JP5416447B2 - Novel organosilicon compound and composition containing the same - Google Patents

Description

  The present invention relates to a novel organosilicon compound and a composition containing the compound.

  The organosilicon compound contains a group that can be converted into a silanol group that is reactive with inorganic substances, and a polymerizable group that is reactive with organic substances, and is an organic group as a spacer that has a high affinity for organic substances. In a molecule. Organosilicon compounds are widely used in many composite materials because they act as adhesion aids at the interface between inorganic and organic materials.

  In recent years, in order to improve the mechanical strength and durability of plastics, it is generally known to add inorganic particles to form a composite material. It is applied in various fields such as materials, sliding materials, sealing materials, damping materials, dental / medical materials, and heat insulating materials. In particular, in recent dental treatment, composite materials for dental restoration materials such as composite resins and resin cements are frequently used.

  By using the organosilicon compound, the adhesion between the inorganic particles and the organic substance is improved, and the mechanical strength of the composite material is improved. However, under high-temperature and high-humidity conditions, the organosilicon compound between inorganic particles and organic matter undergoes hydrolysis over time, resulting in the loss of adhesion, gradually reducing the strength of the composite material, and durability of the material. There is a problem that is low.

  Particularly in the dental field, composite materials are exposed to high-temperature and high-humidity environments in the oral cavity. Conventionally, γ-methacryloxypropyltrimethoxysilane (hereinafter referred to as 3MPS) has been widely used as organosilicon compounds. It has been. When particles surface-treated with the compound are used, water absorption progresses with time, hydrolysis tends to proceed, and the durability of the material is low. Further, when particles surface-treated with the compound are used in a composite resin used as a substitute for teeth, the mechanical strength is not sufficient, and further improvement in strength is required.

  As a method for improving the durability of the material, a method using an organosilicon compound having a long alkyl chain length (Patent Document 1) and a method using an organosilicon compound having a fluoroalkylene group (Patent Document 2) have been proposed. Yes. In addition, as a method for improving the mechanical strength of a material, a method for enhancing adhesion at the interface between an organic substance and an inorganic substance by using an organosilicon compound having a plurality of polymerizable groups capable of polymerizing with a polymerizable monomer (patent) Document 3 and Non-Patent Document 1) have been proposed.

JP-A-2-134307 JP 2007-238567 A US Pat. No. 5,399,738

DENTAL MATERIALS, 2008, 24, 1631-1639

  However, when the methods described in Patent Document 1 and Patent Document 2 are applied to a dental restoration material, there is room for improvement in mechanical strength. When the methods described in Patent Document 3 and Non-Patent Document 1 are applied to a dental restoration material, the water resistance is low and the durability of the material is insufficient. As described above, in the prior art, both durability and mechanical strength of the material using the organosilicon compound are insufficient, and there is room for further improvement.

  Therefore, an object of the present invention is to provide a novel organosilicon compound that gives high adhesion and durability, and thereby gives high mechanical strength and durability when used in a composite material.

  The present invention is an organosilicon compound having m polymerizable groups represented by the following general formula (1).

(Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and (A) does not exist, Or —COO—, —OCO—, —CONH—, —O—, —S—, —CH ₂ O—, —CH ₂ S—, —C ₆ H ₄ O—, —C ₆ H ₄ COO—, and is one kind selected from the group consisting of -C ₆ H ₄ OCO-, m is 2 or 3, R ₄ is a hydrocarbon group which may having 6 to 40 carbon atoms which may have a substituent , Si atoms and polymerizable groups are bonded by a chain in which 5 or more carbon atoms are connected in series, R ₅ is a hydrolyzable group, and R ₆ may have a substituent. -20 hydrocarbon groups, n is an integer of 1-3.)

R ₁ and R ₂ are preferably a hydrogen atom, and R ₃ is preferably a hydrogen atom or a methyl group. A is preferably —COO—. R ₄ is preferably a hydrocarbon group having 6 to 40 carbon atoms.

  The organosilicon compound of the present invention is preferably a compound represented by the following general formula (2).

(Wherein, R ₇ to R ₉ each independently represent a hydrogen atom or a methyl group, R ₁₀ is an alkoxy group, k is an integer of 3 to 16.)

  The present invention also relates to inorganic particles surface-treated with the above organosilicon compound.

  The present invention is also a dental composition comprising the above inorganic particles, a polymerizable monomer, and a polymerization initiator.

  The present invention is also a dental composition comprising the above organosilicon compound.

  According to the organosilicon compound of the present invention, the adhesion between an organic material and an inorganic material such as an inorganic filler or an inorganic base material and water resistance are improved compared to conventional organosilicon compounds, and the mechanical properties of the composite material are improved. Durability can be improved. Therefore, inorganic and organic materials such as FRP, FRTP, elastomer, paint, adhesive, sealant, resin concrete, foundry, sealant, artificial marble, plastic magnet, rubber magnet, magnetic tape, PCB, dental restoration material, etc. It is useful in combined composite materials and is particularly useful in composite materials for dental restorations.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above general formula has a plurality of polymerizable groups and a hydrocarbon group having 6 to 40 carbon atoms that gives a chain in which at least 5 carbon atoms are in series. With the organosilicon compound (hereinafter also referred to as organosilicon compound (I)) shown in (1), the adhesive strength and adhesion durability between the inorganic substance and the organic substance can be increased, and both mechanical strength and durability are achieved. The present inventors have found that a composite material can be provided and have completed the present invention.

  The organosilicon compound (I) of the present invention has m (m is 2 or 3) polymerizable groups represented by the following formula. This polymerizable group enables radical copolymerization with other polymerizable monomers. In addition, since there are a plurality of polymerizable groups, a crosslinking reaction by radical polymerization is possible, a high adhesive strength can be provided between the inorganic material and the organic material, and a high mechanical strength can be provided to the composite material.

R ₁ , R ₂ and R ₃ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the hydrocarbon group that may have a substituent include an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, and a substituent. An aryl group that may have a group, an arylalkyl group that may have a substituent, an arylalkenyl group that may have a substituent, an arylalkynyl group that may have a substituent, and a substituent. And a cycloalkyl group that may be used.

  Here, in the present invention, the alkyl group which may have a substituent is a linear or branched alkyl group which may have a substituent. As the alkyl group, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group Group, isohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like.

  In the present invention, the alkenyl group which may have a substituent is a linear or branched alkenyl group which may have a substituent. Examples of the alkenyl group include a vinyl group and an allyl group. Group, methyl vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group and the like.

  In the present invention, the alkynyl group which may have a substituent is a linear or branched alkynyl group which may have a substituent. Examples of the alkynyl group include an ethynyl group, 1 -Propynyl group, 2-propynyl group, 1-butynyl group, 1-methyl-2-propynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-ethyl-2-propynyl group, 2-pentynyl Group, 3-pentynyl group, 1-methyl-2-butynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 1 -Ethyl-2-butynyl group, 3-hexynyl group, 1-methyl-2-pentynyl group, 1-methyl-3-pentynyl group, 4-methyl-1-pentynyl group, 3-methyl-1-pentynyl group, 5 Hexynyl group, 1-ethyl-3-butynyl group.

  In the present invention, the aryl group that may have a substituent is an aromatic hydrocarbon group that may have a substituent. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group. Group, phenanthryl group and the like.

  In the present invention, the arylalkyl group which may have a substituent is a group in which a linear or branched alkyl group substituted by an aryl group may have a substituent. Are, for example, benzyl group, phenethyl group, 3-phenylpropyl group, trityl group, 1-naphthylmethyl group, 2- (1-naphthyl) ethyl group, 2- (2-naphthylethyl group, 3- (2-naphthyl) A propyl group etc. are mentioned.

  In the present invention, the arylalkenyl group which may have a substituent is a group in which a linear or branched alkenyl group substituted by an aryl group may have a substituent. Examples include styryl group.

  In the present invention, the arylalkynyl group which may have a substituent is a group in which a linear or branched alkynyl group substituted by an aryl group may have a substituent. Examples thereof include a phenylethynyl group.

  In the present invention, the cycloalkyl group which may have a substituent is a cyclic alkyl group which may have a substituent. Examples of the cycloalkyl group include a cyclopropyl group and a cyclobutyl group. , Cyclopentyl group, cyclohexyl group, cycloheptanyl group, cyclooctanyl group, cyclononanyl group, cyclodecanyl group, cycloundecanyl group, cyclododecanyl group and the like.

The number and type of substituents possessed by the hydrocarbon group represented by R ₁ , R ₂ and R ₃ are not particularly limited as long as the purpose of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, an amino group, and a cyano group. And a nitro group.

R ₁ and R ₂ are preferably hydrogen atoms, and this has the advantage of excellent polymerizability. R ₃ is preferably a hydrogen atom or a methyl group, and this has the advantage of excellent polymerizability. In particular, when R ₁ and R ₂ are hydrogen atoms and R ₃ is a methyl group, even when the organosilicon compound (I) undergoes an action such as hydrolysis and the polymerizable group is eliminated, It has the advantage that the irritation to the living body is small.

