JP2015182978A - Organic silicon compound, adhesive composition, and article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic silicon compound used for an adhesive composition and having a catechol structure.SOLUTION: An organic silicon compound comprises a hydrolyzable silyl group and a catechol structure protected with a silyl group in a molecule represented by formula (1), where at least one of R-Ris an organic group having an Si substituent at a terminal, and others are H, an alkyl group or the like; and Ris an univalent hydrocarbon group.

Description

  The present invention relates to an hydrolyzable silyl group and an organosilicon compound having a catechol structure protected with a silyl group in the molecule, an adhesive composition containing the compound, and an article comprising a substrate treated with the composition About.

  In recent years, research has been conducted on the special chemical structure of the adhesion protein of mussels, which is outstanding as an underwater adhesive, and the adhesion mechanism using it skillfully. Although many mysteries remain about the adhesion mechanism, it is known that a compound having a catechol structure contained in the adhesive plays an important role.

  In Patent Document 1 (Japanese Patent Laid-Open No. 2010-144148), the adhesion between the plated lead frame and the epoxy resin or silicone resin is improved by forming a polydopamine thin film. In Non-Patent Document 1 (J. Am. Chem. Soc. 2012, 134, 20139-20145), a silyl group-protected catechol group is obtained by subjecting a silyl group-protected vinyl group-containing catechol compound and a mercapto group-containing silicone to an enethiol reaction. The containing silicone is synthesized and used as a component for the adhesive composition.

  As described above, there are examples in which a compound having a catechol structure is used as a component of an adhesive composition, but organosilicon having a hydrolyzable silyl group and a catechol structure protected by a silyl group in the molecule so far. There are no reports of compounds and adhesive compositions containing them.

JP 2010-144148 A

J. Am. Chem. Soc. 2012, 134, 20139-20145

  The present invention has been made in view of the above circumstances, and an organosilicon compound having a hydrolyzable silyl group and a catechol structure protected with a silyl group in the molecule, an adhesive composition containing the compound, and the composition It is an object to provide an article comprising a treated substrate.

（式中、Ｒ¹〜Ｒ⁴は各々独立に水素原子；置換基を有してもよく、エーテル結合、チオエーテル結合、カルボニル結合及びチオカルボニル結合から選ばれる１以上の結合が介在してもよい一価の炭化水素基；及び下記式（２）〜（５）で表される有機基から選ばれるが、Ｒ¹〜Ｒ⁴の少なくとも一つは下記式（２）〜（５）で表される有機基のいづれかであり、Ｒ⁸は各々独立に置換基を有してもよい一価の炭化水素基である。）

（式中、Ｒ⁵は置換基を有してもよく、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、アミノ結合、ウレタン結合及びウレア結合から選ばれる１以上の結合が介在してもよい二価の炭化水素基であり、Ｒ⁶は炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基であり、Ｒ⁷は炭素数１〜２０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１０のアリール基、又は炭素数１〜２０のアシル基であり、ｎは１〜３の整数を表す。波線はベンゼン環に対する結合位置を示す。）
で表される有機ケイ素化合物。
〔２〕
上記式（２）が、下記式（６）〜（１０）

（式中、ｍは１〜８の整数であり、ｓは１〜８の整数であり、Ｒ⁶、Ｒ⁷、ｎ、波線は上記と同じ。Ｍｅはメチル基を示す。）
のいずれかで表される〔１〕記載の有機ケイ素化合物。
〔３〕
上記式（３）が、下記式（１１）、（１２）

（式中、ｍは１〜８の整数であり、ｓは１〜８の整数であり、Ｒ⁶、Ｒ⁷、ｎ、波線は上記と同じ。）
のいずれかで表される〔１〕記載の有機ケイ素化合物。
〔４〕
上記式（４）が、下記式（１３）、（１４）

（式中、ｍは１〜８の整数であり、ｓは１〜８の整数であり、Ｒ⁶、Ｒ⁷、ｎ、波線は上記と同じ。）
のいずれかで表される〔１〕記載の有機ケイ素化合物。
〔５〕
上記式（５）が、下記式（１５）

