JP2013230991A - Novel coupling agent, modification method of inorganic filler using the same, and composite material using the inorganic filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel coupling agent that is used for modification of a surface of an inorganic filler or the like, and improves affinity to a polymer material; a modification method of the inorganic filler that uses the coupling agent; and a composite material that uses the inorganic filler.SOLUTION: A coupling agent comprises an organosilicon compound shown by formula (A) [in the formula, Z denotes an alicyclic compound that may partially have a double bond, and that may contain a hetero atom; Rdenotes an alkylene group; X denotes a group shown by -Si(OR)a(R)3-a [in the formula, Rdenotes an alkyl group or -(RO)-R(in the formula, Rdenotes an alkylene group; and Rdenotes an alkyl group; and b denotes an integer of at least 1); Rdenotes a hydrogen atom, a hydroxy group, a halogen atom or a hydrocarbon group; and a denotes an integer of 1-3]; and n denotes an integer of 2 to 4].

Description

  The present invention is a novel coupling agent that is used for surface modification treatment of an inorganic filler and the like and increases the affinity for a polymer material, and a method for surface modification treatment of an inorganic filler using the coupling agent And a composite material using the inorganic filler.

  Conventionally, inorganic fillers such as silica, alumina, titania, calcium carbonate, carbon fiber, and glass fiber are surface-treated with a coupling agent to add functional groups to the surface of the inorganic filler, and this inorganic filler becomes a matrix. It is widely used to obtain composite materials with improved physical properties such as mechanical strength, water resistance and adhesiveness by filling the polymer material such as epoxy resin and increasing the affinity between the inorganic filler and the polymer material. Has been done.

  However, there is a description of a coupling agent similar to Patent Documents 1 and 2, but it is a special application, and among inorganic fillers, alumina, titania, zirconia, etc. have poor reactivity with the coupling agent, and the surface There exists a fault that the effect of a process is not fully exhibited, and in the composite material using these inorganic fillers, there existed a subject that physical property improvement was insufficient.

JP 2010-095457 JP2011-190179A

  An object of the present invention is to obtain a novel coupling agent that can sufficiently react with inorganic fillers such as alumina, titanium oxide, and zirconium oxide to achieve a good surface treatment effect.

[式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良く、Ｒ^１は、アルキレン基であり、Ｘは−Ｓｉ(ＯＲ^２)a(Ｒ^３) 3-a［式中、Ｒ^２はアルキル基又は−（Ｒ^４Ｏ）_ｂ−Ｒ^５（式中、Ｒ^４は、アルキレン基であり、Ｒ^５はアルキル基であり、ｂは１以上の整数を示す）、Ｒ^３は、水素原子、ヒドロキシル基、ハロゲン原子又は炭化水素基を示し、ａは１〜３の整数を示す。］で表される基を示し、ｎは２〜４の整数である。]
で示される有機ケイ素化合物からなるカップリング剤を用いることにある。 According to the present invention, the following general formula (A)

[In the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ represents an alkylene group, and X represents —Si (OR ² ) a (R ³ ) 3-a [wherein R ² is an alkyl group or — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group, R ⁵ is an alkyl group, and b is an integer of 1 or more) R ³ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group, and a represents an integer of 1 to 3. ], And n is an integer of 2-4. ]
A coupling agent comprising an organosilicon compound represented by the formula:

  Further, it is obtained by using a novel coupling agent represented by the following general formula (A) and modifying the surface of the inorganic filler with this coupling agent.

（式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良い。Ｒ^１は、アルキレン基であり、Ｘは−Ｓｉ(ＯＲ^２)a(Ｒ^３) 3-a［式中、Ｒ^２はアルキル基又は−（Ｒ^４Ｏ）_ｂ−Ｒ^５（式中、Ｒ^４は、アルキレン基であり、Ｒ^５はアルキル基であり、ｂは１以上の整数を示す）、Ｒ^３は、水素原子、ヒドロキシル基、ハロゲン原子又は炭化水素基を示し、ａは１〜３の整数を示す。］で表される基を示し、ｎは２〜４の整数である。）

(In the formula, Z represents an alicyclic compound which may partially have a double bond, and may contain a hetero atom. R ¹ is an alkylene group, and X is —Si (OR ² ) a (R ³ ) 3-a [wherein R ² is an alkyl group or — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group, R ⁵ is an alkyl group, and b is an integer of 1 or more) R ³ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group, and a represents an integer of 1 to 3. ], And n is an integer of 2-4. )

  Furthermore, the present invention provides a composite material obtained by using a novel coupling agent represented by the general formula (A), an inorganic filler, and a polymer material.