(A) is an arbitrary structural unit. A represents —COO—, —OCO—, —CONH—, —O—, —S—, —CH ₂ O—, —CH ₂ S—, —C ₆ H ₄ O—, —C ₆ H ₄ COO—. , And —C ₆ H ₄ OCO—, but from the viewpoint of easy radical polymerization, A is preferably —COO— or —CONH—, and —COO— It is more preferable that Further, when the organosilicon compound (I) is used in an embodiment in which resistance to hydrolysis is particularly required, A is preferably —CH ₂ O— or —CONH—.

  Specific examples of the polymerizable group include (meth) acryl group, (meth) acrylamide group, vinyl (thio) ether group, allyl (thio) ether group, vinyl ester group, and styryl group. A containing group. Among these, a (meth) acryl group or a (meth) acrylamide group is preferable from the viewpoint of easy radical polymerization. From the viewpoint of ease of production of the organosilicon compound (I), the polymerizable group is preferably a (meth) acryl group. The organosilicon compound (I) of the present invention is preferably used as a component of a dental composition. However, since the oral cavity is a moist environment, there is a possibility that a polymerizable group may be eliminated by hydrolysis or the like. When considering the resistance to hydrolysis, it is more preferable to use a (meth) acrylamide group as the polymerizable group. Furthermore, in consideration of the irritation to the living body of the detached polymerizable group, it is particularly preferable to use a methacryl group or a methacrylamide group.

  m is 2 or 3, and m is preferably 3 when it is desired to increase the point of action that chemically interacts with the adherend. The m polymerizable groups possessed by the organosilicon compound (I) may be the same or different within the above definition.

R ₄ is a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent, and binds a Si atom and a polymerizable group by a chain in which 5 or more carbon atoms are connected in series. Thus, by inserting a chain having 6 to 40 carbon atoms and having 5 or more carbon atoms in series between the Si atom and the polymerizable group, the spacer portion of the organosilicon compound (I) Sufficient hydrophobicity can be provided.

R ₄ is a trivalent to tetravalent hydrocarbon group. The hydrocarbon group may contain an aromatic ring, a double bond, a triple bond, or an aliphatic ring. Accordingly, examples of the hydrocarbon group include groups in which 3 to 4 hydrogen atoms have been removed from alkane, alkene, alkyne, and arene. The hydrocarbon group may be linear or branched, and may contain a ring structure.

  In the case where the organosilicon compound (I) of the present invention is used as an adhesive between an organic material and an inorganic material, the mechanism for developing high adhesion is not always clear. In order to obtain a high adhesive force, it is considered important that the organosilicon compounds are regularly arranged when bonded to the adherend and act on the adherend surface with a high density. In order to regularly arrange the compounds, it is important to select the hydrocarbon group used as a spacer.

From this viewpoint, the hydrocarbon group represented by R ₄ is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group. From the viewpoint of improving adhesiveness, the Si atom and the polymerizable group are preferably located at some distance in the molecule, and the lower limit of the carbon number of R ₄ is 6 or more, preferably 8 or more. is there. Furthermore, the preferred use mode of the organosilicon compound (I) of the present invention is a dental composition. When used in such applications, the oral cavity is a moist environment, so the lower limit of the carbon number of R ₄ is preferably Is 7 or more, particularly preferably 8 or more. By setting the carbon number of R ₄ within such a range, the hydrophobicity of the entire compound is improved, it is less susceptible to hydrolysis even in a moist environment such as the oral cavity, and long-term durability of the material can be maintained. become. On the other hand, when the number of carbon atoms exceeds 40, the degree of freedom of the spacer increases, and it may be difficult to regularly arrange the spacers on the surface of the inorganic material. Therefore, the upper limit of the number of carbon atoms is 40, preferably 35 It is as follows.

In addition, when the organosilicon compound (I) is used in a dental composition as described above, the affinity for the hydrophobic polymerizable monomer can be improved by setting the carbon number of R _{4 in} the above range. And high density packing of inorganic particles becomes possible. As a result, the mechanical strength and durability of a dental restoration material such as a composite resin can be improved.

The number and type of substituents possessed by the hydrocarbon group represented by R ₄ are not particularly limited as long as the object of the present invention is not impaired, and examples thereof include a halogen atom, a hydroxyl group, an amino group, a cyano group, and a nitro group. It is done. R ₄ preferably has no substituent from the viewpoint of hydrophobicity and ease of synthesis.

R ₅ is a hydrolyzable group, more specifically a group that can be converted into an OH group by hydrolysis. Examples of R ₅ include an alkoxy group, a hydrogen atom, a halogen atom and the like, and among these, an alkoxy group is preferable. The alkoxy group may be linear or branched, preferably having 1 to 20 carbon atoms, and having 1 to 4 carbon atoms (eg, methoxy group, ethoxy group, propoxy group, butoxy group). More preferred.

R ₆ is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include R ₁ , R ₂ and This is the same as the hydrocarbon group exemplified for R ₃ . R ₆ is preferably a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, or a phenyl group.

n is an integer of 1 to 3, and thus the organosilicon compound (I) has at least one R ₅ . Thus, by always having R ₅ , it is possible to bond with an inorganic substance. n is preferably 3.

In addition, although there exist a plurality of R ₅ or R ₆ , those present in a plurality may be the same or different.

  The organosilicon compound (I) is optimally a compound represented by the following formula (2).

Wherein, R ₇ to R ₉ each independently represent a hydrogen atom or a methyl group, R ₁₀ is an alkoxy group, k is an integer of 3 to 16. k is preferably 4 or more. R ₁₀ is preferably an alkoxy group having 1 to 4 carbon atoms.

  Compound (I) of the present invention can be produced by combining known methods. As an example, first, a compound serving as a base for a polymerizable site, a spacer site, and an organosilicon site is prepared. The compound that is the basis of the polymerizable site is, for example, a compound containing a polymerizable group (double bond) represented by the following formula (3) and a functional group Y (hereinafter also referred to as a polymerizable compound (3)). is there.

(In the formula, R _{1 to} R ₃ are as defined above, and Y is a functional group capable of reacting with a functional group Z described later.)

  The compound serving as the basis of the spacer moiety is, for example, a compound containing a double bond represented by the following formula (4) and m functional groups Z (hereinafter also referred to as spacer compound (4)).

(In the formula, R ₄ ′ is an optionally substituted hydrocarbon group having 4 to 38 carbon atoms, and Z is a functional group capable of reacting with Y.)

  The compound which becomes the basis of the organosilicon site is, for example, an organosilane compound represented by the following formula (5) (hereinafter also referred to as organosilane compound (5)).

(In the formula, R ₅ , R ₆ , and n are as defined above.)

Here, the functional group Y and the functional group Z are converted into —COO—, —OCO—, —CONH—, —O—, —S—, —CH ₂ O—, —CH ₂ S—, —C by these reactions. Selection is made such that either a ₆ H ₄ O—, —C ₆ H ₄ COO—, or —C ₆ H ₄ OCO— bond is formed. Methods for generating these bonds are well known to those skilled in the art. For example, when a —COO— bond is formed, —COOH or —COCl is selected as Y, —OH is selected as Z, and esterification may be performed according to a known method. Further, for example, when a —CONH— bond is formed, —COOH is selected as Y, —NH ₂ is selected as Z, and a dehydration condensation reaction may be performed according to a known method. For example, in the case of forming an —O— bond, an etherification reaction (Williamson synthesis) may be performed with one of X and Y being a halogen atom and the other being —ONa. Further, for example, in the case of forming an —S— bond, one of X and Y may be a halogen atom and the other may be —SH, and a coupling reaction may be performed under alkaline conditions.

  The double bond of the spacer compound (4) reacts and bonds with Si-H of the organosilane compound (5). The said reaction is well-known and can be performed in accordance with a well-known method.

  Many of the above-mentioned compounds (3) to (5) are commercially available, and can be easily synthesized according to known methods. And according to a well-known method, organosilicon compound (I) can be manufactured by making m equivalent polymeric compound (3), spacer compound (4), and organosilane compound (5) react. Any of the polymerizable compound (3) and the spacer compound (4), and the spacer compound (4) and the organosilane compound (5) may be reacted first. Moreover, in the above-mentioned example, the spacer compound (4) has a double bond at the terminal, but it is also possible to form a spacer site in the same manner using a spacer compound having a double bond at the terminal. it can.

  Moreover, when A of Formula (1) does not exist, an organosilicon compound (I) can be manufactured by making a diene compound and an organosilane compound (5) react according to a well-known method, for example.

  When the organosilicon compound (I) of the present invention is a compound represented by the formula (2), it can be produced, for example, by the following method.

  First, an alkenyl aldehyde represented by the following formula (6) (hereinafter also referred to as alkenyl aldehyde (6)) is reacted with formaldehyde, an aldol condensation reaction and a cannula allo reaction (that is, a methylolation reaction) in the presence of an alkali compound. A trimethylol compound represented by the formula (7) (hereinafter also referred to as trimethylol compound (7)) is synthesized.