（式中、ｍは１〜８の整数であり、Ｒ⁶、Ｒ⁷、ｎ、波線は上記と同じ。）
で表される〔１〕記載の有機ケイ素化合物。
〔６〕
〔１〕〜〔５〕のいずれかに記載の有機ケイ素化合物を含有する接着性組成物。
〔７〕
〔６〕記載の接着性組成物にて表面処理された基材を含む物品。
〔８〕
表面処理される基材が、ガラスクロス、ガラステープ、ガラスマット、ガラスペーパーから選ばれるガラス繊維製品である〔７〕記載の物品。
〔９〕
表面処理される基材が、無機フィラーである〔７〕記載の物品。
〔１０〕
表面処理される基材が、セラミック又は金属である〔７〕記載の物品。 The said subject can be achieved by the organosilicon compound shown by following formula (1).
[1]
Following formula (1)

(In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom; may have a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond, and a thiocarbonyl bond may intervene. A monovalent hydrocarbon group; and an organic group represented by the following formulas (2) to (5), but at least one of R ^{1 to} R ⁴ is represented by the following formulas (2) to (5). And each R ⁸ is independently a monovalent hydrocarbon group which may have a substituent.)

(In the formula, R ⁵ may have a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an amino bond, a urethane bond, and a urea bond may intervene. A divalent hydrocarbon group, R ⁶ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 20 carbon atoms and 2 to 10 carbon atoms An alkenyl group, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3. A wavy line indicates a bonding position to a benzene ring.)
An organosilicon compound represented by
[2]
The above formula (2) is converted into the following formulas (6) to (10).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, R ⁶ , R ⁷ , n, and wavy lines are the same as above. Me represents a methyl group.)
[1] The organosilicon compound represented by any one of the above.
[3]
The above formula (3) is converted into the following formulas (11) and (12).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, and R ⁶ , R ⁷ , n, and the wavy line are the same as above.)
[1] The organosilicon compound represented by any one of the above.
[4]
The above formula (4) is converted into the following formulas (13) and (14).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, and R ⁶ , R ⁷ , n, and the wavy line are the same as above.)
[1] The organosilicon compound represented by any one of the above.
[5]
The above formula (5) is replaced by the following formula (15)

(In the formula, m is an integer of 1 to 8, and R ⁶ , R ⁷ , n and wavy lines are the same as above.)
[1] The organosilicon compound represented by
[6]
[1] An adhesive composition containing the organosilicon compound according to any one of [5].
[7]
[6] An article comprising a substrate surface-treated with the adhesive composition according to [6].
[8]
The article according to [7], wherein the substrate to be surface-treated is a glass fiber product selected from glass cloth, glass tape, glass mat, and glass paper.
[9]
The article according to [7], wherein the substrate to be surface-treated is an inorganic filler.
[10]
The article according to [7], wherein the substrate to be surface-treated is ceramic or metal.

  The organosilicon compound of the present invention has a catechol structure protected with a hydrolyzable silyl group and a silyl group in one molecule, and the adhesive composition containing the organosilicon compound of the present invention is used as a surface treatment agent. The used modified resin is excellent in adhesion to various inorganic materials such as glass and metal. Further, since the catechol group is protected with a silyl group, the storage stability when mixed with a polymer material is excellent.

  Hereinafter, the present invention will be specifically described. In the present invention, the “silane coupling agent” is included in the “organosilicon compound”.

[Organic silicon compound (silane coupling agent)]
A characteristic of the organosilicon compound (silane coupling agent) of the present invention is that it has both the following structures (i) and (ii).
(I) Hydrolyzable silyl group (ii) Catechol structure protected with silyl group

（式中、Ｒ¹〜Ｒ⁴は各々独立に水素原子、置換基を有してもよく、エーテル結合、チオエーテル結合、カルボニル結合及びチオカルボニル結合から選ばれる１以上の結合が介在してもよい一価の炭化水素基、下記式（２）〜（５）で表される有機基から選ばれるが、Ｒ¹〜Ｒ⁴の少なくとも一つは下記式（２）〜（５）で表される有機基のいづれかであり、Ｒ⁸は各々独立に置換基を有してもよい一価の炭化水素基である。）

（式中、Ｒ⁵は置換基を有してもよく、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、アミノ結合、ウレタン結合及びウレア結合から選ばれる１以上の結合が介在してもよい二価の炭化水素基であり、Ｒ⁶は炭素数１〜１０のアルキル基又は炭素数６〜１０のアリール基であり、Ｒ⁷は炭素数１〜２０のアルキル基、炭素数２〜１０のアルケニル基、炭素数６〜１０のアリール基、又は炭素数１〜２０のアシル基であり、ｎは１〜３の整数を表す。波線はベンゼン環に対する結合位置を示す。） An organosilicon compound represented by the following formula (1) can be shown as a series of structures having both (i) and (ii).

