JPH07138535A - Adhesion promoter - Google Patents

Abstract

PURPOSE:To obtain an adhesion promoter which imparts excellent adhesive properties having excellent durability under an acidic condition to a curable resin compsn. (e.g. a curable silicone resin compsn.) without foaming the compsn. CONSTITUTION:An adhesion promoter mainly comprises a reaction product of an amine compd. of the formula; RnNH(3-n) (wherein R is a monovalent hydrocarbon group; and n is 1 or 2) with an epoxy compd. having an aliph. unsatd. bond or mainly comprises a condensate of the above-mentioned reaction product with a silicon compd. having at least two alkoxy groups directly bonded to silicon atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesion promoter, and more specifically, it provides a curable resin composition such as a curable silicone resin composition with excellent adhesiveness without foaming and under acidic conditions. The present invention relates to an adhesion promoter capable of imparting excellent durability and adhesiveness.

[0002]

2. Description of the Related Art Generally, curable resin compositions such as sealing materials, potting materials and coating materials include curable silicone resin compositions, curable polyurethane resin compositions, curable phenol resin compositions and curable polyester resins. A curable resin composition such as a composition, a curable epoxy resin composition, or a curable polysulfide resin composition is used. Such a curable resin composition has a problem that it has poor adhesion to inorganic materials such as glass, porcelain, and ceramics; metal materials such as aluminum, copper, stainless steel, and nickel; and substrates such as organic resins. It was necessary to pre-treat the above substrate.

For this reason, many attempts have been made to blend these curable resin compositions with an adhesion promoter to improve the self-adhesiveness of the composition. For example, aminoalkylalkoxysilane and Adhesion promoter formed by reaction with epoxyalkylalkoxysilane
-75633), and active hydrogen group-containing amine compounds or aminoalkylalkoxysilanes, epoxy group-containing organic compounds or epoxyalkylalkoxysilanes and alkoxysilanes (provided that amine compounds or aminoalkylalkoxysilanes or epoxy group-containing organic compounds or Any one of the epoxyalkylalkoxysilanes is an alkoxysilane.)
And an adhesion promoter (Japanese Patent Application Laid-Open No. 61-7207).
7).

However, the adhesion promoters proposed in JP-A-48-75633 and JP-A-61-72077 are
Although it is possible to impart relatively good adhesiveness to the curable resin composition, the adhesion promoter itself is very unstable because it has both a hydroxyl group and a silicon atom-bonded alkoxy group in its molecule, Further, when the curable resin composition containing this is heat-cured, there is a problem that the obtained cured resin foams.

Further, in the semiconductor manufacturing process, when the semiconductor is fixed to the copper frame, the copper frame is plated in advance and then fixed by soldering. Therefore, a masking for protecting a portion of the copper frame which should not be plated. Although a cured resin is used as the material, the cured resin used as the masking material has a problem that the adhesiveness to the copper frame is significantly reduced in the cleaning step such as acid cleaning and the resin is peeled off.

The present inventor has arrived at the present invention as a result of extensive studies on the above problems.

That is, the object of the present invention is to provide a curable resin composition with excellent adhesiveness without foaming and with excellent durability under acidic conditions. To provide an adhesion promoter.

[0008]

Means for Solving the Problem and Its Action The present invention provides (A) a general formula: R _n NH _(3-n) (wherein R is a monovalent hydrocarbon group and n is 1 or 2). . present) represented by amine compound with (B) relates to an adhesion promoter for a main agent and the reaction product of an epoxy compound having an aliphatic unsaturated bond, further the present invention, (a) the general formula: R _n NH _(3-n) (wherein R is a monovalent hydrocarbon group and n is 1 or 2) and (B) an epoxy compound having an aliphatic unsaturated bond The present invention relates to an adhesion promoter containing (C) a reaction product obtained by subjecting a silicon compound having at least two silicon atom-bonded alkoxy groups in one molecule to a condensation reaction as a main component.