(Wherein k is as defined above.)

  Formaldehyde is usually used in the form of an aqueous solution. The concentration of formaldehyde in the aqueous formaldehyde solution is not particularly limited, but it is advantageous to use a formaldehyde aqueous solution having a concentration of 5 to 50% by weight that is easily available. The amount of formaldehyde used is in the range of 5/1 to 7/1 in molar ratio to alkenyl aldehyde (6).

  As the alkali compound, alkali metal hydroxide or alkaline earth metal hydroxide (hereinafter referred to as alkali (earth) metal hydroxide) can be used, and specific examples include lithium hydroxide, sodium hydroxide, hydroxide. Examples include potassium, calcium hydroxide, barium hydroxide, and the like, preferably sodium hydroxide or potassium hydroxide. The amount of these alkali (earth) metal hydroxides used is usually within the range of 1.1 to 2.5 gram equivalent, preferably 1.3 to 1.8 gram per mole of alkenyl aldehyde (6). Within the equivalent range. The alkali (earth) metal hydroxide is usually advantageous in terms of operation when used in the form of an aqueous solution having a concentration of 50% by weight or less.

  The methylolation reaction of alkenyl aldehyde (6) is carried out in an aqueous medium. The medium may be water alone or a mixture of water and an organic solvent that is at least partially miscible with water. Examples of the organic solvent include cyclic ethers such as tetrahydrofuran and dioxane; lower alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. The organic solvent is preferably used in an amount such that its concentration in the methylolation reaction mixture is in the range of 20 to 80% by weight, more preferably in an amount in the range of 40 to 60% by weight. . Water is usually used at a weight in the range of about 4 to 100 times the weight of formaldehyde used.

  The reaction temperature employed in the methylolation reaction is usually in the range of about 20 to 100 ° C, preferably in the range of about 30 to 70 ° C. In a methylolation reaction, an aqueous solution of an alkali (earth) metal hydroxide and an alkenyl aldehyde (6) are usually mixed in a low concentration aqueous medium solution of formaldehyde with respect to the alkenyl aldehyde (6). It is preferable to adopt a method of gradually adding at a rate such that the pH value of the liquid does not change suddenly.

  Since the methylolation reaction is usually carried out using an excess of formaldehyde relative to the alkenyl aldehyde (6) and the alkali (earth) metal hydroxide, the reaction mixture obtained by such a methylolation reaction is Reaction products derived from alkenyl aldehydes (6) such as methylol compounds (7), ditrimethylol compounds (compounds in which two molecules of trimethylol compounds are bonded via an ether bond), dimethylol compounds and formals; alkali metals Or an alkaline earth metal formate; unreacted formaldehyde; an aqueous medium and optionally unreacted alkenyl aldehyde (6). In order to remove most of the unreacted formaldehyde in the reaction mixture obtained by methylolation, an alkali (earth) metal hydroxide is added to the reaction mixture, and the trimethylol compound (7 ) May be converted to formate and methanol by treatment at a temperature at which crystals do not precipitate (preferably at a temperature of 60 ° C. or higher). When this treatment is carried out, it may be neutralized by adding an acid such as formic acid to the reaction mixture as necessary.

  When a mixture of water and an organic solvent is used as an aqueous medium, the reaction mixture is distilled with or without the treatment with the alkali (earth) metal hydroxide or the treatment with acid. By attaching, most or all of the organic solvent is distilled off. The reaction mixture is allowed to stand at a temperature such that crystals of the trimethylol compound (7) do not substantially precipitate in a state of containing no or little of such organic solvent, whereby alkenyl such as trimethylol compound (7) is obtained. The organic layer containing the reaction product derived from the aldehyde (6) and the aqueous layer are separated. The temperature at which the reaction mixture is allowed to stand is preferably 60 ° C. or higher. From the organic layer, the trimethylol compound (7) can be isolated with high purity by a crystallization operation. More specifically, it can be isolated by an operation of mixing an aromatic hydrocarbon with the organic layer containing the above-mentioned reaction product. Although it does not specifically limit as an aromatic hydrocarbon, Since it has the solubility characteristic of extremely high temperature dependence with respect to a trimethylol compound (7), a C6-C9 aromatic hydrocarbon is preferable, for example, benzene , Toluene, xylene, ethylbenzene, propylbenzene, mesitylene and the like. The aromatic hydrocarbon is used in an amount in the range of 0.5 / 1 to 50/1, in particular in the range of 5/1 to 20/1, by weight ratio to the reaction mixture derived from alkenyl aldehyde (6). It is preferable. The crystals of the precipitated trimethylol compound (7) can be obtained by separating from the aromatic hydrocarbon according to a conventional method such as filtration.

  Next, the trimethylol compound (7) and a compound represented by the following formula (8) are esterified according to a known method, and a compound represented by the following formula (9) (hereinafter also referred to as compound (9)). Get.

(In the formula, R ₁₁ is a hydrogen atom or a methyl group, and X is a hydroxyl group or a halogen atom.)

(Wherein R _{7 to} R ₉ and k are as defined above.)

  For esterification, the Schotten-Baumann reaction is preferred. In this method, sodium hydroxide or the like is added to the reaction system in which the trimethylol compound (7) is uniformly dissolved to make the pH alkaline, and an acid halide (X) in formula (8) where X is a halogen atom ( Hereinafter, acid halide (8) is also added dropwise. After the dropwise addition, the reaction solution is acidified to cause precipitation, and the precipitate is purified to obtain compound (9). Although the usage-amount of an acid halide (8) and a trimethylol compound (7) is not specifically limited, It is preferable to use 0.5-5.0 mol of acid halides (8) with respect to 1 mol of trimethylol compounds (7). More preferably, 0.6 to 4.0 mol is used.

  The reaction temperature when the acid halide (8) and the trimethylol compound (7) are reacted is not particularly limited. Preferably, a method of gradually dropping the acid halide (8) while stirring a solution containing the trimethylol compound (7) is employed. The acid halide (8) may be added dropwise neat, or may be added dropwise after diluting with a solvent. Although the temperature at the time of dripping is not specifically limited, Preferably it is -10-10 degreeC, More preferably, it is -5-5 degreeC. After completion of the dropwise addition, stirring is performed until the reaction is completed. The reaction temperature at that time is usually 10 to 60 ° C., preferably 15 to 45 ° C.

  The reaction time when the acid halide (8) and the trimethylol compound (7) are reacted is not particularly limited, and is usually 1 to 6 hours, preferably 2 to 4 hours. In this reaction, it is important to maintain the pH of the reaction system. Since the reactivity of the trimethylol compound (7) decreases under acidic conditions, the reaction may not proceed. In this case, the pH of the reaction system is preferably 8-9. As the acid halide (8) is dropped and the reaction proceeds, the pH in the system decreases and shifts to the acidic side, so a basic solution is added while observing the pH in the system using a pH meter or the like. Thus, it is preferable to appropriately adjust the pH of the reaction system. Although it does not specifically limit as a basic solution, The solution of a triethylamine, sodium hydroxide, or potassium hydroxide is used suitably.

  By reacting compound (9) with an organic silane compound represented by formula (10) (hereinafter also referred to as organosilane compound (10)) according to a known method, an organosilicon compound represented by formula (2) is obtained. Can be obtained.

(Wherein R ₁₀ has the same meaning as described above.)

  Many of the organosilane compounds (10) are available as commercial products, and can also be produced by reacting trichlorosilane and alkyl alcohol.

  Specifically, the hydrosilylation reaction of the compound (9) having an unsaturated carbon-carbon bond and the organosilane compound (10) is advanced by adding a catalyst for hydrosilylation reaction in a polar solvent.

  The addition amount of the catalyst for hydrosilylation reaction is not limited, but the metal atom in the catalyst is 0.1 to 1000 ppm by weight with respect to the total amount of the compound (9) and the organosilane compound (10). The amount may be within the range, and more preferably, the amount is within the range of 0.1 to 500 ppm.

  The temperature of the hydrosilylation reaction is preferably in the range of 0 to 100 ° C, and particularly preferably in the range of 5 to 70 ° C. The amount of the organic silane compound (10) used is in the range of 1.0 to 3.0 equivalents, preferably in the range of 1.5 to 2.0 equivalents, in terms of the molar ratio to the compound (9). The reaction time is not particularly limited, and is 5 to 48 hours, preferably 12 to 24 hours.