  Still further, there is provided a method for modifying a substrate obtained by coating a surface on a substrate using a novel coupling agent represented by the general formula (A) and applying a heat treatment to form a thin film. provide.

  Furthermore, the present invention provides an organic-inorganic hybrid film characterized in that a hybrid film is formed by a sol-gel reaction by mixing a coupling agent or other known coupling agents.

  According to the present invention, a high reforming treatment effect can be obtained even for inorganic fillers such as alumina and titania, for which a sufficient reforming treatment effect was not obtained by the treatment with the conventional silane coupling agent. A composite material in which a polymer material is filled with an inorganic filler also has significantly improved physical properties such as mechanical strength, water resistance, adhesion, and electrical characteristics.

  Hereinafter, the present invention will be specifically described. First, a novel coupling agent will be described. The novel coupling agent of the present invention is represented by the general formula (A).

式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良く、Ｒ^１はアルキレン基であり、Ｘは−Ｓｉ(ＯＲ^２)a(Ｒ^３) 3-a［式中、Ｒ^２はアルキル基又は−（Ｒ^４Ｏ）_ｂ−Ｒ^５（式中、Ｒ^４は、アルキレン基であり、Ｒ^５はアルキル基であり、ｂは１以上の整数を示す）、Ｒ^３は、水素原子、ヒドロキシル基、ハロゲン原子又は炭化水素基を示し、ａは１〜３の整数を示す。］で表される基を示し、ｎは２〜４の整数である。
好ましくは、式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良く、Ｒ^１は炭素数２〜８のアルキレン基であり、Ｘは−Ｓｉ(ＯＲ^２)a(Ｒ^３) 3-a［式中、Ｒ^２は炭素数１〜６のアルキル基又は基−（Ｒ^４Ｏ）_ｂ−Ｒ^５（式中、Ｒ^４は、炭素数１〜６のアルキレン基であり、Ｒ^５は炭素数１〜６のアルキル基であり、ｂは１〜６の整数を示す)、Ｒ^３が炭素数１〜４のアルキル基または炭素数が１〜８のアルコキシアルキル基を示し、ａは２〜３の整数を示し、ｎは２〜４の整数である。
さらに好ましくは、式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良く、Ｒ^１は炭素数２〜４のアルキレン基、Ｘは−Ｓｉ（ＯＲ^２）3、Ｒ^２は炭素数１〜６のアルキル基を示し、ｎは２〜４の整数である。

In the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ is an alkylene group, and X is —Si (OR ² ) a (R ³ ) 3-a [wherein R ² is an alkyl group or — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group, R ⁵ is an alkyl group, and b is an integer of 1 or more) R ³ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group, and a represents an integer of 1 to 3. ], And n is an integer of 2-4.
Preferably, in the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ is an alkylene group having 2 to 8 carbon atoms, X is ^{-Si (OR 2) a (R} 3) 3-a [wherein R ² is an alkyl group having 1 to 6 carbon atoms or a group — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group having 1 to 6 carbon atoms; R ⁵ represents an alkyl group having 1 to 6 carbon atoms, b represents an integer of 1 to 6), R ³ represents an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 8 carbon atoms, a Represents an integer of 2 to 3, and n is an integer of 2 to 4.
More preferably, in the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ represents an alkylene group having 2 to 4 carbon atoms, X —Si (OR ² ) 3, R ² represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 4.

In the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ represents an alkylene group having 2 to 4 carbon atoms, and X represents —Si ( OR ² ) 3, R ² represents an alkyl group having 1 to 6 carbon atoms, and n is an organic silicon compound having an integer of 2 to 4, and the coupling agents (A) represented by the following general formulas (1) to (24) It is illustrated by.

  Next, a method for modifying the surface of the inorganic filler using this coupling agent will be described.

  In the modification treatment method of the present invention, as a specific surface modification method, an aqueous solution in which a coupling agent is first dissolved in a mixed solvent of a water-soluble organic solvent such as alcohol or acetone and water, and an alkoxy group is hydrolyzed. And Subsequently, this aqueous coupling agent solution is brought into contact with the inorganic filler. In this modification treatment method, an inorganic filler is added to and stirred in the aqueous solution, and then the inorganic filler is dried, or the aqueous solution is sprayed or poured onto the inorganic filler, and then inorganic. A method of drying the filler is used. Further, the modification treatment can be performed by dissolving the coupling agent in an organic solvent such as toluene, xylene, hexane, cyclohexane, etc. without using a water-soluble organic solvent, and mixing and drying with an inorganic filler. .