(In the formula, R ^{1 to} R ⁴ may each independently have a hydrogen atom or a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond and a thiocarbonyl bond may intervene. The monovalent hydrocarbon group is selected from organic groups represented by the following formulas (2) to (5), but at least one of R ^{1 to} R ⁴ is represented by the following formulas (2) to (5). Any of organic groups, and R ⁸ is each independently a monovalent hydrocarbon group which may have a substituent.)

(In the formula, R ⁵ may have a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an amino bond, a urethane bond, and a urea bond may intervene. A divalent hydrocarbon group, R ⁶ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 20 carbon atoms and 2 to 10 carbon atoms An alkenyl group, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3. A wavy line indicates a bonding position to a benzene ring.)

Here, the monovalent hydrocarbon group in which one or more bonds selected from a substituted or unsubstituted ether bond, thioether bond, carbonyl bond, and thiocarbonyl bond may be present as R ^{1 to} R ⁴ includes Examples thereof include 1 to 10, preferably 1 to 6, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl. Group, alkyl group such as octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenyl Examples include aralkyl groups such as an ethyl group and a phenylpropyl group. R ^{1 to} R ⁴ may have a substituent. Examples of the substituent include an epoxy group, an acrylic group, a methacryl group, an alcohol group (OH group), a mercapto group, and an amino group. Is mentioned. Further, as described above, an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond may intervene.

Examples of the monovalent hydrocarbon group for R ⁸ include those having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group. , Alkyl groups such as pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aryl groups, benzyl groups, phenylethyl groups, phenylpropyl groups, and the like, and among them, a methyl group, an ethyl group, a tert-butyl group, and a phenyl group are preferable.

Examples of the divalent hydrocarbon group for R ⁵ include alkylene such as methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, tert-butylene group, pentylene group, neopentylene group, hexylene group, and octylene group. Group, cycloalkylene group such as cyclohexylene group, alkenylene group such as vinylene group, arylene group, propenylene group, arylene group such as phenylene group, tolylene group, xylylene group, naphthylene group, benzylene group, phenylethylene group, phenylpropylene group Examples thereof include divalent hydrocarbon groups having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, such as aralkylene groups, and the like, substituted with hydroxyl groups, and the like, and further include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, amino Bond (-NR-: R is H, carbon number is 1 3 alkyl group or a phenyl group), one or more bond selected from a urethane bond and urea bond may be interposed.

R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to ⁶ carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tert-butyl group. , Alkyl groups such as pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aryl groups such as aryl groups, benzyl groups, phenylethyl groups, phenylpropyl groups, and the like. Among these, methyl groups, ethyl groups, and phenyl groups are preferable.

R ⁷ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group. , Alkyl groups such as pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl groups such as cyclohexyl group, alkenyl groups such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aryl groups such as aryl group, benzyl group, phenylethyl group, phenylpropyl group, and the like. Among these, a methyl group and an ethyl group are preferable.

（式中、ｍは１〜８の整数であり、ｓは１〜８の整数であり、Ｒ⁶、Ｒ⁷、ｎ、波線は上記と同じ。Ｍｅはメチル基を示す。） More specifically, the following formulas (6) to (10) can be shown as the above formula (2).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, R ⁶ , R ⁷ , n, and wavy lines are the same as above. Me represents a methyl group.)

（式中、Ｒ⁶、Ｒ⁷、ｍ、ｎ、ｓ、波線は上記と同じ。） Moreover, following formula (11), (12) can be shown as said formula (3).

(In the formula, R ⁶ , R ⁷ , m, n, s and wavy lines are the same as above.)

（式中、Ｒ⁶、Ｒ⁷、ｍ、ｎ、ｓ、波線は上記と同じ。） The following formulas (13) and (14) can be shown as the above formula (4).

(In the formula, R ⁶ , R ⁷ , m, n, s and wavy lines are the same as above.)

