mm and a height of 2 mm is fixed to the adhesion regulating face frame, and a photopolymerization type composite resin “Beauty Fill II” (manufactured by Matsukaze Co., Ltd.) is filled in the mold, and Griplight II (manufactured by Matsukaze Co., Ltd.) The composite resin was photocured by irradiation with light for 20 seconds, and then the mold was removed to prepare an adhesion test body. After the adhesion test specimen was immersed in distilled water at 37 ° C. for 24 hours, the test specimen was set on a jig for shear bond strength, and an Instron universal testing machine (Instron 5567, manufactured by Instron) was used. The shear bond strength was measured in min. Furthermore, in addition to “immediately after preparation—adhesion strength” in the case of using a primer immediately after preparation, after thermal cycling (shear bond strength test specimens were immersed in cold water at 4 ° C. for 1 minute and then at warm water at 60 ° C. for 1 minute. The adhesion durability test of measuring the shear bond strength after repeating the immersion 3000 times was also performed.

Table 5 (Results of Shear Adhesive Strength Test 2) shows the results of Shear Adhesive Strength Test 2 using the dental one-step bonding agent prepared based on the examples. As is clear from these results, the shear bond strength using the dental one-step bonding agent containing the dental inorganic filler prepared according to the present invention is a dental having only an acidic monomer conventionally used in dentistry. It has a significantly higher shear bond strength compared to a system treated with a one-step bonding agent (C-BD2). In particular, the effect on the shear bond strength after the thermal cycle was remarkable. In addition, the dental one-step bonding agent (C-BD1) using particles containing acidic groups and radical polymerizable groups disclosed in Patent Document 12 also shows a significant decrease in shear bond strength after thermal cycling. It was. These reductions in shear bond strength are presumed to be caused by degradation of the adhesion interface due to hydrolysis. As is apparent from these evaluation results, it has become possible to provide a dental material having a high adhesive strength that could not be achieved by the prior art.

Preparation of dental glass ionomer liquid material (GI-1 to GI-4)
According to the formulation of Table 6, the dental glass ionomer liquid materials (GI-1 to GI-4) were prepared using the dental inorganic filler prepared in Example 29.

Shear bond strength test 3
A shear adhesion test was performed using dental glass ionomer liquid materials (GI-1 to GI-4) and dental glass ionomer cement powder (manufactured by Shofu CX-Plus Matsukaze). As for the tooth quality, freshly extracted bovine anterior teeth were used, the roots were deleted, the pulp was removed, and the epoxy resin was embedded. Polished enamel was prepared by polishing the lip enamel of the bovine teeth under water pouring with water resistant polishing paper No. 600. Similarly, the dentin was polished to prepare a polished dentin. The polished tooth surface was dried with compressed air containing no oil, and a Teflon mold having a diameter of 4 mm and a height of 2 mm was fixed to the tooth surface to define an adhesive surface. Next, 2.0 g of Shofu CX-Plus powder is kneaded with the prepared dental glass ionomer liquid materials (GI-1 to GI-4) at a ratio of 1.0 g on a paper kneading board for 30 seconds. Cement mud was prepared, filled in a Teflon mold, and pressed with a cover glass. The specimen was stored in an environment of 37 ° C. and 100% humidity for 1 hour. Thereafter, the cover glass was removed and stored in distilled water at 37 ° C. for 24 hours, and the Teflon mold was removed. The test specimens were measured for shear bond strength using an Instron universal testing machine (Instron 5567, manufactured by Instron) at a crosshead speed of 1 mm / min. Further, adhesion durability test after thermal cycle (shear bond strength test specimen is immersed in cold water at 4 ° C. for 1 minute, and then immersed in warm water at 60 ° C. for 1 minute is repeated 3000 times). Also went.

Table 7 (Results of Shear Bond Strength Test 3) Preparation of Dental Glass Ionomer Liquid Material (GI-1 to GI-4)
The result of the shear bond strength test 3 by the combination of the liquid material prepared based on the above and glass ionomer cement powder (ShofuCX-Plus) is shown. As is clear from these results, the dental glass ionomer liquid material containing the dental inorganic filler by the high-toughness tooth-adhesive silane coupling agent of the present invention contains only polyacrylic acid as a reaction component to the tooth. Compared to conventional dental glass ionomer liquid material, it showed higher adhesion to the tooth. In particular, the effect on the shear bond strength after the thermal cycle was remarkable in a system containing a dental inorganic filler with a high-toughness tooth-bonding silane coupling agent. In addition, GI-2, which is a 50 wt% PAA system, did not undergo a shear bond strength test because gelation occurred during liquid material preparation.