First, the adhesion promoter of the invention of claim 1 will be described in detail.

The adhesion promoter of the present invention is represented by the general formula (A): R _n NH _(3-n) (wherein R is a monovalent hydrocarbon group and n is 1 or 2). The reaction product of the amine compound (B) and the epoxy compound having an aliphatic unsaturated bond as a main component.

The amine compound as the component (A) is represented by the general formula: R _n NH _(3-n) . In the above formula, R is a monovalent hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl group such as pentyl group, hexyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group; benzyl group, phenethyl group Aralkyl groups such as, and the like, and preferably an allyl group or a phenyl group. In the above formula, n is 1 or 2, when n is 1, the amine compound is a primary amine compound, and when n is 2, the amine compound is a secondary amine compound.

Specifically as such an amine compound,
Methylamine, ethylamine, n-propylamine, n
-Butylamine, t-butylamine, dimethylamine,
Diethylamine, dipropylamine, di (n-butyl)
Examples are amine, di (t-butyl) amine, allylamine, butenylamine, diallylamine, methylaniline, allylaniline and aniline, and allylamine and aniline are preferable.

The epoxy compound as the component (B) is an epoxy compound having an aliphatic unsaturated bond in the molecule. Specific examples of the epoxy compound as the component (B) include allyl glycidyl ether and butenyl glycidyl. ether,
Pentenyl glycidyl ether, 4-vinyl-1,2-
Epoxycyclohexane, 4-allyl-1,2-epoxycyclohexane, 4-butenyl-1,2-epoxycyclohexane, 4-pentenyl-1,2-epoxycyclohexane, glycidyl methacrylate and glycidyl acrylate are exemplified, and preferably allyl glycidyl ether. Is.

The adhesion promoter of the present invention can be prepared by reacting a nitrogen atom-bonded hydrogen atom in the component (A) with an epoxy group in the component (B). Although the above reaction proceeds at room temperature, it is dangerous because the reaction rapidly proceeds with considerable heat generation, so it is a method of gradually dropping the component (B) into the component (A), or in the component (B). It is preferable to carry out the method by gradually dropping the component (A). Further, in the above reaction, when the obtained adhesion promoter is added to a curable silicone resin composition which is cured by an addition reaction, (B)
The blending amount of the component is the nitrogen atom bonded hydrogen atom 1 in the component (A).
It is preferable to add an amount such that the number of moles of the epoxy groups in the component (B) is slightly excessive with respect to the moles, and more preferably, relative to 1 mole of the nitrogen atom-bonded hydrogen atom in the component (A).
The amount is such that the epoxy group in the component (B) becomes 1.01 to 2 mol. The temperature of the above reaction is not particularly limited, and it is preferable to gradually add the component (A) while heating the component (B) to 70 ° C. or higher in the flask. After completion of the reaction, the adhesion promoter of the present invention can be purified by distilling unreacted component (B) under reduced pressure.

When allyl glycidyl ether is used as the component (B) in the adhesion promoter of the present invention, the obtained adhesion promoter has the general formula:

[Chemical 1] (In the formula, R is a monovalent hydrocarbon group, and n is 1 or 2.) The main component is the reaction product. In the above formula, R is a monovalent hydrocarbon group, and specifically,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group; vinyl group, allyl group,
Alkenyl groups such as butenyl group, pentenyl group, hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group, etc., preferably allyl group or phenyl group. is there. Further, in the above formula, n is 1 or 2.

Next, the adhesion promoter of the invention of claim 2 will be described in detail.

The adhesion promoter of the present invention is a reaction product of the amine compound as the component (A) and the epoxy compound having an aliphatic unsaturated bond as the component (B), and further in one molecule of the component (C). A main product is a reaction product obtained by subjecting a silicon compound having at least two silicon atom-bonded alkoxy groups to a condensation reaction. As a result, the versatility of the adhesion promoter of the present invention is increased, and it can be applied to more curable resin compositions.