（式中、Ｒ⁶、Ｒ⁷、ｍ、ｎ、波線は上記と同じ。） The following formula (15) can be shown as the above formula (5).

(In the formula, R ⁶ , R ⁷ , m, n and wavy lines are the same as above.)

  There are a plurality of methods for producing the organosilicon compound of the present invention. That is, the above formula (2) is an organosilicon compound having the above formula (6), the above formula (3) is an organosilicon compound having the above formula (11), and the above formula (3) is an organic having the above formula (13). The silicon compound can be obtained by hydrosilylating a compound having a catechol structure protected with a silyl group and a terminal alkenyl group and a hydrogen organosilane compound in the presence of a catalyst.

  The organosilicon compound in which the above formula (2) represents the above formula (7), the above formula (3) represents the organosilicon compound that represents the above formula (12), and the above formula (3) represents the organosilicon compound that represents the above formula (14). Then, it can be obtained by subjecting a catechol structure protected with a silyl group, a compound having a terminal alkenyl group, and an organosilicon compound having a mercapto group to an enethiol reaction.

  The organosilicon compound in which the above formula (2) represents the above formula (8) is obtained by reacting a catechol structure protected with a silyl group, an organosilicon compound having an aliphatic alcohol, and an organosilicon compound having an isocyanate group. .

  The organosilicon compound in which the above formula (2) represents the above formula (9) is obtained by reacting a catechol structure protected with a silyl group, an organosilicon compound having a secondary amino group, and an organosilicon compound having an isocyanate group. It is done.

  The organosilicon compound in which the above formula (2) represents the above formula (10) is obtained by reacting a catechol structure protected with a silyl group, an organosilicon compound having a secondary amino group, and an organosilicon compound having an epoxy group. It is done.

  The organosilicon compound in which the above formula (5) represents the above formula (15) is obtained by reacting a catechol structure protected with a silyl group, an organosilicon compound having an aromatic alcohol group, and an organosilicon compound having an isocyanate group. It is done.

  Examples of the adhesive composition containing the general formula (1) include an organosilicon compound having a catechol structure protected by a silyl group represented by the general formula (1) and an inorganic material, and a general formula (1). An organosilicon compound having a catechol structure protected by a silyl group and a low molecular material, an organosilicon compound having a catechol structure protected by a silyl group represented by the general formula (1) and a polymer material, and a general formula (1) Examples include combinations of the organic silicon compound having a catechol structure protected with a silyl group and a solvent, which can be used alone or as a mixed composition. In addition, the organosilicon compound having a catechol structure protected by a silyl group represented by the general formula (1) may be combined with the above-mentioned material or solvent with a reaction.

  Although there is no restriction | limiting in particular in the quantity of General formula (1) contained in an adhesive composition, since an effect will become low when there is too little content, and it may become economically disadvantageous when there is too much content, Preferably it is 0.001-50 mass%, More preferably, it is 0.1-10 mass%.

More specifically, the organosilicon compound of the general formula (1) is preferably used after being dissolved in a solvent. In this case, the solvent is not particularly limited, but hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ethyl acetate. Ester solvents such as butyl acetate, aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, protic polar solvents such as methanol, ethanol, alcohol and water, and halogenated hydrocarbon solvents such as dichloromethane and chloroform Among them, a protic polar solvent is preferable from the viewpoint of improving the stability of the catechol group. These solvents may be used alone or in combination of two or more.
Moreover, you may use an acid or a base as a pH adjuster, In this case, it is preferable that pH of a composition is 2-13, especially 3-12.

  The organosilicon compound of the general formula (1) is dissolved in the solvent at a concentration of 0.001 to 50% by mass, particularly 0.1 to 10% by mass, so that both adhesion and cost are compatible. This is preferable.

  The adhesive composition of the present invention can contain an inorganic material, and examples of the inorganic material include titanium oxide, silicon oxide, aluminum oxide, zirconium oxide, etc., and 0 to 80% by mass in the composition. Content.