  The amount of the coupling agent used is an aqueous solution so that the weight increase before and after the surface modification treatment of the inorganic filler is 0.2 to 5%, preferably 1 to 3% with respect to the inorganic filler before the treatment. It is preferable to determine the concentration of. By such surface modification treatment, the alkoxy group of the coupling agent is hydrolyzed to become a terminal OH group, and this OH group is hydrogen-bonded with oxygen in the thin oxide film on the surface of the inorganic filler, thereby filling the inorganic filler. The coupling agent binds to the surface of the agent.

  The inorganic filler whose surface has been modified in this way is filled (added) into the polymer material serving as a matrix to form a composite material. The polymer material here is not particularly limited, and general thermoplastic resins such as polyethylene, polypropylene, polystyrene, and polyester, and thermosetting resins such as acrylic resin, melamine resin, epoxy resin, and alkyd resin are used. . The amount of the inorganic filler to be filled in the polymer material is determined depending on the use of the resulting composite material, and is usually determined in the range of 20 to 500 parts by weight with respect to 100 parts by weight of the polymer material. Since the affinity of the agent for the polymer material is improved by the surface modification treatment, a large amount of the compound can be blended and phase separation does not occur.

  Examples of the inorganic filler used in the present invention include metal oxides such as silica, alumina, zinc oxide, titanium oxide, iron oxide, and zirconium oxide, fluorides such as magnesium fluoride, calcium fluoride, and aluminum fluoride, and carbonic acid. Examples thereof include metal carbonates such as calcium, magnesium carbonate, and zinc carbonate, sulfides such as iron sulfide, magnesium sulfide, and zinc sulfide, and nitrides such as magnesium nitride and carbon nitride.

  In addition, the surface of the substrate can be modified using the coupling agent of the present invention. In the modification method of the substrate, a surface is coated on the substrate using a coupling agent, and a heat treatment is performed to form a thin film. As the base material used in the present invention, a film-like, plate-like or cylindrical one is used, and as the material, an inorganic material such as a metal, an alloy or glass, or a plastic material such as polyimide, polyester or polycarbonate is used. It is done.

  The specific filling method is that the matrix polymer material is uncured and liquid, such as epoxy resin, urethane resin, silicone resin, UV curable resin such as epoxy acrylate, urethane acrylate, etc. A method is used in which a filler is added and mixed, and then cured by an appropriate curing means. In addition, when the polymer material is in the form of thermoplastic powder or pellet, a method of mixing both with a blender, high-speed mixer, etc. and kneading with an extruder is used, and the conventional inorganic filler filling method is used as it is. Can be used.

  In the present invention, the composite material can be obtained by directly mixing the inorganic filler, the polymer material, and the coupling agent without subjecting the inorganic filler to surface treatment with the coupling agent. Specifically, a method of adding an inorganic filler and a coupling agent to the polymer material and mixing these three is employed.

  In this method, a minute amount of moisture adsorbed on the surface of the inorganic filler particles reacts with the alkoxy group of the coupling agent to bond the coupling agent to the inorganic filler, thereby preliminarily modifying the material. And almost the same effect can be obtained. This method simplifies the manufacturing operation and reduces the cost, but unreacted coupling agent and alcohol remain in the resulting composite material, and the softening temperature, heat resistance, hardness, Young's modulus, etc. of the composite material The physical properties are slightly lower than those using a surface-treated filler.

  In the present invention, an inorganic filler that has not been sufficiently treated by a surface treatment with a conventional silane coupling agent such as alumina or titania by the coupling agent represented by the general formula (A) can also be used. A sufficient treatment effect is obtained, the affinity between the inorganic filler and the polymer material is improved, and the physical properties of the resulting composite material are also highly improved.

(Production method)
The coupling agent (A) of the organosilicon compound of the present invention is not particularly limited, but for example, the following formula (B)

（式中、Ｚは部分的に二重結合を有してもよい脂環式化合物を表わし、ヘテロ原子を含んでいても良い。ｎは２〜４の数字を示す。）
で表される化合物と、下記式（Ｃ）

（式中、Ｒ^１はアルキレン基であり、Ｒ^２はアルキル基又は−（Ｒ^４Ｏ）_ｂ−Ｒ^５（式中、Ｒ^４は、アルキレン基であり、Ｒ^５はアルキル基であり、ｂは１以上の整数を示す）、Ｒ^３は、水素原子、ヒドロキシル基、ハロゲン原子又は炭化水素基を示し、ａは１〜３の整数を示す。）
で表される化合物とを反応（エンチオール反応）させることにより得られる。

(In formula, Z represents the alicyclic compound which may have a double bond partially, and may contain the hetero atom. N shows the number of 2-4.)
And a compound represented by the following formula (C)

(Wherein R ¹ is an alkylene group, R ² is an alkyl group or — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group, R ⁵ is an alkyl group, b Represents an integer of 1 or more), R ³ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group, and a represents an integer of 1 to 3).
It is obtained by reacting with the compound represented by (enethiol reaction).