As the silicon compound as the component (C), alkoxysilane having at least two silicon atom-bonded alkoxy groups in one molecule and alkoxysilylalkylalkoxy having at least two silicon atom-bonded alkoxy groups in one molecule. Sisilane is exemplified. Specific examples of the alkoxysilane as the component (C) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, Methylvinyldimethoxysilane, methylphenyldimethoxysilane,
Examples are diphenyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, with tetramethoxysilane being preferred. Further, as the alkoxysilylalkylalkoxysilane of the component (C), specifically, bis (trimethoxysilyl) ethane, bis (trimethoxysilyl)
Propane, bis (trimethoxysilyl) butane, bis (trimethoxysilyl) pentane, bis (trimethoxysilyl) hexane, bis (methyldimethoxysilyl) ethane, bis (methyldimethoxysilyl) propane, bis (dimethylmethoxysilyl) ethane, Bis (dimethylmethoxysilyl) propane, bis (triethoxysilyl)
Examples are ethane and bis (triethoxysilyl) propane, with bis (trimethoxysilyl) hexane being preferred. Further, as the component (C), two or more kinds of the above-mentioned alkoxysilane or alkoxysilylalkylalkoxysilane can be used in combination.

When allyl glycidyl ether is used as the component (B) in the adhesion promoter of the present invention,
The resulting adhesion promoter has the general formula:

[Chemical 2] (In the formula, R is a monovalent hydrocarbon group, X is an alkoxysilyl group or an alkoxysilylsilyl group, and n is 1 or 2.) In the above formula, R
Is a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group. Examples thereof include alkenyl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and other aryl groups; benzyl group, phenethyl group, and other aralkyl groups, and allyl group and phenyl group are preferable. Further, in the above formula, X is an alkoxysilyl group or an alkoxysilylalkylsilyl group, and the alkoxysilyl group of X has the general formula: —SiR ² _a (OR ¹ ) _(3-a) (wherein R ¹ is It is an alkyl group, R ² is a monovalent hydrocarbon group, and a is an integer of 0 to 2). In the above formula, R ¹ is an alkyl group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group are exemplified, and a methyl group is preferable. Further, in the above formula, R ² is a monovalent hydrocarbon group, and specific examples thereof include the same monovalent hydrocarbon groups as described above. In the above formula, a is an integer of 0-2. Specific examples of the alkoxysilyl group of X include trimethoxysilyl group, triethoxysilyl group, methyldimethoxysilyl group, vinyldimethoxysilyl group, phenyldimethoxysilyl group, dimethylmethoxysilyl group, methylvinylmethoxysilyl group, Examples thereof include a methylphenylmethoxysilyl group, a diphenylmethoxysil group, a 3-glycidoxypropyldimethoxysilyl group, and a 3-methacryloxypropyldimethoxysilyl group. Further, alkoxysilyl alkylsilyl group X has the general _{^{formula: -SiR 2 b (OR 1)}} (2-b) -R 3 -SiR 2 a (OR 1)
_(3-a) (In the formula, R ¹ is an alkyl group, R ² is a monovalent hydrocarbon group, R ³ is an alkylene group, a is an integer of 0 to 2, and b is 0 to It is an integer of 2.). In the above formula, R ¹ is an alkyl group, and specific examples thereof include the same alkyl groups as described above. Further, in the above formula, R ² is a monovalent hydrocarbon group, and specific examples thereof include the same monovalent hydrocarbon groups as described above. In the above formula, R ³ is an alkylene group, and specifically, methylene group, ethylene group, methylmethylene group, methylethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group. Is preferred, and a hexylene group is preferred. In the above formula, a is an integer of 0 to 2 and b is 0.
Is an integer of ˜2. Specific examples of the alkoxysilylalkylsilyl group of X include trimethoxysilylethyldimethoxysilyl group, triethoxysilylethyldiethoxysilyl group, trimethoxysilylpropyldimethoxysilyl group, triethoxysilylpropyldiethoxysilyl group, Trimethoxysilylbutyldimethoxysilyl group, trimethoxysilylpentyldimethoxysilyl group, trimethoxysilylhexyldimethoxysilyl group,
Methyldimethoxysilylethyldimethoxysilyl group, methyldimethoxysilylpropyldimethoxysilyl group, methyldimethoxysilylbutyldimethoxysilyl group, methyldimethoxysilylpentyldimethoxysilyl group, methyldimethoxysilylhexyldimethoxysilyl group, dimethylmethoxysilylethyldimethoxysilyl group, dimethylmethoxy Examples thereof include a silylpropyldimethoxysilyl group, a dimethylmethoxysilylbutyldimethoxysilyl group, a dimethylmethoxysilylpentyldimethoxysilyl group, and a dimethylmethoxysilylhexyldimethoxysilyl group. Further, in the above formula, n is 1 or 2.