  Moreover, the polymeric monomer (low molecular material) which melt | dissolves the said organosilicon compound and / or melt | dissolves in the said solvent can be contained. Examples of the low molecular weight material include compounds having a molecular weight of 1,000 or less, and there is no particular limitation. However, when having a functional group, for example, a hydroxy group, a carbonyl group, a carboxyl group, an amino group, a thiol group, a cyano group , Sulfonyl group, nitro group, isocyanate group, isothiocyanate group, silyl group, sulfide bond, amide bond, urea bond, ester bond, siloxane bond, vinyl group, acrylic group, radical polymerizable group, cyclic ether group, vinyl ether group, etc. Examples thereof include those having a ring-opening metathesis polymerizable group such as a cationic polymerizable group, a norbornenyl group, and a dicyclopentadienyl group, and the number of these functional groups is not limited. These low molecular materials may be used individually by 1 type, or may mix and use 2 or more types.

Specifically, the low-molecular material is a hydrocarbon having 1 to 50 carbon atoms, which may include a chain, branched, cyclic structure or aromatic group, and part or all of the hydrogen atoms of the hydrocarbon. May be substituted. Specific examples of the substituent include hydroxy group, carbonyl group, carboxyl group, amino group, thiol group, cyano group, sulfonyl group, nitro group, isocyanate group, isothiocyanate group, alkylsilyl group, alkoxysilyl group, Examples include radically polymerizable groups such as vinyl groups and acrylic groups, cationic polymerizable groups such as cyclic ether groups and vinyl ether groups, ring-opening metathesis polymerizable groups such as norbornenyl groups and dicyclopentadienyl groups, sulfide bonds, amide bonds, A urea bond, an ester bond, and a siloxane bond may be included, and a plurality of these functional groups may be contained.
The blending amount of the low molecular weight material is preferably 99% by mass or less, more preferably 50% by mass or less, and particularly preferably 1 to 30% by mass in the composition.

  Furthermore, the adhesive composition of this invention can contain the polymer (polymer material) which melt | dissolves in this solvent with the said solvent. As the polymer material, a polymer compound having a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) of more than 1,000, preferably more than 1,000 to 100,000, particularly 2,000 to 50,000 is preferable. . In this case, the polymer material is not particularly limited, but when it has a functional group, for example, hydroxy group, carbonyl group, carboxyl group, amino group, thiol group, cyano group, sulfonyl group, nitro group, isocyanate Group, isothiocyanate group, silyl group, sulfide bond, amide bond, urea bond, ester bond, siloxane bond, radical polymerizable group such as vinyl group and acrylic group, cationic polymerizable group such as cyclic ether group and vinyl ether group, norbornenyl group Examples thereof include a ring-opening metathesis polymerizable group such as a dicyclopentadienyl group, and the number of these functional groups is not limited, and polymer materials obtained by reacting these functional groups are also included. These polymer materials may be used alone or in a combination of two or more.

Specifically, natural polymer materials such as proteins, nucleic acids, lipids, polysaccharides, natural rubber, phenol resins, epoxy resins, melamine resins, urea resins, polyurethanes, polyimides, polyamideimides, polyethylenes, polypropylenes, polyvinyl chlorides, Polystyrene, polyvinyl acetate, acrylic resin, nitrile resin, isoprene resin, urethane resin, ethylene propylene resin, epichlorohydrin resin, chloroprene resin, butadiene resin, styrene / butadiene resin, polyamide, polyacetal, polycarbonate, polyphenylene ether, polyethylene terephthalate, polybutylene Terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyetherether Mentioned synthetic polymer material ketone or the like, can be used a copolymer thereof, a polymer alloy or the like.
The blending amount of the polymer material is preferably 99% by mass or less, more preferably 50% by mass or less, and particularly preferably 1 to 30% by mass in the composition.

  As the adhesive composition of the present invention, in addition to the above composition, additives such as a surfactant, an antiseptic, a discoloration inhibitor, and an antioxidant are blended within a range that does not impair the object of the present invention. be able to.

  As a substrate to be treated with the adhesive composition of the present invention, any organic material such as an organic material that generally reacts with a hydrolyzable silyl group to form a bond and interacts with a catechol group is applicable. The shape of the substrate is not particularly specified. Among them, typical inorganic materials include silicon, titanium, zirconium, magnesium, aluminum, indium, tin and inorganic fillers composed of single or composite oxides thereof, glass cloth including glass fiber, glass tape, glass Examples thereof include glass fiber products such as mats and glass paper, and metal substrates such as ceramics, iron, aluminum, copper, silver, gold, and magnesium. Representative organic materials include epoxy resin, phenol resin, polyimide resin, unsaturated polyester resin, cardboard, wood, solid wood, chipboard and the like. Note that the present invention is not limited to those exemplified here.