There are no particular limitations on the type of hydrosilylation catalyst, for example, platinum catalyst, rhodium catalyst (for example, RhCl (PPh ₃ ) ₃ , RhAl ₂ O ₃ ), ruthenium catalyst (for example, RuCl ₃ ), iridium catalyst (for example, , IrCl ₃ ), iron catalyst (eg, FeCl ₃ ), aluminum catalyst (eg, AlCl ₃ ), palladium catalyst (eg, PdCl ₂ .2H ₂ O), nickel catalyst (eg, NiCl ₂ ), titanium catalyst (eg, TiCl ₄ ) and the like, and platinum catalyst is preferable. The platinum catalyst is selected from platinum metal, platinum compounds and platinum complexes on a support. Platinum compounds and platinum complexes include chloroplatinic acid, chloroplatinic acid hexahydrate, chloroplatinic acid and alcohol, aldehyde, ketone and other complexes, platinum-olefin complexes (for example, Pt (CH ₂ ═CH ₂ ) ₂ Cl ₂ ), A platinum-vinylsiloxane complex (for example, Pt _p (ViMe ₂ SiOSiMe ₂ Vi) _q , Pt [(MeViSiO) ₄ ] _r ), wherein Me represents a methyl group, Vi represents a vinyl group, and p, q , And r represent integers), and dicarbonyldichloroplatinum.

  Alternatively, the compound represented by the formula (9) may be reacted with trichlorosilane and further with an alkyl alcohol according to a known method.

  The organosilicon compound (I) of the present invention obtained by the method as described above can be used alone, for example, as a surface treatment agent for inorganic materials, and can also be used as a composition by mixing with other components. .

Therefore, the present invention is also inorganic particles surface-treated with the organosilicon compound (I). When the inorganic particles are surface-treated with the organosilicon compound (I), R _{5 of the} organosilicon compound becomes an OH group by hydrolysis to produce a silanol group, and this silanol group reacts with the surface hydroxyl group of the inorganic particle. And combine. In some cases, R _{5 of the} organosilicon compound directly reacts with and binds to the surface hydroxyl groups of the inorganic particles. In the inorganic particles of the present invention, the organosilicon compound (I) is thus bonded to the inorganic particles.

  Inorganic particle materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, and glass ceramic. , Aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass, etc. . These can be used alone or in admixture of two or more. It can also be used as an aggregate of silicon dioxide and at least one other metal oxide. Further, for example, composite inorganic particles (organic modified inorganic particles) obtained by mixing fine particles silica and a polymerizable monomer, polymerizing and curing them, and then pulverizing may be used. The shape of the inorganic particles is not particularly limited, and the particle diameter of the particles can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle diameter of the inorganic particles is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  Examples of the shape of the inorganic particles include amorphous particles and spherical particles. From the viewpoint of improving the mechanical strength of the composite material containing inorganic particles, it is preferable to use spherical particles as the inorganic particles. Furthermore, when the spherical particles are used in a dental composite resin, there is an advantage that a composite resin having excellent surface lubricity can be obtained. Here, the spherical particle is a particle diameter in a direction perpendicular to the maximum diameter of the particle observed in the unit field of view by taking a photograph of the particle with a scanning electron microscope (hereinafter abbreviated as SEM). Is a particle having an average uniformity divided by its maximum diameter of 0.6 or more. The average particle diameter of the spherical particles is preferably 0.1 to 5 μm. When the average particle diameter is less than 0.1 μm, the filling rate of the spherical particles in the composition is lowered, and the mechanical strength may be lowered. On the other hand, when the average particle diameter exceeds 5 μm, the surface area of the spherical particles is decreased, and a cured body having high mechanical strength may not be obtained.

  If necessary, a surface treatment agent such as a known silane coupling material may be used in combination with the organosilicon compound (I) of the present invention. Examples of the surface treatment agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltri (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, and 11-methacryloyloxyundecyltrimethoxysilane. , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and the like.

  The surface treatment method of the inorganic particles with the organosilicon compound (I) is not particularly limited as long as the organosilicon compound (I) is adsorbed on the surface of the inorganic particles. For example, while stirring the inorganic particles in a mixing tank A method of spraying a solution obtained by diluting an organosilicon compound (I) with a solvent and heating and drying in a tank for a certain period of time while stirring, or stirring and mixing inorganic particles and an organosilicon compound (I) in a solvent Then, the method of heat-drying etc. are mentioned.

  The treatment amount of the inorganic particles with the organosilicon compound (I) is preferably 0.5 to 60 parts by weight, more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the inorganic particles before the treatment.

  Since the inorganic particles surface-treated with the organosilicon compound (I) of the present invention have a highly hydrophobic spacer, they have a high affinity for organic substances (particularly polymerizable monomers). Excellent water resistance. Moreover, since it has several polymeric group, the reactivity with respect to a polymerizable monomer is high. Therefore, the inorganic particles of the present invention have high adhesiveness and adhesion durability with organic matter, and the composite material using the inorganic particles of the present invention has excellent mechanical strength and durability.

  The organosilicon compound (I) of the present invention is suitable for applications exposed to high-temperature and high-humidity conditions as a composition and as inorganic particles surface-treated with the organosilicon compound (I). It is suitable for.

  As the first mode for using the organosilicon compound (I) of the present invention in a composition (particularly a dental composition), the organosilicon compound of the present invention is used as it is as a polymerizable monomer. The form to do is mentioned. That is, it is a composition (particularly a dental composition) containing the organosilicon compound (I) of the present invention. Next, as a 2nd form, the composition (especially dental composition) containing the inorganic particle surface-treated with the organosilicon compound (I) is mentioned. In any form, the composition preferably contains a polymerizable monomer (II) copolymerizable with the organosilicon compound (I). Further, the composition preferably contains a polymerization initiator (III), and more preferably used in combination with a polymerization initiator (III) and a polymerization accelerator (IV).

  The polymerizable monomer (II) copolymerizable with the organosilicon compound (I) is not particularly limited, but is preferably a (meth) acrylate compound or a (meth) acrylamide compound. Specific examples of the (meth) acrylate compound and the (meth) acrylamide compound are shown below.

  Examples of monofunctional monomers having no acidic group are methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) Acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (Meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Sil (meth) acrylate, glycerol mono (meth) acrylate, erythritol mono (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 2,4-dihydroxybutyl (meth) acrylate, 2-hydroxymethyl-3-hydroxy Propyl (meth) acrylate, 2,2-bis (hydroxymethyl) -3-hydroxypropyl (meth) acrylate, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) Acrylamide, N, N-(dihydroxyethyl) (meth) acrylamide, 3-methacryloxypropyltrimethoxysilane such as acryloyloxy propyl trimethoxy silane.

  Examples of monofunctional monomers having one carboxyl group or acid anhydride group in the molecule include (meth) acrylic acid, N- (meth) acryloylglycine, and N- (meth) acryloylaspartic acid. 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxyethyl hydrogen maleate, O- (meth) acryloyl tyrosine, N- (meta ) Acryloyl tyrosine, N- (meth) acryloylphenylalanine, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2- (meth) acryloyl Oxybenzoic acid, 3- (meth) acryloyloxybenzoic acid 4- (meth) acryloyloxybenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid and the like, and acid anhydrides thereof, and these acid halides Can also be used.

  Examples of monofunctional monomers having a plurality of carboxyl groups or acid anhydride groups in the molecule include 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane -1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 6- (meth) acryloyloxyhexane-1,1-dicarboxylic acid, 2- (meth) acryloyloxyethyl-3 '-Methacryloyloxy-2'-(3,4-dicarboxybenzoyloxy) propyl succinate, 4- (meth) acryloyloxyethyl trimellitate, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth ) Acryloyloxyhexyl trimellitate, 4- (meth) acryloyloxydecylto Melitate, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 6- (meth) acryloyloxyethylnaphthalene-2,3,6-tricarboxylic acid, 4- (meth) acryloyloxyethylcarbonylpro Pionoyl-1,8-naphthalic acid, 4- (meth) acryloyloxyethylnaphthalene-1,8-tricarboxylic acid, 9- (meth) acryloyloxynonane-1,1-dicarboxylic acid, 13- (meth) acryloyloxy Examples include tridecane-1,1-dicarboxylic acid, 11- (meth) acrylamide undecane-1,1-dicarboxylic acid, and acid anhydrides thereof.

  Examples of monofunctional monomers having a phosphinyloxy group or phosphonooxy group in the molecule (sometimes referred to as monofunctional radically polymerizable acidic phosphate ester) include 2- (meth) acryloyloxyethyldi Hydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 2- ( And (meth) acryloyloxyethyl-2-bromoethyl hydrogen phosphate, 2- (meth) acrylamidoethyl dihydrogen phosphate, and the like.

  Other monofunctional monomers having an acidic group, such as 2- (meth) acrylamido-2-methylpropanesulfonic acid, 10-sulfodecyl (meth) acrylate, and other monofunctional monomers having a sulfone group in the molecule Etc.

  Bifunctional monomers are roughly divided into two types, aromatic compounds and aliphatic compounds. Examples of aromatic bifunctional monomers include 2,2-bis ((meth) acryloyloxyphenyl) propane, 2,2-bis [4- (3- (meth) acryloyloxy) -2. -Hydroxypropoxyphenyl] propane (commonly known as “Bis-GMA”), 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) ) Acryloyloxytetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphene) ) Propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxyethoxyphenyl) ) Propane, 2- (4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2 -(4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxyisopropoxyphenyl) Propane, 1,4-bis (2- (meth) acryloyloxye Le) pyromellitate and the like.