The reaction between the adhesion promoter of claim 1 and the component (C) is a dealcoholization condensation reaction between the hydroxyl group in the adhesion promoter of claim 1 and the silicon atom-bonded alkoxy group in the component (C). The condensation reaction can be accelerated by the alcohol exchange catalyst. Further, the desired reaction product can be obtained by heating and / or removing the by-produced alcohol under reduced pressure. The above reaction can be represented, for example, by the following formula.

[Chemical 3] (In the formula, R is a monovalent hydrocarbon group, R ¹ is an alkyl group, X is an alkoxysilyl group or an alkoxysilylalkylsilyl group, and n is 1 or 2.)

The alcohol exchange catalyst is not particularly limited as long as it is a compound that promotes alcohol exchange, and specifically, basic catalysts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, and potassium methylate; Titanium-based catalysts such as tetrabutoxytitanium are exemplified, and when the basicity on the nitrogen atom in the adhesion-imparting agent is strong, it itself acts as an alcohol exchange catalyst. You don't have to. The above reaction proceeds at room temperature but is extremely slow.
The reaction is preferably carried out by heating in the range of 00 ° C., and the by-produced alcohol is preferably removed under normal pressure or reduced pressure.

The adhesion promoter of the present invention imparts excellent adhesiveness immediately after curing of various curable resin compositions such as curable silicone resin compositions, and improves the durability of the adhesiveness under acidic conditions. Therefore, it can be used as an adhesion promoter for masking materials, sealing materials, potting materials, coating materials and the like. Further, together with the adhesion promoter thus obtained, by combining the organoalkoxysilane and the silicon atom-bonded alkoxy group-containing organic compound already known as an adhesion promoter into the curable resin composition, The curable resin composition can be provided with better adhesiveness to various base materials.

[0023]

EXAMPLES The adhesion promoter of the present invention will be described in detail with reference to Examples. The adhesiveness was evaluated by peeling the cured resin composition with a spatula immediately after curing the curable resin composition on the adherend by heating or after performing an adhesive durability test under acidic conditions. The state of time was observed, and the case where the cured resin was well adhered to the adherend was indicated by ◯, the case where the cured resin was partially peeled off, and the case where the cured resin was completely peeled off by x.

Example 1 285 g of allyl glycidyl ether was put into a 500 ml-4 neck flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel. Thereafter, 57 g of allylamine was added dropwise from the dropping funnel while adjusting the system so that the temperature did not exceed 150 ° C. After adding allylamine dropwise, the system was heated at 150 ° C for 2
Reacted for hours. Then, unreacted allyl glycidyl ether was removed by stripping to obtain a slightly brown liquid product. This liquid product was analyzed by ¹ H-nuclear magnetic resonance spectral analysis (hereinafter, NMR), infrared spectroscopic analysis (hereinafter, IR) and gas chromatography-gravimetric analysis (hereinafter, GC-MASS). It was confirmed to be an adhesion promoter (A) containing as a main component.