Although it does not specifically limit as a processing method, hardening conditions, etc. of the adhesive composition of this invention, Specifically, the method in case a flow coat (dipping method), a spin coat, etc. process to a base material directly. It is also applied to a kneading process by adding and mixing in advance to a compound comprising an untreated inorganic filler and a dispersion medium resin.
Typical curing conditions include heating and drying. After surface treatment, heating and drying at 60 to 180 ° C., preferably 80 to 150 ° C. for 5 minutes to 2 hours, and simultaneously with removal of the solvent in the surface treatment agent It is preferable to chemically react the silane coupling agent which is the main component of the base material and the substrate surface.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated in detail, this invention is not restrict | limited to these Examples. Et represents an ethyl group, and Me represents a methyl group.

Synthesis of organosilicon compounds (16) to (19) [Synthesis Example 1]
In a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 164.2 g (1 mol) of eugenol, 400 g of toluene and 0.4 g of pentafluorophenyl boron were placed, and 244 g of triethylsilane (1.1 mol) ) Was added dropwise at an internal temperature of 90 ° C. over 2 hours. Thereafter, after cooling to room temperature, 2 g of KYOWARD 500 (manufactured by Kyowa Chemical Industry) was added and stirred for 2 hours. Then, 374g of organosilicon compounds (16) were able to be obtained by performing filtration and stripping. ^{From the 1} H-NMR spectrum, the reaction product was confirmed to be a product having a structure represented by the following chemical structural formula (16).

[Synthesis Example 2]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 189 g (0.5 mol) of an organosilicon compound (16), platinum-1,3-divinyl-1,1,3, A toluene solution of 3-tetramethyldisiloxane complex (0.5 × 10 −4 mol as platinum atom) was placed, and 61 g (0.5 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours. . Then, it stirred at 80 degreeC for 1 hour, and the solution containing an organosilicon compound (17) was able to be obtained by performing stripping. ^{From the 1} H-NMR spectrum, the reaction product was confirmed to be a product having a structure represented by the following chemical structural formula (17). The obtained organosilicon compound is designated as Silane A.

[Synthesis Example 3]
In a 1 L separable flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 189 g (0.5 mol) of organosilicon compound (16) and perbutyl O (manufactured by NOF Corporation) were placed, and 3-mercaptopropyl 98 g (0.5 mol) of trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise at an internal temperature of 80 to 90 ° C. over 1 hour. Then, it stirred at 90 degreeC for 1 hour, and the solution containing an organosilicon compound (18) was able to be obtained by performing stripping. ^{From the 1} H-NMR spectrum, the reaction product was confirmed to be a product having a structure represented by the following chemical structural formula (18). The obtained organosilicon compound is designated as Silane B.

[Synthesis Example 4]
To a 2 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 150 g (1 mol) of 4-allylcatechol, platinum-1,3-divinyl-1,1,3,3-tetramethyldi A toluene solution of a siloxane complex (1 × 10 ⁻⁴ mol as platinum atom) was placed, and 122 g (1 mol) of trimethoxysilane was added dropwise at an internal temperature of 75 to 85 ° C. over 2 hours. Then, it stirred at 90 degreeC for 1 hour, and the solution containing an organosilicon compound (19) was able to be obtained by performing stripping. The obtained organosilicon compound is designated as silane C.

Epoxy resin mixed with organosilicon compound [Example 1]
In a 100 mL beaker, 20 g of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: JER828) was added, and 1 g of silane A was added with stirring, and the epoxy resin was obtained by uniformly dissolving. The resulting epoxy resin could be stored at room temperature for 1 month or more while being uniformly transparent.

[Example 2]
In a 100 mL beaker, 20 g of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: JER828) was added, and 1 g of Silane B was added while stirring, and uniformly dissolved to obtain an epoxy resin. The resulting epoxy resin could be stored at room temperature for 1 month or more while being uniformly transparent.