ＳＣ１，ＳＣ２・・・ＳＣ２８は各々、合成例１にて合成された高靭性シランカップリング剤，合成例２にて合成された高靭性シランカップリング剤・・・合成例２８にて合成された高靭性シランカップリング剤に対応する。

SC1, SC2,..., SC28 are the high toughness silane coupling agents synthesized in Synthesis Example 1, the high toughness silane coupling agents synthesized in Synthesis Example 2, and so on. Corresponds to high toughness silane coupling agent.

Industrial applicability

By introducing functional groups such as acidic groups and aldehyde groups into silicon atoms via thiourethane bonds, thioester bonds, and thioether bonds, inorganic fillers with extremely high adhesive toughness, durability and reactivity to tooth The present inventors completed the present invention by discovering a high-toughness tooth-adhesive silane coupling agent that can be imparted to an adhesive. More specifically, an inorganic filler that combines hydrogen bonding and covalent bonding (radical polymerization) by combining functional groups such as acidic groups and aldehyde groups and radical polymerizable groups with the same inorganic filler. did. More specifically, by bonding a silane coupling agent having a functional group such as an acid group or an aldehyde group and a silane coupling agent having a radical polymerizable group to the same inorganic filler, tooth adhesion and radical polymerization can be improved. Inorganic fillers have been developed. Inorganic filler that can react in the presence of water with fluoroaluminosilicate powder (glass ionomer cement powder) instead of polyacrylic acid by bonding only high-toughness tooth adhesive silane coupling agent to inorganic filler Developed. As a result, acidic groups such as carboxyl groups, which have been difficult with the prior art, can be contained in a high proportion of the dental glass ionomer cement powder. Since these acidic groups are also bonded to the inorganic powder through a thiourethane bond, a thioester bond, and a thioether bond, the toughness of the cured product is increased as compared with polyacrylic acid. The dental primer and the dental adhesive containing the inorganic filler of the present invention have a remarkable adhesive strength due to the synergistic effect of the ionic bond of the functional group such as acidic group or aldehyde group to the tooth and the covalent bond to the radical polymerizable monomer. Improved, durable and high refractive index. That is, the inorganic filler treated / condensed with the silane coupling agent according to the present invention was hardly hydrolyzed and exhibited very high adhesive toughness and durability against the tooth. These inorganic fillers can be regarded as adhesive inorganic fine particles having high toughness. By using the silane coupling agent according to the present invention, the adhesion performance of dental primer, dental adhesive, dental cement, dental resin cement, dental resin modified cement and dental composite resin can be improved. The present invention has been completed. This effect greatly shows the possibility of industrial use.

Claims (5)

A high-toughness tooth-adhesive silane coupling agent represented by the following formula.

A is —COOH, —P (O) (OH) ₂ , —S (O) ₂ OH, —O—P (O) (OH) ₂ , —CHO, —NH—C (O) —CHO, — A C (O) —CHO group, which may contain a —C (O) —O—C (O) — group only when R ¹ is aromatic, where R ¹ is a C ₂ -C ₆₀ straight or branched chain An alkylene group of the chain, which is at least trivalent aromatic, and Z is —C (O) —O—, —C (O) —S—, —NH—C (O) —, —NH—C (O ) —NH—, —NH—C (O) —S—, —NH—C (O) —O—, —S— group, wherein D is a C _{2 to} C ₆₀ divalent to tetravalent Represents a chain or branched alkylene group, -C (O) -O-, -C (O) -S-, -NH-C (O)-, -NH-C (O) -NH-, -S -, -NH-C (O) -S-, -NH-C (O) -O- group And / or a trivalent triazine molecular skeleton or a divalent barbituric acid molecular skeleton, and E represents —NH—C (O) —S—, —NH—C (O) —NH—, —C (O) —S— group, R ³ is a C _{1 to} C ₆₀ linear or branched alkylene group, —S—, —NH—, —NR ⁴ — (R ⁴ is an alkylene group) ), —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), —C (O) —O—, —O— group, and R ² represents C _{1 to} C _16. A linear or branched alkyl group, a phenyl group or a halogen atom, and when n is 0, at least one halogen atom is bonded to Si. R ⁴ represents a C _{1 to} C ₆ linear or branched alkyl group. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, n is 0 to 3, a is 1 to 2, and R1 is aromatic only when a is 2. Represents. A dental inorganic filler surface-treated with the high-toughness tooth-adhesive silane coupling agent according to claim 1. A high-toughness dental adhesive silane coupling agent according to claim 1, or a dental inorganic filler condensed and granulated in the presence of a metal alkoxide. The dental inorganic filler according to claim 2 and 3, which is surface-treated or condensed into a particle by coexisting with a radically polymerizable silane coupling agent. A dental adhesive composition comprising the dental inorganic filler according to claim 2.