  In addition, the compound represented by said Formula (B) and (C) may use a commercial item, and may use what was synthesize | combined by the conventional method. For example, the compound represented by the formula (B) can be obtained by allylation of a corresponding carboxylic acid or acid anhydride. Typically, it may be obtained by reacting carboxylic acid or acid anhydride with allyl halide (eg, allyl chloride).

  In addition, in order to trap (capture) by-produced hydrogen halide, the allylation reaction using allyl halide may be performed in the presence of a base.

In the formula (C), R ¹ , R ² , R ³ and a are the same as described above, including preferred embodiments. Typical compounds represented by the formula (C) (alkoxysilanes) include mercaptoalkyltrialkoxysilanes (for example, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethylsilane). Mercapto C _2-4 alkyltri-C _1-4 alkoxysilane) such as ethoxysilane, mercaptoalkyldialkoxysilane (eg, mercapto C _2-4 such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane). Alkyl C _1-4 alkyl diC _1-4 alkoxysilane) and the like.

  In the enthiol reaction, the use ratio of the compound represented by the formula (C) is, for example, 2 to 20 mol, preferably 2 to 10 mol, relative to 1 mol of the compound represented by the formula (B). Preferably it is 2-8 mol, More preferably, it is 2-5 mol.

  The reaction (enthiol reaction) between the compound represented by the formula (B) and the compound represented by the formula (C) may be usually performed in the presence of a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator (thermal radical generator) and a photopolymerization initiator (photo radical generator), and a preferred polymerization initiator is a photopolymerization initiator.

  Examples of the photopolymerization initiator include benzoins (benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether); acetophenones (acetophenone, p-dimethylacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2 -Hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc .; propiophenones (p-dimethylaminopropiophenone, 2-hydroxy-2- Butyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones [1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl- 1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, etc.] Aminoacetophenones [2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2; -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2-methyl-1-phenyl Pan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1 -(4-methylphenyl) propan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl)- 2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -Butan-1-one etc.]; benzophenones (benzophenone, benzyl, N, N′-bis (dimethylamino) benzophenone (Michler's ketone), 3 N, N′-dialkylaminobenzophenone, such as 1,3-dimethyl-4-methoxybenzophenone); ketals (acetophenone dimethyl ketal, benzyldimethyl ketal, etc.); thioxanthenes (thioxanthene, 2-chlorothioxanthene, 2, 4-diethylthioxanthene); anthraquinones (2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (thio) xanthones (thioxanthone, 2,4-dimethyl) Thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone); acridines (1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acrylic) Nyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines (2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (eg benzyldiphenyl sulfide); acyl Examples include phosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like); titanocenes; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

  In addition, a photoinitiator can be obtained as a commercial item, for example, a brand name "Irgacure" "Darocur" (made by BASF Japan), a brand name "Syracure" (made by Union Carbide), etc.

  Examples of thermal polymerization initiators include dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, etc.), diacyl peroxides [dialkanoyl peroxide (such as lauroyl peroxide), and dialoyl peroxide (benzoyl peroxide). Oxide, benzoyl toluyl peroxide, toluyl peroxide, etc.)], peracid esters (percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctate, t-butyl peroxybenzoate, etc.), Organic peroxides such as ketone peroxides, peroxycarbonates, peroxyketals; azonitrile compounds [2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyro) Nitrile) 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc.], azoamide compound {2,2′-azobis {2-methyl -N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like}, azoamidine compounds {2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, etc.}, azoalkane compounds [2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis (4-cyano) Azo compounds, etc.], and azo compounds having an oxime skeleton [2,2′-azobis (2-methylpropionamide oxime, etc.)]. You may use a thermal-polymerization initiator individually or in combination of 2 or more types.

  The ratio of the polymerization initiator is 0.1 to 15 parts by weight, preferably 0.2 to 100 parts by weight of the total amount of the compound represented by the formula (B) and the compound represented by the formula (C). It can be selected from the range of -10 parts by weight, more preferably 0.3-10 parts by weight, still more preferably 0.5-7 parts by weight, and particularly preferably 0.7-5 parts by weight.