[Comparative Example 1]
In a 100 mL beaker, 20 g of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: JER828) was added, 1 g of silane C was added with stirring, and the epoxy resin was obtained by uniformly dissolving. The obtained epoxy resin was thickened and gelled in one month at room temperature.

[Comparative Example 2]
Add 20 g of epoxy resin (Japan Epoxy Resin Co., Ltd .: JER828) to a 100 mL beaker, add 1 g of 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903) with stirring, and dissolve uniformly. Thus, an epoxy resin was obtained. The obtained epoxy resin was thickened and gelled in one month at room temperature.

Evaluation of adhesion between glass fiber and epoxy resin [Examples 3 and 4, Comparative Examples 3 and 4]
Surface treatment agent obtained by diluting the silane A, B or 3-aminopropyltriethoxysilane obtained above (with Shin-Etsu Chemical Co., Ltd., KBE-903) with an acetic acid aqueous solution and methanol so as to be 1% by mass. Then, the glass fiber (diameter 20 μm) was processed, and then the surface-treated glass fiber was obtained by drying at 100 ° C. for 30 minutes. On the surface-treated glass fiber, a droplet having a diameter of several tens to several hundreds of μm of a thermosetting composition composed of an epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: JER828) and a curing agent (triethylenetetramine) After adhering so that the droplets do not come into contact with each other, thermosetting (treated at 80 ° C. for 1.5 hours and then treated at 100 ° C. for 2 hours) to form a spherical resin molded product, a composite interface property evaluation apparatus (Toei) The shear strength between the surface-treated glass fiber and the epoxy resin was measured by a microdroplet method using an industrial company (HM410). Here, the fiber diameter is D [μm], the length of the fiber embedded in the spherical resin molded product is L [μm], and the load when the spherical resin molded product is pulled out in the fiber axis direction is F [mN]. ], The shear strength τ [MPa] per unit area is obtained by τ = F / πDL. Table 1 shows the results of the main component and shear strength of the surface treatment agent used.

  The results of the above examples and comparative examples demonstrate that the modified surface formed using the adhesive composition of the present invention has an adhesion effect to the epoxy resin.

Claims (10)

Following formula (1)

(In the formula, R ^{1 to} R ⁴ are each independently a hydrogen atom; may have a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond, and a thiocarbonyl bond may intervene. A monovalent hydrocarbon group; and an organic group represented by the following formulas (2) to (5), but at least one of R ^{1 to} R ⁴ is represented by the following formulas (2) to (5). And each R ⁸ is independently a monovalent hydrocarbon group which may have a substituent.)

(In the formula, R ⁵ may have a substituent, and one or more bonds selected from an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an amino bond, a urethane bond, and a urea bond may intervene. A divalent hydrocarbon group, R ⁶ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁷ is an alkyl group having 1 to 20 carbon atoms and 2 to 10 carbon atoms An alkenyl group, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3. A wavy line indicates a bonding position to a benzene ring.)
An organosilicon compound represented by The above formula (2) is converted into the following formulas (6) to (10).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, R ⁶ , R ⁷ , n, and wavy lines are the same as above. Me represents a methyl group.)
The organosilicon compound of Claim 1 represented by any one of these. The above formula (3) is converted into the following formulas (11) and (12).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, and R ⁶ , R ⁷ , n, and the wavy line are the same as above.)
The organosilicon compound of Claim 1 represented by any one of these. The above formula (4) is converted into the following formulas (13) and (14).

(In the formula, m is an integer of 1 to 8, s is an integer of 1 to 8, and R ⁶ , R ⁷ , n, and the wavy line are the same as above.)
The organosilicon compound of Claim 1 represented by any one of these. The above formula (5) is replaced by the following formula (15)

(In the formula, m is an integer of 1 to 8, and R ⁶ , R ⁷ , n and wavy lines are the same as above.)
The organosilicon compound of Claim 1 represented by these.   The adhesive composition containing the organosilicon compound of any one of Claims 1-5.   An article comprising a substrate surface-treated with the adhesive composition according to claim 6.   The article according to claim 7, wherein the substrate to be surface-treated is a glass fiber product selected from glass cloth, glass tape, glass mat, and glass paper.   The article according to claim 7, wherein the substrate to be surface-treated is an inorganic filler.   The article according to claim 7, wherein the substrate to be surface-treated is ceramic or metal.