[0025]

[Chemical 4]

Example 2 201 g of allyl glycidyl ether was placed in a 500 ml-4 neck flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel. Then heat the system to 140 ° C.,
While adjusting this system so that it does not exceed 160 ℃,
65.9 g aniline was added dropwise from the dropping funnel. After dropping aniline, the system was reacted at 150 ° C. for 2 hours. Then, unreacted allyl glycidyl ether was removed by stripping to obtain a slightly brown liquid product. This liquid product is further subjected to a thin film distillation apparatus at 150 ° C.,
Distillation under conditions of 0.2 torr gave a slightly yellow liquid product. This liquid product was analyzed by NMR, IR and GC-
When analyzed by MASS, it was confirmed to be an adhesion promoter (B) containing the following compounds as main components.

[0027]

[Chemical 5]

[Example 3] To a 500 ml-four-necked flask equipped with a stirrer, a thermometer and a distillation device, 100 g of the compound prepared in Example 1 and 213.3 g of tetramethoxysilane were charged. Then add 0.0
4 g of potassium hydroxide was added, and the mixture was heated and stirred. At this time, 20 cm of biglyu was used in the distillation column to remove the by-product methanol. After completion of methanol by-product, the system was cooled to room temperature and
g of propionic acid was added to neutralize sodium hydroxide. Unreacted propionic acid and tetramethoxysilane were removed by stripping to obtain a liquid product. When this liquid product was analyzed by IR, it was confirmed that the peak derived from the hydroxyl group had disappeared, and further analyzed by NMR and GC-MASS, an adhesion promoter containing the following compound as the main component ( It was confirmed to be C).

[0029]

[Chemical 6]

Example 4 In a 500 ml-four-necked flask equipped with a stirrer, a thermometer and a distillation device, 51.1 g of the compound prepared in Example 2, 100 g of bistrimethoxysilylhexane and 1.5 g of tetrabutoxytitanium. , And under reduced pressure with an aspirator,
Heated to 0 ° C. When the by-produced methanol was recovered by a dry ice-acetone trap, the amount of by-produced methanol was 11 g. After completion of the by-product of methanol, the system was cooled to obtain a liquid product.
When this liquid product was analyzed by IR, it was confirmed that the peak derived from the hydroxyl group had disappeared, and further it was an adhesion promoter (D) containing the following compounds as main components by NMR and GC-MASS. It was confirmed.

[0031]

[Chemical 7]

Comparative Example 1 495.6 g of 3-glycidoxypropyltrimethoxysilane and 221 g of 3-aminopropyltriethoxysilane were charged into a 1 liter-four-necked flask equipped with a stirrer and a thermometer. The system was heated and stirred at 100 ° C. for 3 hours to obtain a viscous adhesion promoter (E). When this adhesion promoter was analyzed by IR, it was confirmed that the peak derived from the N—H bond disappeared.

[Application Example 1] The average degree of polymerization is 300,
100 parts by weight of dimethylpolysiloxane (vinyl group content = 0.24% by weight) with both ends of the molecular chain blocked with dimethylvinylsiloxy groups, an average degree of polymerization of 40, and both ends of the molecular chain were blocked with trimethylsiloxy groups Methyl hydrogen polysiloxane (content of silicon atom-bonded hydrogen atoms = 1.5% by weight; the amount is such that silicon atom-bonded hydrogen atoms are 1.5 mols relative to 1 mol of alkenyl groups in the present composition). ), And fumed silica 1 having a specific surface area of 200 mm ² / g, which has been surface-treated with hexamethyldisilazane 1.
1 part by weight of each of the adhesion promoters (B), (D) and (E)
2 parts by weight, a complex of chloroplatinic acid and vinyl siloxane (the content of platinum metal in the composition is 10 ppm) and 0.02 parts by weight of phenylbutynol are uniformly mixed to obtain 3 parts. A variety of curable silicone resin compositions were prepared.