  In addition, you may combine a photoinitiator with a photosensitizer. Examples of the photosensitizer include conventional components such as tertiary amines [for example, trialkylamine, trialkanolamine (such as triethanolamine), ethyl N, N-dimethylaminobenzoate, N, N-dimethyl. Dialkylaminobenzoic acid alkyl esters such as amyl aminobenzoic acid, bis (dialkylamino) benzophenones such as 4,4-bis (dimethylamino) benzophenone (Michler's ketone), 4,4′-diethylaminobenzophenone], triphenylphosphine, etc. Examples include phosphine, toluidines such as N, N-dimethyltoluidine, anthracene such as 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. It is done. The photosensitizers may be used alone or in combination of two or more.

  The amount of the photosensitizer used is, for example, 0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 75 parts by weight, and still more preferably 100 parts by weight of the photopolymerization initiator. Is 10 to 50 parts by weight.

  The reaction may be performed in a solvent. Examples of the solvent include alcohols (alkyl alcohols such as ethanol, propanol, and isopropanol, glycols such as ethylene glycol and propylene glycol), hydrocarbons (aliphatic hydrocarbons such as hexane, and alicyclic rings such as cyclohexane). Formula hydrocarbons, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, etc.), ethers (chain ethers such as dimethyl ether, diethyl ether, dioxane, tetrahydrofuran, etc.) Cyclic ethers), esters (methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate, etc.), ketones (acetone, ethyl methyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-2-pyrrole) Cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (methylcarbitol, ethylcarbitol, butylcarbitol, etc.), propylene glycol monoalkyl ethers (propylene glycol monomethyl ether, propylene glycol mono) Ethyl ether, propylene glycol mono n-butyl ether, etc.), glycol ether esters (ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate etc.), amides (N, N-dimethylformamide, N, N-dimethylacetamide etc.), Sulfoxides (dimethyl sulfoxide, etc.), nitriles (acetonitrile, benzonitrile, etc.), N-methylpyrrolidone Which organic solvents. The solvent can be used alone or as a mixed solvent.

  The ratio of the total amount of the compound represented by the formula (B) and the compound represented by the formula (C) in the solvent is 1 to 90% by weight, preferably 5 to 80% by weight, and more preferably 10 to 50%. % By weight.

  The enthiol reaction proceeds by bringing the compound represented by the formula (B) into contact with the compound represented by the formula (C). Usually, the compound represented by the formula (B) and the formula You may make it react (enthiol reaction) by providing active energy to the reaction system containing the compound represented by (C). By applying active energy, the enethiol reaction can be easily advanced.

  As the active energy, thermal energy and / or light energy (particularly, at least light energy) can be used depending on the type of the polymerization initiator.

  When heat energy is applied (for example, when a thermal polymerization initiator is used), the heating temperature is, for example, 50 to 250 ° C, preferably 60 to 200 ° C, and more preferably 80 to 180 ° C.

  In addition, when light energy is applied (for example, when a photopolymerization initiator is used), as light, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, etc. can be used. There are many cases.

  As the light source, for example, in the case of ultraviolet rays, a deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as helium-cadmium laser or excimer laser), etc. Can be used. The wavelength of light may be, for example, about 150 to 800 nm, preferably 150 to 600 nm, more preferably about 200 to 400 nm (particularly 300 to 400 nm). The amount of irradiation (irradiation energy) is not particularly limited, and may be, for example, 1 to 10000 mW, preferably 5 to 5000 mW, and more preferably about 10 to 1000 mW. Further, the irradiation time is not particularly limited, and is 5 seconds to 60 minutes, preferably 10 seconds to 30 minutes, and more preferably 30 seconds to 10 minutes.

  Note that heat energy (heating) and light energy (light irradiation) may be combined.

  As described above, the compound represented by the formula (A) is obtained. Separation and purification of the compound represented by the formula (A) from the reaction mixture can be performed using a conventional method.

[Polymerizable composition and cured product]
Organosilane compounds of the present invention, the hydrolysis condensable group (i.e., in the formula (A), X is -Si (OR ²⁾ _a (groups represented by ^{R _{3) 3-a)}} has a Therefore, it can be polymerized (or cured) by hydrolysis condensation (sol-gel reaction), and a polymerizable composition can be formed. Therefore, it is also possible to form a hybrid film by mixing with other known coupling agents by a sol-gel reaction.