  Examples of aliphatic compound-based bifunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, 2,2,4-trimethylhexamethylenebis ( 2-ka Vamoyloxyethyl) dimethacrylate (commonly known as “UDMA”), bis [2- (meth) acryloyloxyethyl] hydrogen phosphate, bis (6- (meth) acryloyloxyhexyl) hydrogen phosphate, bis (10- ( And (meth) acryloyloxydecyl) hydrogen phosphate, bis {2- (meth) acryloyloxy- (1-hydroxymethyl) ethyl} hydrogen phosphate, and the like.

  Examples of trifunctional or higher monomers include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N- (2,2 , 4-Trimethylhexamethylene) bis [2- (aminocarboxy) propane-1,3-diol] tetramethacrylate, and 1,7-diaacryloyloxy-2,2,6,6-tetraacryloyloxy Methyl-4-oxy-heptane, and the like.

  The said (meth) acrylate compound and (meth) acrylamide compound may be used individually by 1 type, and may be used in combination of multiple types. In addition to (meth) acrylate compounds or (meth) acrylamide compounds, esters of unsaturated organic acids such as α-cyanoacrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid , Vinyl esters, vinyl ethers, mono-N-vinyl derivatives, styrene derivatives and other polymerizable monomers may be used in combination as necessary.

  The polymerization initiator (III) used in the present invention can be selected from polymerization initiators used in the general industry, and among them, polymerization initiators used for dental applications are preferably used. In particular, polymerization initiators for photopolymerization and chemical polymerization are used alone or in combination of two or more.

  Among the polymerization initiators (III) used in the present invention, as the photopolymerization initiator, (bis) acylphosphine oxides, water-soluble acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, Examples include α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone compounds, and the like.

  Among the (bis) acylphosphine oxides used as the photopolymerization initiator, acylphosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2, 6-dichlorobenzoyldiphenylphosphine 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.

  The water-soluble acylphosphine oxides used as the photopolymerization initiator preferably have an alkali metal ion, alkaline earth metal ion, pyridinium ion, or ammonium ion in the acylphosphine oxide molecule. For example, water-soluble acylphosphine oxides can be synthesized by the method disclosed in European Patent No. 0009348 or Japanese Patent Application Laid-Open No. 57-197289.

  Specific examples of the water-soluble acyl phosphine oxides include monomethyl acetyl phosphonate / sodium, monomethyl (1-oxopropyl) phosphonate / sodium, monomethyl benzoyl phosphonate / sodium, monomethyl (1-oxobutyl) phosphine. Phosphonate sodium, monomethyl (2-methyl-1-oxopropyl) phosphonate sodium, acetyl phosphonate sodium, monomethyl acetyl phosphonate sodium, acetyl methyl phosphonate sodium, methyl 4- (hydroxy Methoxyphosphinyl) -4-oxobutanoate sodium salt, methyl-4-oxophosphonobutanoate mononatrium salt, acetyl phenyl phosphinate Sodium salt, (1-oxopropyl) pentylphosphinate sodium, methyl-4- (hydroxypentylphosphinyl) -4-oxobutanoate sodium salt, acetylpentylphosphinate sodium, acetylethylphosphite Nate sodium, methyl (1,1-dimethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium, (1,1-diethoxyethyl) methyl phosphinate sodium Methyl-4- (hydroxymethylphosphinyl) -4-oxobutanoate lithium salt, 4- (hydroxymethylphosphinyl) -4-oxobutanoic acid dilithium salt, methyl (2-methyl- 1,3-dioxolan-2-yl) Phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidin-2-yl) phosphonite sodium salt, (2-methylperhydro-1,3-diazin-2-yl) phosphonite sodium Salt, acetyl phosphinate sodium salt, (1,1-diethoxyethyl) phosphonite sodium salt, (1,1-diethoxyethyl) methyl phosphonite sodium salt, methyl (2-methyloxathio) Lan-2-yl) phosphinate sodium salt, methyl (2,4,5-trimethyl-1,3-dioxolan-2-yl) phosphinate sodium salt, methyl (1,1-propoxyethyl) phos Finate sodium salt, (1-methoxyvinyl) methyl phosphinate sodium salt, (1-ethylthiovinyl) methyl phosphinate sodium salt, methyl (2-methylperhydro-1,3-diazin-2-yl) phosphonate sodium salt, methyl (2-methylperhydro-1, 3-thiazin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-diazolidin-2-yl) phosphinate sodium salt, methyl (2-methyl-1,3-thiazolidine- 2-yl) phosphinate sodium salt, (2,2-dicyano-1-methylethynyl) phosphinate sodium salt, acetyl methyl phosphinate oxime natrium salt, acetyl methyl phosphinate-O-benzyl Oxime sodium salt, 1-[(N-ethoxyimino) ethyl] methyl phosphinate na Lithium salt, methyl (1-phenyliminoethyl) phosphinate sodium salt, methyl (1-phenylhydrazone ethyl) phosphinate sodium salt, [1- (2,4-dinitrophenylhydrazono) ethyl] methyl phos Finate sodium salt, acetyl methyl phosphinate semicarbazone sodium salt, (1-cyano-1-hydroxyethyl) methyl phosphinate sodium salt, (dimethoxymethyl) methyl phosphinate sodium salt, formyl Methyl phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate sodium salt, methyl (1-oxopropyl) phosphinate sodium salt, (1,1-dimethoxypropyl) methyl phosphinate・ Dodeci Guanidine salt, (1,1-dimethoxypropyl) methylphosphinate-isopropylamine salt, acetylmethylphosphinate thiosemicarbazone sodium salt, 1,3,5-tributyl-4-methylamino-1,2, 4-triazolium (1,1-dimethoxyethyl) -methylphosphinate, 1-butyl-4-butylaminomethylamino-3,5-dipropyl-1,2,4-triazolium (1,1-dimethoxyethyl)- Methyl phosphinate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide ammonium salt Etc. Furthermore, the compound described in Unexamined-Japanese-Patent No. 2000-159621 is also mentioned.

  Among these (bis) acylphosphine oxides and water-soluble acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis (2 , 4,6-Trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are particularly preferred.

  Examples of thioxanthones or quaternary ammonium salts of thioxanthones used as the photopolymerization initiator include 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-trime Ru-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-propanaminium chloride and the like can be used.

  Among these thioxanthones or quaternary ammonium salts of thioxanthones, a particularly preferred thioxanthone is 2-chlorothioxanthen-9-one, and a particularly preferred quaternary ammonium 厶 salt of thioxanthones is 2 -Hydroxy-3- (3,4-dimethyl-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride.

  Examples of ketals used as the photopolymerization initiator include benzyl dimethyl ketal and benzyl diethyl ketal.

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

  Examples of the coumarin compound used as the photopolymerization initiator include 3,3′-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoylcoumarin, and 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′-carbonylbiscuc Marine, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl Nzo [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- (4-nitrobe) Zoyl) benzo [f] coumarin, 3- (4-ethoxycinnamoyl) -7-methoxycoumarin, 3- (4-dimethylaminocinnamoyl) coumarin, 3- (4-diphenylaminocinnamoyl) coumarin, 3- [ (3-Dimethylbenzothiazol-2-ylidene) acetyl] coumarin, 3-[(1-methylnaphtho [1,2-d] thiazol-2-ylidene) acetyl] coumarin, 3,3′-carbonylbis (6-methoxy) Coumarin), 3,3′-carbonylbis (7-acetoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3- (2-benzothiazoyl) -7- (diethylamino) coumarin, 3 -(2-Benzothiazoyl) -7- (dibutylamino) coumarin, 3- (2-benzimidazolyl) -7- (diethi Ruamino) 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, etc. 3109 JP, compounds described in JP-A-10-245525 can be cited.

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

  Examples of the anthraquinones used as the photopolymerization initiator include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1-bromoanthraquinone, 1,2-benzanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1 -Hydroxyanthraquinone and the like.

  Examples of benzoin alkyl ethers used as the photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of α-aminoketones used as the photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one.

  Among these photopolymerization initiators, it is preferable to use at least one selected from the group consisting of (bis) acylphosphine oxides and salts thereof, α-diketones, and 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 initiator (III) used in 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.

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

  Examples of the hydroperoxide used as the chemical polymerization initiator include 2,5-dimethylhexane-2,5-dihydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and 1, 1,3,3-tetramethylbutyl hydroperoxide and the like.

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

  Examples of the dialkyl peroxide used as the chemical polymerization initiator include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne and the like.

  Examples of the peroxyketal used as the chemical polymerization initiator include 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 4,4-bis (t-butylperoxy) valeric acid-n-butyl ester, etc. Can be mentioned.