Further, dimethylpolysiloxane having an average degree of polymerization of 300 and having both ends of the molecular chain blocked with dimethylvinylsiloxy groups (vinyl group content = 0.24% by weight)
100 parts by weight, an average degree of polymerization of 40, and a methylhydrogenpolysiloxane whose both molecular chain ends were blocked with trimethylsiloxy groups (silicon atom-bonded hydrogen atom content =
1.5% by weight; an amount such that silicon atom-bonded hydrogen atoms are 1.5 mol with respect to 1 mol of the alkenyl group in the present composition. ), 11 parts by weight of fumed silica having a specific surface area of 200 mm ² / g obtained by surface treatment with hexamethyldisilazane, 2.2 parts by weight of adhesion promoters (A) and (C), rhodium chloride and di (n). -Butyl) Sulfur complex (the content of rhodium metal in the composition is 10 ppm) and 0.02 part by weight of phenylbutynol are uniformly mixed to obtain two curable silicone resins. A composition was prepared.

As a blank, the average degree of polymerization is 30.
0, and both ends of the molecular chain were blocked with dimethylvinylsiloxy groups (dimethyl group content = vinyl group content =
0.24% by weight) 100 parts by weight, the average degree of polymerization is 40, and both ends of the molecular chain are blocked with trimethylsiloxy groups, methylhydrogenpolysiloxane (silicon atom-bonded hydrogen atom content = 1.5% by weight; With respect to 1 mol of the alkenyl group in the composition, the number of silicon atom-bonded hydrogen atoms is 1.5.
The amount is molar. ), 11 parts by weight of fumed silica having a specific surface area of 200 mm ² / g formed by surface treatment with hexamethyldisilazane, a complex of chloroplatinic acid and vinylsiloxane (the content of platinum metal in the composition is 10 ppm). And 0.02 part by weight of phenylbutynol were uniformly mixed to prepare a curable silicone resin composition.

After coating these 6 kinds of curable silicone resin compositions on the adherends shown in Table 1, these are applied to
It was cured by heating at 0 ° C. for 1 hour. The silicone cured product on the adherend was peeled off with a spatula and the adhesion state was observed. The results are shown in Table 1.

[0037]

[Table 1]

[Application Example 2] The average degree of polymerization is 300,
80 parts by weight of dimethylpolysiloxane (vinyl group content = 0.24% by weight) having both ends of its molecular chain blocked with dimethylvinylsiloxy groups, a siloxane unit represented by the formula: (CH ₃ ) ₃ SiO _1/2 and a formula : (CH ₂ = CH) (CH ₃ ) ₂ S
20 parts by weight of a silicone resin (vinyl group content = about 2% by weight) composed of a siloxane unit represented by io _1/2 and a siloxane unit represented by the formula: SiO _4/2 , having an average degree of polymerization of 4
Methyl hydrogen polysiloxane whose molecular chain ends are blocked with trimethylsiloxy groups (content of hydrogen atoms bonded to silicon atom = 1.5% by weight; silicon based on 1 mol of alkenyl group in the composition). Amounts of atomically bonded hydrogen atoms are 1.5 moles), 14.3 parts by weight of fumed silica having a specific surface area of 200 mm ² / g formed by surface treatment with hexamethyldisilazane, an adhesion promoter (B),
(D), 2.3 parts by weight each of tetramethylmethoxysilane and bistrimethoxysilylhexane, and a complex of chloroplatinic acid and vinylsiloxane (in the composition, platinum metal is 1
The amount is 0 ppm. ) And 0.02 part by weight of phenylbutynol were uniformly mixed to prepare four curable silicone resin compositions.