  The allyl ester compound of the present invention may be used for raw material applications such as active energy ray-curable or thermosetting inks, paints, and coating agents such as ultraviolet rays and electron beams.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited at all by an Example.

<Synthesis Example 1>
Diallyl hexahydrophthalate (5.05 g, 20 mmol) and 3-mercaptopropyltrimethoxysilane (7.85 g, 40 mmol) were dissolved in toluene (73 mL). After adding 401 mg of Irgacure 819 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator to the obtained solution, the solution was reacted by irradiating with ultraviolet rays (100 mW / cm ^{2 for} 3 minutes) while stirring the solution. The reaction solution was concentrated under reduced pressure, and toluene was distilled off to obtain 12.9 g of bis (7-trimethoxysilyl-4-thioheptyl) hexahydrophthalate (compound (1)). Physical property values are shown below.
1H NMR (270 MHz, CDCl3) δ 0.75 (m, 4H,), 1.33-1.60 (m, 4H), 1.63-1.80 (m, 4H), 1.83-1. 95 (m, 4H), 3.47-2.61 (m, 8H), 2.81 (t, 2H), 3.57 (s, 18H), 4.10-4.25 (m, 4H)
13C NMR (68 MHz, CDCl3) δ 8.6, 23.0, 23.8, 26.3, 28.4, 28.8, 35.0, 42.6, 50.5, 63.0, 173. 3

<Synthesis Example 2>
Diallyl 3or4-methylhexahydrophthalate (3-position 35%, 4-position 65%) 5.33 g (20 mmol) and 3-mercaptopropyltrimethoxysilane 7.85 g (40 mmol) were dissolved in toluene 73 mL. After adding 401 mg of Irgacure 819 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator to the obtained solution, the solution was reacted by being irradiated with ultraviolet rays (100 mW / cm ² , 3 minutes) while stirring the solution. The reaction solution was concentrated under reduced pressure, and toluene was distilled off to obtain 13.1 g of bis (7-trimethoxysilyl-4-thioheptyl) isophthalate (compound (2)).

Modification treatment example 1 (treatment of titanium oxide (titania) particles)
50 g of toluene was put into a beaker having an internal volume of 100 ml, and while stirring with a magnetic stirrer, 0.5 g of the coupling agent obtained in Synthesis Example 1 was added and uniformly dissolved to obtain a surface treatment agent. Titanium oxide particles (average particle diameter 0.5 μm) (manufactured by Titanium Industry Co., Ltd.) 50 g were immersed in this surface treatment agent for 30 minutes and dried in an oven at 70 ° C. for 2 hours to modify the titanium oxide particles. Got.

Modification example 2 (Alumina particle treatment)
50 g of toluene was put into a beaker having an internal volume of 100 ml, and while stirring with a magnetic stirrer, 0.5 g of the coupling agent obtained in Synthesis Example 2 was added and uniformly dissolved to obtain a surface treatment agent. The surface treatment agent was immersed in 50 g of alumina particles (average particle diameter 3 μm) (manufactured by Showa Denko KK) for 30 minutes, and dried in an oven at 70 ° C. for 2 hours to obtain modified alumina particles.

Modification treatment example 3 (treatment of zirconium oxide (zirconia) particles)
50 g of toluene was put into a beaker having an internal volume of 100 ml, and while stirring with a magnetic stirrer, 0.5 g of a coupling agent represented by the general formula (5) was added and uniformly dissolved to obtain a surface treatment agent. The surface treatment agent was modified by dispersing 20 g of zirconium oxide particles (average particle size 20 nm) (Daiichi Rare Element Chemical Co., Ltd.) with a homogenizer for 10 minutes and drying at 70 ° C. for 2 hours in an oven. Zirconium oxide particles were obtained.

Modification example 4 (treatment of zinc oxide particles)
50 g of toluene was put into a beaker having an internal volume of 100 ml, and while stirring with a magnetic stirrer, 0.5 g of a coupling agent represented by the general formula (7) was added and uniformly dissolved to obtain a surface treatment agent. Zinc oxide that was modified by dispersing 20 g of zinc oxide particles (average particle size 25 nm) (manufactured by Sakai Chemical Industry Co., Ltd.) for 10 minutes in this surface treatment agent and drying in an oven at 70 ° C. for 2 hours. Particles were obtained.

[Example 1]
200 parts by weight of titanium oxide and 30 parts by weight of amine-based curing agent modified in Modification Example 1 were added to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 1001) (manufactured by Mitsubishi Chemical) (main agent). The mixture was kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition. This was cast-molded to obtain a test piece 1.