  Peroxyesters used as the chemical polymerization initiator include α-cumylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 2,2,4-trimethylpentyl. Peroxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t- Examples include butyl peroxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate, t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid. It is done.

  Examples of the peroxydicarbonate used as the chemical polymerization initiator include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and diisopropyl. Examples include peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, and diallyl peroxydicarbonate.

  Among these 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 among them.

  In a preferred embodiment, the above-mentioned polymerization initiator (III) is used together with a polymerization accelerator (IV). The polymerization accelerator (IV) used in the present invention includes amines, sulfinic acid and its salts, borate compounds, barbituric acid derivatives, triazine compounds, copper compounds, tin compounds, vanadium compounds, halogen compounds, aldehydes, thiols. Compound etc. are mentioned.

  The amines used as the polymerization accelerator (IV) are classified into aliphatic amines and aromatic amines. Examples of the aliphatic amine include primary aliphatic amines such as n-butylamine, n-hexylamine and n-octylamine; secondary aliphatic amines such as diisopropylamine, dibutylamine and N-methyldiethanolamine; N -Methylethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, N-lauryldiethanolamine, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine monomethacrylate , Tertiary fats such as triethanolamine dimethacrylate, triethanolamine trimethacrylate, triethanolamine, trimethylamine, triethylamine, tributylamine Amine and the like. 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.

  Examples of the aromatic amine include N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di (2-hydroxyethyl) -p-toluidine, and N, N-bis. (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, N, N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-isopropylaniline, N, N-bis (2-hydroxyethyl)- 3,5-di-t-butylaniline, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine N, N-dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N , N-dimethyl-4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, 4- Examples include butyl dimethylaminobenzoate. 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. At least one selected from the group consisting of dimethylaminobenzoic acid n-butoxyethyl ester and 4-N, N-dimethylaminobenzophenone is preferably used.

  Examples of the sulfinic acid and its salt used as the polymerization accelerator (IV) include p-toluenesulfinic acid, sodium p-toluenesulfinate, potassium p-toluenesulfinate, lithium p-toluenesulfinate, p-toluenesulfine. Acid calcium, benzenesulfinic acid, sodium benzenesulfinate, potassium benzenesulfinate, lithium benzenesulfinate, calcium benzenesulfinate, 2,4,6-trimethylbenzenesulfinate, sodium 2,4,6-trimethylbenzenesulfinate, Potassium 2,4,6-trimethylbenzenesulfinate, lithium 2,4,6-trimethylbenzenesulfinate, calcium 2,4,6-trimethylbenzenesulfinate, 2,4,6-triethylben Sulfinic acid, sodium 2,4,6-triethylbenzenesulfinate, potassium 2,4,6-triethylbenzenesulfinate, lithium 2,4,6-triethylbenzenesulfinate, calcium 2,4,6-triethylbenzenesulfinate 2,4,6-triisopropylbenzenesulfinic acid, sodium 2,4,6-triisopropylbenzenesulfinate, potassium 2,4,6-triisopropylbenzenesulfinate, 2,4,6-triisopropylbenzenesulfinic acid Lithium, calcium 2,4,6-triisopropylbenzenesulfinate, and the like. Sodium benzenesulfinate, sodium p-toluenesulfinate, sodium 2,4,6-triisopropylbenzenesulfinate are particularly preferable. .

  The borate compound used as the polymerization accelerator (IV) is preferably an aryl borate compound. Specific examples of suitably used aryl borate compounds include trialkylphenyl boron, trialkyl (p-chlorophenyl) boron, trialkyl (p-fluoro) as borate compounds having one aryl group in one molecule. Phenyl) 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-butyloxy) Phenyl) boron, trialkyl (m-butyloxyphenyl) boron, Alkyl (p-octyloxyphenyl) boron and trialkyl (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl, n-octyl, n-dodecyl, etc.) A) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinori Examples thereof include a nium salt and a butyl quinolinium salt.

  Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenyl boron, 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-nitro Phenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) Boron and di Sodium salt, lithium salt, potassium salt of rualkyldi (m-octyloxyphenyl) boron (the alkyl group is at least one selected from the group consisting of n-butyl group, n-octyl group, n-dodecyl group, etc.) Magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt, etc. It is done.

  Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, 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-butyloxyphenyl) boron, monoal Rutri (p-octyloxyphenyl) boron and monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is one selected from n-butyl, n-octyl, n-dodecyl, etc.) Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, A butyl quinolinium salt etc. are mentioned.

  Further, borate compounds having four aryl groups in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl) phenylboron. Tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m-nitrophenyl) ) Boron, Tetrakis (p-butylphenyl) boron, Tetrakis (m-butylphenyl) boron, Tetrakis (p-butyloxyphenyl) boron, Tetrakis (m-butyloxyphenyl) boron, Tetrakis (p-octyloxyphenyl) boron , Tetrakis (m-octyloxyf Nyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyltriphenylboron, (p-nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, ( p-Butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron and (p-octyloxyphenyl) triphenylboron sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetra Examples thereof include methylammonium 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.

  Examples of the barbituric acid derivative used as the polymerization accelerator (IV) include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, and 5-butylbarbituric acid. Tool acid, 5-ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1, 3-dimethyl-n-butylbarbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethylbarbituric acid, 1,3-dimethyl-5-cyclopentylbarbituric acid, 1,3- Dimethyl-5-cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl 1-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 5-methylbarbituric acid, 5-propylbarbituric acid, 1,5-diethylbarbituric acid, 1-ethyl-5-methylbarbituric 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 preferred are alkali metals or alkaline earth metals), these Examples of the salt of barbituric acid include sodium 5-butyl barbiturate, sodium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate.

  Particularly preferred barbituric acid derivatives include 5-butyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, And sodium salts of these barbituric acids.

  Examples of the triazine compound used as the polymerization accelerator (IV) 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 (trichloromethyl) ) -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-to Lyazine, 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 3,6-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.

  As the copper compound used as the polymerization accelerator (IV), for example, acetylacetone copper, cupric acetate, copper oleate, cupric chloride, cupric bromide and the like are preferably used.

  Examples of the tin compound used as the polymerization accelerator (IV) include di-n-butyltin dimaleate, di-n-octyltin dimaleate, di-n-octyltin dilaurate, and di-n-butyltin dilaurate. It is done. Particularly suitable tin compounds are di-n-octyltin dilaurate and di-n-butyltin dilaurate.

  The vanadium compound used as the polymerization accelerator (IV) is preferably IV-valent and / or V-valent vanadium compounds. Examples of the IV-valent and / or V-valent vanadium compounds include divanadium tetroxide (IV), vanadium oxide acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1- Japanese Patent Application Laid-Open Publication No. 2003, such as phenyl-1,3-butanedionate) vanadium (IV), bis (maltolate) oxovanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), and ammonium metavanadate (V) The compound described in -96122 is mentioned.

  Examples of the halogen compound used as the polymerization accelerator (IV) include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride, dilauryldimethylammonium bromide and the like. Are preferably used.

  Examples of aldehydes used as the polymerization accelerator (IV) 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.

  Examples of the thiol compound used as the polymerization accelerator (IV) include 3-mercaptopropyltrimethoxysilane, 2-mercaptobenzoxazole, decanethiol, and thiobenzoic acid.

  In the first embodiment in which the organosilicon compound is used as the polymerizable monomer as it is, the compounding ratio of the compound (I) and the polymerizable monomer (II) is not particularly limited. When the total of I) and (II) is 100 parts by weight, the blending ratio is 1 to 99 parts by weight of (I) and 1 to 99 parts by weight of (II). The blending ratio is more preferably 2 to 90 parts by weight of (I) and 10 to 98 parts by weight of (II), 3 to 80 parts by weight of (I) and 20 to 97 parts of (II). More preferably, it is a part.

  The blending amount of the polymerization initiator (III) is not particularly limited. From the viewpoint of curability and the like of the resulting composition, the polymerization initiator (III) is 0.01 to 15 with respect to a total of 100 parts by weight of the compound (I) and the polymerizable monomer (II). It is preferable to mix | blend a weight part, and it is more preferable to mix | blend 0.03-10 weight part.

  The blending amount of the polymerization accelerator (IV) is not particularly limited. From the viewpoint of curability and the like of the resulting composition, the polymerization accelerator (IV) is 0.01 to 15 with respect to 100 parts by weight of the total of the compound (I) and the polymerizable monomer (II). It is preferable that a part by weight is blended.

  In the second embodiment using the inorganic particles surface-treated with the organosilicon compound (I), the amount of the polymerizable monomer (II) used is not particularly limited. 0.1 to 2000 parts by weight of inorganic particles are added to 100 parts by weight of the total of the compound (I) and the polymerizable monomer (II).

  The blending amount of the polymerization initiator (III) is not particularly limited. From the viewpoint of curability and the like of the resulting composition, the polymerization initiator (III) is 0.01 to 15 with respect to a total of 100 parts by weight of the compound (I) and the polymerizable monomer (II). It is preferable to mix | blend a weight part, and it is more preferable to mix | blend 0.03-10 weight part.