80 parts by weight of dimethylpolysiloxane (vinyl group content = 0.24% by weight) having an average degree of polymerization of 300 and having both ends of the molecular chain blocked with dimethylvinylsiloxy groups, formula: (CH ₃ ) ₃ siloxane units of the formula _{SiO 1/2: (CH 2 = CH} ) siloxane units of the formula (CH _{3) 2} SiO _1/2: silicone resins comprising siloxane units represented by SiO _4/2 (vinyl Group content =
20 parts by weight), the average degree of polymerization is 40, and both ends of the molecular chain are blocked with trimethylsiloxy groups. Methyl hydrogen polysiloxane (silicon atom-bonded hydrogen atom content = 1.5% by weight; Alkenyl group in composition 1
The amount is such that silicon atom-bonded hydrogen atoms are 1.5 mols based on mols. ), 14.3 parts by weight of fumed silica having a specific surface area of 200 mm ² / g, which is surface-treated with hexamethyldisilazane, 2.3 parts by weight of adhesion promoters (A) and (C), respectively, rhodium chloride and diamine. A complex with (n-butyl) sulfur (the amount of rhodium metal in the composition is 10 ppm) and 0.02 part by weight of phenylbutynol are uniformly mixed to obtain two curable silicone resin compositions. The thing was prepared.

As a blank, the average degree of polymerization is 30.
0, and both ends of the molecular chain were blocked with dimethylvinylsiloxy groups (dimethyl group content = vinyl group content =
0.24% by weight) 80 parts by weight, formula: (CH ₃ ) ₃ SiO
Siloxane unit represented by _1/2 and formula: (CH ₂ = CH)
A siloxane unit represented by (CH ₃ ) ₂ SiO _1/2 and a formula:
20 parts by weight of a silicone resin (vinyl group content = about 2% by weight) consisting of a siloxane unit represented by SiO _4/2 ,
Methyl hydrogen polysiloxane having an average degree of polymerization of 40 and having both ends of its molecular chain blocked with trimethylsiloxy groups (silicon atom-bonded hydrogen atom content = 1.5% by weight;
The amount is such that the silicon atom-bonded hydrogen atom is 1.5 mol with respect to 1 mol of the alkenyl group in the composition. ), A specific surface area 20 obtained by surface-treating with hexamethyldisilazane
14.3 parts by weight of 0 mm ² / g fumed silica, a complex of chloroplatinic acid and vinylsiloxane (the amount of platinum metal in the composition is 10 ppm) and 0.02 parts by weight of phenylbutynol. The mixture was uniformly mixed to prepare a curable silicone resin composition.

These seven kinds of curable silicone resin compositions were applied on a copper plate to a thickness of 50 μm and then applied to
It was cured by heating at 0 ° C. for 1 hour. The silicone rubber on the copper plate was peeled off with a spatula and the adhesion state was observed. Further, the silicone cured product adhered on these copper plates was immersed in a 10% hydrochloric acid aqueous solution at 50 ° C. for 10 minutes, and the adhesiveness thereof was observed. The results are shown in Table 2.

[0042]

[Table 2]

[0043]

EFFECT OF THE INVENTION The adhesion promoter of the present invention imparts excellent adhesiveness to a curable resin composition such as a curable silicone resin composition without foaming, and has excellent durability under acidic conditions. It has a feature that excellent adhesiveness can be imparted.

Claims (2)

[Claims] 1. An amine compound represented by the general formula (A): R _n NH _(3-n) (wherein R is a monovalent hydrocarbon group and n is 1 or 2), and B) An adhesion promoter whose main component is a reaction product with an epoxy compound having an aliphatic unsaturated bond. 2. An amine compound represented by the general formula (A): R _n NH _(3-n) (wherein R is a monovalent hydrocarbon group and n is 1 or 2), and The main component is a reaction product obtained by subjecting (B) a reaction product of an epoxy compound having an aliphatic unsaturated bond to (C) a silicon compound having at least two silicon atom-bonded alkoxy groups in one molecule. Adhesion promoter.