[Example 2]
200 parts by weight of alumina modified in Modification Example 2 and 30 parts by weight of an amine curing agent were added to 100 parts by weight of bisphenol A type epoxy resin (Epicoat 1001) (manufactured by Mitsubishi Chemical Corporation) (main agent), The mixture was kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition. This was cast-molded to obtain a test piece 2.

[Example 3]
Bisphenol A type epoxy resin (Epicoat 1001) (manufactured by Mitsubishi Chemical) (main agent) 100 parts by weight of alumina (average particle size 30 μm) 200 parts by weight, coupling agent 5 parts by weight represented by general formula (10), amine-based 30 parts by weight of a curing agent was added, kneaded at 95 ° C. for 8 minutes using a hot roll, cooled and pulverized to obtain an epoxy resin composition. This was cast and made into a test piece 3.

[Comparative Example 1]
A test piece 4 was obtained in exactly the same manner as in Example 3 except that no coupling agent was added.

[Comparative Example 2]
A test piece 5 was obtained in exactly the same manner as in Example 3 except that 5 parts by weight of a commercially available silane coupling agent (γ-aminopropyltrimethoxysilane) was added as a coupling agent instead of the general formula (10). .

Bending strength (Kg / mm 2) and tan δ were measured for these test pieces. Further, the water absorption (%), bending strength (Kg / mm 2) and tan δ after the test piece was immersed in warm water at 70 ° C. for 24 hours were measured. The bending strength was measured by a three-point bending method based on JIS K7171 using a test piece of 80 mm × 10 mm × 4 mm. As for tan δ, the test piece was measured at 2 GHz using a cavity resonator perturbation method dielectric constant measuring apparatus [manufactured by Kanto Electronics Application Development Co., Ltd.].
The results are shown in Table 1.

表１から、無添加や従来のシランカップリング剤に比べて、吸水後の全ての物性値において、本発明のカップリング剤が高い改質処理効果を示していることが判る。

From Table 1, it can be seen that the coupling agent of the present invention exhibits a high modification treatment effect in all physical property values after water absorption as compared with the additive-free or conventional silane coupling agent.

[Example 4]
20 parts by weight of zirconium oxide particles and 80 parts by weight of methyl ethyl ketone treated in Modification Example 3 were treated for 30 minutes at a peripheral speed of 8 m / s in bead mill conditions, and 100 parts by weight of the resulting treatment liquid was subjected to polyester resin ( 2 parts by weight of Byron 200 manufactured by Toyobo Co., Ltd. was blended and treated with an ultrasonic disperser for 30 minutes to obtain a metal oxide filler dispersion having an average particle size of 20.3 nm.

[Example 5]
20 parts by weight of zinc oxide particles and 80 parts by weight of methyl ethyl ketone treated in the modification treatment example 4 were treated for 30 minutes at a peripheral speed of 8 m / s in bead mill conditions, and a polyester resin ( 2 parts by weight of Byron 200 manufactured by Toyobo Co., Ltd. was blended and treated with an ultrasonic disperser for 30 minutes to obtain a metal oxide filler dispersion having an average particle size of 25.2 nm.

[Example 6]
2 parts by weight of the coupling agent represented by the general formula (22) and 78 parts by weight of methyl ethyl ketone are treated with 20 parts by weight of zirconium oxide particles (average particle size 15 nm) at a peripheral speed of 8 m / s for bead mill conditions for 30 minutes. Recovered. 2 parts by weight of bisphenol F type epoxy resin (Epicoat 806) (manufactured by Mitsubishi Chemical Co., Ltd.) is blended with 100 parts by weight of the resulting treatment liquid, and treated with an ultrasonic disperser for 30 minutes to obtain an average particle size of 15.6 nm A metal oxide filler dispersion was obtained.

[Comparative Example 3]
2 parts by weight of 3-methacryloxypropyltrimethoxysilane, which is a commercially available silane coupling agent, and 78 parts by weight of methyl ethyl ketone are adjusted to a bead mill peripheral speed of 8 m / s with respect to 20 parts by weight of zirconium oxide particles (average particle size 15 nm). And collected for 30 minutes. 2 parts by weight of bisphenol F type epoxy resin (Epicoat 806) (manufactured by Mitsubishi Chemical Co., Ltd.) is blended with 100 parts by weight of the obtained treatment liquid, and treated with an ultrasonic disperser for 30 minutes to disperse the metal oxide filler. Got.