  The blending amount of the polymerization accelerator (IV) is not particularly limited. From the viewpoint of curability and the like of the resulting composition, the polymerization accelerator (IV) is 0.01 to 15 with respect to 100 parts by weight of the total of the compound (I) and the polymerizable monomer (II). It is preferable that a part by weight is blended.

  Moreover, it is preferable that a composition contains the solvent (V) depending on the specific embodiment. Examples of the solvent (V) include water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, hexane, toluene, chloroform, ethyl acetate, butyl acetate and the like. Among these, at least one selected from the group consisting of water, ethanol and acetone is preferably used in view of safety with respect to the living body.

  The composition may contain organic particles or organic-inorganic composite particles. Examples of the organic particle material include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polymethyl methacrylate, cross-linked polyethyl methacrylate, polyamide, polyvinyl chloride, and polystyrene. Chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and the like. These may be used alone or in combination of two or more. Can be used as a mixture. The shape of the organic particles is not particularly limited, and the particle diameter of the particles can be appropriately selected and used. From the viewpoints of handleability and mechanical strength of the resulting composition, the average particle diameter of the organic particles is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  The organic-inorganic composite particles are obtained by adding a monomer compound to the above-mentioned inorganic particles in advance, forming a paste, polymerizing, and pulverizing. Examples of the organic-inorganic composite particles include TMPT particles (trimethylolpropane methacrylate and silica particles mixed and polymerized and then pulverized). The shape of the organic-inorganic composite particles is not particularly limited, and the particle diameter of the particles can be appropriately selected and used. From the viewpoint of handling properties and mechanical strength of the resulting composition, the average particle diameter of the organic-inorganic composite particles is preferably 0.001 to 50 μm, and more preferably 0.001 to 10 μm.

  In addition, the composition may contain a pH adjuster, a polymerization inhibitor, an ultraviolet absorber, a thickener, a colorant, an antibacterial agent, a fragrance, and the like as long as the effects of the present invention are not impaired.

  The composition of the first aspect is particularly suitably used as a dental adhesive composition and a primer that exhibit excellent adhesive strength to ceramic materials such as zirconia and alumina and glass fiber. The adhesive composition has high adhesiveness and adhesion durability. The dental adhesive composition is preferably a composition comprising (I), (II), (III), (IV), and (V), and a normal amount of the above-mentioned inorganic particles, organic particles, or Organic-inorganic composite particles may further be included.

  The composition of the second aspect can be used as a primer, a bonding material, a composite resin, a cement, a foveal fissure filling material, a denture base resin, and the like, especially for dental use. , Composite resin, or cement. The dental restorative material exhibits high mechanical strength and durability. At this time, the composition is preferably a composition containing inorganic particles (II), (III), (IV), and (V) surface-treated with the organosilicon compound (I).

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.

Synthesis example 1
[Synthesis of trimethylol-6-heptene]
To a 3 L three-necked flask, 909 g (3.64 mol) of 12 wt% formaldehyde aqueous solution was added, then 909 g of THF (tetrahydrofuran) was added, and while stirring vigorously, 7-octen-1-al 126 g (1.00 mol), 40 wt% NaOH aqueous solution. 120 g (1.20 mol) was simultaneously added dropwise from separate dropping funnels over 5 hours. During this time, the internal temperature was maintained at 35 ° C. After completion of the dropwise addition, the mixture was stirred at 35 ° C. for 3 hours and then stirred under reflux for 6 hours. After completion of the reaction, the mixture was allowed to stand at room temperature and separated into two layers. The upper layer was taken and THF was distilled off under reduced pressure using a rotary evaporator. Toluene (500 ml) was added, and toluene was distilled off again under reduced pressure using an evaporator, followed by azeotropic dehydration. A small amount of toluene was added and allowed to stand to obtain 93.4 g of trimethylol-6-heptene.

[Tris (methacryloyloxymethyl) -6-heptene synthesis]
After adding 400 ml of chloroform to 40.4 g (0.22 mol) of trimethylol-6-heptene obtained by the above method in a 2 L three-necked flask, stirring and dissolving, 153 ml (5 equivalents) of triethylamine and MEHQ (hydroquinone monomethyl ether) ) 0.05 g was added in order, and the mixture was cooled in an ice bath until the internal temperature became 10 ° C. or lower. Using a dropping funnel, 75 ml (3.5 equivalents) of methacrylic acid chloride was added dropwise over 2 hours. During the dropping, the internal temperature of the reaction system was kept at 10 ° C. or lower. After stirring at room temperature for 2 hours, the amine salt was removed by filtration. Washing was performed 3 times with 3 volumes of distilled water with respect to chloroform, and magnesium sulfate was added to the resulting lower layer for dehydration. After dehydration, chloroform was removed under reduced pressure using a rotary evaporator to obtain crude tris (methacryloyloxymethyl) -6-heptene (hereinafter abbreviated as 6-TMH). Of crude 6-TMH, 30.0 g was purified by a silica gel column (hexane: ethyl acetate = 9: 1) to obtain 19.5 g of 6-TMH (GC purity: 84.7%, net amount: 16.5 g). 40.6 mmol).

[Synthesis of Tris (methacryloyloxymethyl) heptyltrichlorosilane]
To a 25 ml three-necked flask, 6.0 g (16.7 mmol) of 6-TMH and 0.01 g of MEHQ were added, and 1.0 ml of 1% chloroplatinic acid hexahydrate / anhydrous THF solution (platinum 17.4 μmol) was further added. . 3.3 ml (2.0 equivalents) of trichlorosilane was added in an ice bath and stirred at room temperature for 18 hours. The reaction was stopped when the GC area ratio of the raw material to the product became constant (reaction time 18 hours). The obtained reaction solution was subjected to the next step.

[Synthesis of Tris (methacryloyloxymethyl) heptyltrimethoxysilane]
To a 200 ml three-necked flask, 16 ml of methanol dehydrated in advance with magnesium sulfate and 21 ml of triethylamine were added and cooled to an internal temperature of 5 ° C. The tris (methacryloyloxymethyl) heptyltrichlorosilane solution obtained by the above method was added dropwise over 20 minutes while maintaining the internal temperature at 15 ° C. or lower. After completion of dropping, the mixture was stirred at room temperature for 2 hours. About half of the solvent was distilled off using a rotary evaporator. Extraction was performed with 20 ml of diisopropyl ether, and the resulting extract was filtered. After adding 20 mg of MEHQ, the solvent was removed by an evaporator to obtain crude tris (methacryloyloxymethyl) heptyltrimethoxysilane as an oil containing needle crystals.

When ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of tris (methacryloyloxymethyl) heptyltrimethoxysilane (organosilicon compound (I) of the present invention) obtained by the above method was measured, chemical shift δ (ppm) Was as follows.
¹ H-NMR (300 MHz, CDCl ₃ , TMS) δ = 0.60 (t, 2H), 1.2 (m, 10H), 1.9 (s, 9H), 3.5 (s, 9H), 4.1 (s, 6H), 5.5 (s, 3H), 6.0 (s, 3H).

  Abbreviations used below are as follows.

[Organic silicon compounds]
7-TMHS: Tris (methacryloyloxymethyl) heptyltrimethoxysilane 3-MPS: 3-methacryloyloxypropyltrimethoxysilane 11-MUS: 11-methacryloyloxyundecyltrimethoxysilane UDMS: 3-[(1,3 (2 ) -Dimethacryloyloxypropyl) -2 (3) -oxycarbonylamido] propyltriethoxysilane

[Acid group-containing polymerizable monomer]
MDP: 10-methacryloyloxydecyl dihydrogen phosphate MDP used was dehydrated by distillation.

[Polymerizable monomer having crosslinkability]
Bis-GMA: 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane 3G: 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane

[Primary alcohol]
As the alcohol, commercially available ethanol was distilled and dehydrated.

[Photopolymerization initiator]
TMDPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide CQ: camphorquinone

[Amines]
Amine: N, N-dimethylaminobenzoic acid n-butoxyethyl ester

[Polymerization inhibitor]
BHT: Butylhydroxytoluene

[Preparation of polymerizable monomer composition (1)]
Bis-GMA 75 parts by weight 3G 25 parts by weight CQ 0.3 part by weight TMDPO 0.1 part by weight Amine 0.5 part by weight BHT 0.05 part by weight

[Preparation of inorganic particles (a-1)]
Barium glass “RaySolb E-3000” (specialty glass) was pulverized with a vibration ball mill, and the volume ratio of particles having a volume median particle size of 2.5 μm and a particle size of 0.2 to 50 μm was 99% by volume. A regular inorganic particle fine powder was obtained. 100 g of amorphous inorganic particles having an average particle diameter of 2.5 μm, 2.0 g of 7-TMHS, and 200 ml of toluene were placed in a three-necked flask and stirred at room temperature for 2 hours. Toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and further heating at 90 ° C. for 3 hours to obtain inorganic particles (a-1) having an average particle size of 2.5 μm.

[Preparation of inorganic particles (a-2)]
Barium glass “RaySolb E-3000” (specialty glass) was pulverized with a vibration ball mill, and the volume ratio of particles having a volume median particle size of 2.5 μm and a particle size of 0.2 to 50 μm was 99% by volume. A regular inorganic particle fine powder was obtained. 100 g of amorphous inorganic particles having an average particle size of 2.5 μm, 2.0 g of 3-MPS, and 200 ml of toluene were placed in a three-necked flask and stirred at room temperature for 2 hours. Toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and further heating at 90 ° C. for 3 hours to obtain inorganic particles (a-2) having an average particle size of 2.5 μm.

[Preparation of inorganic particles (a-3)]
Barium glass “RaySolb E-3000” (made by Specialty Glass) was pulverized with a vibrating ball mill, and the volume ratio of particles having a median particle size of 2.5 μm and a particle size of 0.2 to 50 μm was 99% by volume. A regular inorganic particle fine powder was obtained. 100 g of amorphous inorganic particles having an average particle size of 2.5 μm, 2.0 g of 11-MUS, and 200 ml of toluene were placed in a three-necked flask and stirred at room temperature for 2 hours. Toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and further heating at 90 ° C. for 3 hours to obtain inorganic particles (a-3) having an average particle size of 2.5 μm.

[Preparation of inorganic particles (a-4)]
Barium glass “RaySolb E-3000” (made by Specialty Glass) was pulverized with a vibrating ball mill, and the volume ratio of particles having a median particle size of 2.5 μm and a particle size of 0.2 to 50 μm was 99% by volume. A regular inorganic particle fine powder was obtained. 100 g of amorphous inorganic particles having an average particle size of 2.5 μm, 2.0 g of UDMS, and 200 ml of toluene were placed in a three-necked flask and stirred at room temperature for 2 hours. Toluene was distilled off under reduced pressure, followed by vacuum drying at 40 ° C. for 16 hours and further heating at 90 ° C. for 3 hours to obtain inorganic particles (a-4) having an average particle size of 2.5 μm.

[Preparation of inorganic particles (b-1)]
100 g of substantially spherical fine particle filler (“Ar130” silica, manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 0.02 μm, 40 g of 11-MUS, and 610 ml of toluene were placed in a flask and vigorously stirred at 30 ° C. for 20 minutes. Toluene was distilled off at 30 ° C. under reduced pressure, followed by vacuum drying to obtain inorganic particles (b-1) having an average particle size of 0.02 μm.

[Production Example of Dental Adhesive Composition]
The polymerizable monomer and distilled ethanol shown in Table 1 were mixed at room temperature to obtain dental adhesive compositions of Example 1 and Comparative Examples 1 to 3.

[Production example of dental composite resin]
The inorganic particles shown in Table 2 and the polymerizable monomer composition (1) described above were mixed to prepare paste-like dental composite resins of Example 2 and Comparative Examples 4-6.

[Measurement of adhesive strength]
A dental porcelain block (made by VITA, trade name “Vita Serei”) is polished smoothly with # 1000 silicon carbide paper (made by Nihon Kenshi Co., Ltd.), ultrasonically cleaned, and then the surface water is used as dental air. It was blown off using a syringe to obtain an adherend surface. The adhesive composition was applied to the adherend surface using a small brush and spread thinly using a dental air syringe. At this time, ethanol was sufficiently volatilized. Next, a 150 μm thick adhesive tape having a 5 mm diameter round hole is attached to the surface to be adhered, and a dental composite resin (trade name “AP-X” manufactured by Kuraray Medical Co., Ltd.) is filled in the round hole. After applying a release film (Kuraray Co., Ltd., trade name “EVAL”), a slide glass was placed on the release film and pressed, and a dental light irradiator (Morita, trade name “JETLITE 3000”) was applied. )) For 20 seconds to cure. Next, one end face of a stainless steel cylindrical rod having a diameter of 7 mm and a length of 1.5 cm was bonded to the cured surface using a dental resin cement (trade name “Panavia 21” manufactured by Kuraray Medical Co., Ltd.). Sample.

  After bonding, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water. The sample immersed in the distilled water was allowed to stand for 24 hours in a thermostat maintained at 37 ° C., thereby preparing a sample for adhesion test. A total of five samples for adhesion test were prepared. As a durability test, evaluation after storage in distilled water at 50 ° C. for 2 weeks and at 50 ° C. for 4 weeks was also performed.

  Tensile bond strength of the above five adhesion test samples was measured with a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set to 2 mm / min, and the average value was determined as the bond strength (tensile Adhesive strength).

[Bending strength measurement]
After filling the paste into a stainless steel mold (dimensions 2 mm x 2 mm x 25 mm), press the top and bottom with glass slides, and light for 2 minutes each from both sides with a dental laboratory light irradiator (Morita, Alpha Light II) Was cured by irradiation. About each Example and the comparative example, 5 hardened | cured material was produced for every one, and after taking out from the metal mold | die, the hardened | cured material was preserve | saved for 24 hours at 37 degreeC distilled water. As a durability test, evaluation was also conducted after storage in distilled water at 50 ° C. for 2 weeks.

  Using an Instron universal testing machine, the bending strength was measured under the conditions of span: 20 mm and crosshead speed: 1 mm / min, and the average value of the measured values of each test piece was calculated to obtain the bending strength.

  As shown in Table 1, when the composition of Example 1 was used, high initial adhesion was exhibited. Furthermore, Example 1 maintained high adhesive force even after storage at 50 ° C. for 2 weeks and at 50 ° C. for 4 weeks, and was excellent in durability. On the other hand, in Comparative Example 1, the adhesive strength decreased after storage at 50 ° C. for 2 weeks and at 50 ° C. for 4 weeks, which is probably because the material absorbed water and the hydrolysis of the organosilicon compound proceeded. Comparative Example 2 maintains the initial adhesive strength even after storage at 50 ° C. for 2 weeks and at 50 ° C. for 4 weeks, and is excellent in durability, but the adhesive strength is not sufficient as compared with Example 1. There wasn't. In Comparative Example 3, the initial adhesive strength is higher than those in Comparative Examples 1 and 2, and this is due to the fact that the adhesive strength with the resin is improved by having two polymerizable groups. Conceivable. However, after 2 weeks of storage at 50 ° C. and 4 weeks at 50 ° C., the adhesive strength of Comparative Example 3 was significantly reduced. This is because the composition of Comparative Example 3 uses a highly hydrophilic organosilicon compound. As a result, the water absorption of the material has progressed, and it is considered that the hydrolysis has progressed rapidly.

  As shown in Table 2, when the composition of Example 2 was used, the initial bending strength was high, and the decrease in strength was less than 20% even after storage at 50 ° C. for 2 weeks, indicating excellent durability. It was. When the composition of Comparative Example 4 was used, the strength after storage at 50 ° C. for 2 weeks was greatly reduced, which is thought to be due to the hydrolysis of the organosilicon compound by water absorption. In Comparative Example 5, the strength decrease after storage at 50 ° C. for 2 weeks is relatively small at 30%, but the initial strength and durability are not sufficient as compared with Example 2. When the composition of Comparative Example 6 was used, the initial strength was as high as that of Example 2. This is because it has two polymerizable groups, and the interfacial adhesion with the resin is strengthened, and as a result, the strength of the material is improved. However, the strength after storage at 50 ° C. for 2 weeks was remarkably reduced as compared to after storage at 37 ° C. for 1 day. This is presumably because the composition of Comparative Example 6 uses inorganic particles treated with a highly hydrophilic organosilicon compound, the material has high water absorption, and hydrolysis progressed rapidly.

  The organosilicon compound of the present invention includes FRP, FRTP, elastomer, paint, adhesive, sealant, resin concrete, foundry, sealant, artificial marble, plastic magnet, rubber magnet, magnetic tape, PCB, dental restoration material, etc. It is useful in a composite material combining an inorganic material and an organic material, and is particularly useful in a composite material for a dental restoration material.

Claims (4)

An organosilicon compound represented by the following general formula (2).

(Wherein, R ₇ to R ₉ each independently represent a hydrogen atom or a methyl group, R ₁₀ is an alkoxy group, k is an integer of 3 to 16.) The inorganic particles surface-treated with the organosilicon compound according to claim 1, wherein R _{10 of the} organosilicon compound is converted into an OH group by hydrolysis to form a silanol group, and the silanol group is converted into a surface of the inorganic particle. An inorganic particle which reacts with a hydroxyl group and binds to inorganic particles, or R _{10 of the} organosilicon compound directly reacts with a surface hydroxyl group of the inorganic particles and binds to inorganic particles. A composite material for a dental restorative material comprising the inorganic particles according to claim 2, a polymerizable monomer, and a polymerization initiator. The composite material for dental restoration materials containing the organosilicon compound of Claim 1.