(Evaluation method)
(appearance)
The appearance of the produced metal oxide filler dispersion was observed to confirm the dispersibility. A sample that was dispersed and transparent was marked with ◯, a sample that had settled but was dispersed was marked by Δ, and a sample that was not transparent and was not dispersed was marked with ×.
The results are shown in Table 2.

表２から、従来のシランカップリング剤に比べて本発明のカップリング剤が高い分散効果を示していることが判る。

From Table 2, it can be seen that the coupling agent of the present invention exhibits a higher dispersion effect than the conventional silane coupling agent.

(Preparation of coating liquid A-1)
30 parts by weight of the coupling agent represented by the compound (14) was diluted with 100 parts by weight of toluene to prepare a coating liquid A-1.

(Preparation of coating liquid A-2)
30 parts by weight of a coupling agent represented by the compound (17) was diluted with 100 parts by weight of toluene to prepare a coating liquid A-2.

(Preparation of coating solution B)
A diallyl phthalate polymer (manufactured by Daiso Corporation) is dissolved in acetone to give a 20 wt% acetone solution, and 60 mg of Irgacure 907 (manufactured by BASF Japan) is added as a photopolymerization initiator to 100 g of the acetone solution. Liquid B was prepared.

[Example 7]
After coating the coating liquid A-1 on a glass substrate and forming a coating film having a thickness of 10 μm by treating at 150 ° C. for 2 hours, the coating liquid B is applied to a thickness of 50 μm and irradiated with ultraviolet rays (100 mW / cm ² for 30 seconds).

[Example 8]
After coating the coating liquid A-2 on a glass substrate and forming a coating film having a thickness of 10 μm by treating at 150 ° C. for 2 hours, the coating liquid B is applied to a thickness of 50 μm and irradiated with ultraviolet rays (100 mW / cm ² for 30 seconds).

[Comparative Example 4]
The same operation as in Example 7 was performed, except that the coating liquid A-1 was not used and the coating liquid B was directly applied to the glass to a thickness of 50 μm.

The adhesiveness of the obtained coating film was evaluated by a cross cut test (JIS K5600).
The results are shown in Table 3.

比較例４はグリッドをカッターで入れた段階で剥離した。
表３に示した結果から、本発明のカップリング剤が高いアンカー効果を示していることが判った。

The comparative example 4 peeled in the step which put the grid with the cutter.
From the results shown in Table 3, it was found that the coupling agent of the present invention showed a high anchor effect.

  As described above, according to the present invention, a high reforming treatment effect can be obtained even for inorganic fillers such as alumina and titania, in which a sufficient reforming treatment effect was not obtained by the treatment with the conventional silane coupling agent. The composite material in which the modified inorganic filler is filled in the polymer material also has significantly improved physical properties such as mechanical strength, water resistance, adhesion, and electrical characteristics. Furthermore, a solution in which an inorganic filler is dispersed in a polymer material has good dispersibility as a coating liquid, and can be applied to various coating liquids. The polymer film itself can also be used as an anchor coat layer.

Claims (6)

The following general formula (A)

[In the formula, Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ represents an alkylene group, and X represents —Si (OR ² ). a (R ³ ) 3-a [wherein R ² is an alkyl group or — (R ⁴ O) _b —R ⁵ (wherein R ⁴ is an alkylene group, R ⁵ is an alkyl group, and b is an integer of 1 or more) R ³ represents a hydrogen atom, a hydroxyl group, a halogen atom or a hydrocarbon group, and a represents an integer of 1 to 3. ], And n is an integer of 2-4. ]
A coupling agent comprising an organosilicon compound represented by In the formula (A), Z represents an alicyclic compound which may partially have a double bond, may contain a hetero atom, R ¹ is an alkylene group having 2 to 4 carbon atoms, and X is ^{-Si (OR 2) 3, R} 2 represents an alkyl group having 1 to 6 carbon atoms, n represents an integer of 2 to 4, a coupling agent consisting of an organic silicon compound according to claim 1, wherein.   A method for modifying an inorganic filler, wherein the surface treatment of the inorganic filler is performed using the coupling agent according to claim 1.   The method for modifying a polymer material according to claim 3, wherein the coupling agent according to claim 1 or 2, an inorganic filler, and a polymer material are used.   5. The reforming treatment method according to claim 3, wherein the inorganic filler is titanium oxide, zinc oxide, silica, alumina, or zirconium oxide.   A method for modifying a substrate, comprising: coating the surface of the substrate with the coupling agent according to claim 1 or 2 and performing a heat treatment to form a thin film.