JPH0753870A - Curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition, excellent in fluidity before curing and flexibility and adhesion after the curing and useful as a sealing resin for electrical and electronic elements by blending a curable resin with a specific organopolysiloxane. CONSTITUTION:This curable resin composition comprises (A) 100 pts.wt. curable resin and (B) 0.1-500 pts.wt. organopolysiloxane, expressed by the formula {R<1> is a <=5C alkyl or phenyl; R<2> is a $ 5C alkyl, phenyl or H; R<3> is an epoxy group-containing organic group, an alkoxysilylalkyl or a >=6C alkyl; (a) is 0 or a positive number; (b) and (c) are positive numbers; (a/c) is 0-4; (b/c) is 0.05-4; [(a+b)/c] is 0.2-4} and having at least one each of the alkoxysilylalkyl group and >=6C alkyl group in one molecule. Furthermore, the component (A) is preferably selected from the group consisting of an epoxy resin, a phenolic resin, an imide resin and a silicone resin and the component (B) has preferably further an epoxy group-containing organic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more specifically, a curable resin composition which is a cured resin having excellent fluidity before curing and excellent flexibility and adhesiveness after curing. Regarding

A curable resin composition is a cured resin obtained by curing the resin composition, which has electrical properties such as dielectric properties, volume resistivity and dielectric breakdown strength, or mechanical properties such as bending strength, compressive strength and impact strength. Therefore, it is used as a sealing resin for electric / electronic elements, an adhesive, a resin for FRP, and the like.

A curable resin composition is a cured resin obtained by curing the curable resin composition, which is generally rigid and poor in flexibility, and has a large curing shrinkage ratio upon curing. When it is used as a stop resin, a large stress is applied to the electric / electronic element, so that the cured resin itself may crack, or the electric / electronic element may be destroyed, and the adhesiveness of the cured resin to the electric / electronic element may be increased. Since it is low, there is a problem that a gap is generated between the electric / electronic element and the cured resin. Further, in the curable resin composition, the cured resin obtained by curing the curable resin composition has a higher thermal expansion coefficient than the thermal expansion coefficient of the electric / electronic element, so that the resin-sealed electric / electronic element undergoes a heat cycle. And since a large stress is applied to the electric / electronic element, a crack may be generated in the cured resin itself, or the electric / electronic element may be destroyed, or the adhesiveness of the cured resin to the electric / electronic element is low,
There has been a problem that a gap is created between the electric / electronic element and the cured resin. In addition, cracks caused by curing contraction or thermal expansion and contraction of the curable resin composition or water entering the gap between the cured resin and the electric / electronic element promotes deterioration of the resin-sealed electric / electronic element. There was a problem.

Thus, in the curable resin composition,
Various curable resin compositions have been proposed in which the flexibility of the cured resin is improved in order to reduce the stress of the cured resin, and the adhesiveness of the cured resin to electric / electronic elements is improved. For example, an epoxy resin, a methylphenylpolysiloxane, an organopolysiloxane composed of a bifunctional siloxane unit (D unit) having an epoxy group and a trifunctional siloxane unit (T unit), a curability composed of an inorganic filler and a curing catalyst. Resin composition (Japanese Patent Laid-Open No. 56-1459)
No. 42), an epoxy resin, a monofunctional siloxane unit (M unit) or a trifunctional siloxane unit (T unit) having at least one epoxy group or amino group and at least one hydroxyl group or hydrolyzable group, respectively. A curable resin composition comprising an organopolysiloxane composed of a functional siloxane unit (D unit), a curing agent and an inorganic filler (see JP-A-56-136816), an epoxy resin, a phenol resin, a side chain of a molecular chain. Curable resin composition comprising dimethylpolysiloxane having an epoxy group and a polyoxyalkylene group (JP-A-60-58425)
And a curable resin composition comprising a curable resin and silicone rubber spherical fine powder (JP-A-64-514).
No. 67 publication) is proposed.

However, the curable resin compositions proposed by JP-A-56-145942 and JP-A-56-136816 contain an organopolysiloxane in which a difunctional siloxane unit (D unit) is essential. Since it is used, it has a drawback that the glass transition point (Tg) of the obtained cured resin is lowered, and in particular, an organopolypolycarbonate composed of (CH ₃ ) ₂ SiO _2/2 units (D units) having an epoxy group is used. This was remarkable when using siloxane as the siloxane. Since the curable resin composition proposed by JP-A-60-58425 uses dimethylpolysiloxane having an epoxy group and a polyoxyalkylene group in the side chain of the molecular chain, the resulting cured resin has a water-absorbing property. Big, electricity
It has a drawback that it is not suitable as a sealing resin for electronic devices. Further, the curable resin composition proposed in JP-A-64-51467 has excellent flexibility of the cured resin obtained by curing the curable resin composition, but the curable resin composition has poor fluidity. However, the workability of resin-sealing the electric / electronic element is poor, and the cured resin has a drawback of poor adhesion to the electric / electronic element.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have arrived at the present invention as a result of diligent efforts to solve the above problems.

That is, an object of the present invention is to provide a curable resin composition which becomes a cured resin having excellent fluidity before curing and excellent flexibility and adhesiveness after curing.

[0008]

MEANS FOR SOLVING PROBLEMS AND ACTION THEREOF The present invention provides (A) curable resin 100
Parts by weight and (B) general formula:

[Chemical 2] {In the formula, R ¹ is a lower alkyl group having 5 or less carbon atoms or a phenyl group, R ² is a group selected from the group consisting of a lower alkyl group having 5 or less carbon atoms, a phenyl group and a hydrogen atom; ³ is a group selected from the group consisting of an epoxy group-containing organic group, an alkoxysilylalkyl group and an alkyl group having 6 or more carbon atoms. Also, a is 0 or a positive number, b is a positive number, c is a positive number, a / c is a number from 0 to 4, b / c is a number from 0.05 to 4. ,
And (a + b) / c is a number of 0.2-4. } And has an alkoxysilylalkyl group and 6 carbon atoms in one molecule.
The present invention relates to a curable resin composition comprising 0.1 to 500 parts by weight of an organopolysiloxane having at least one of the above alkyl groups.

The curable resin composition of the present invention will be described in detail.

The curable resin (A) is the base material of the present invention.
The component (A) is not particularly limited as long as it is a conventionally known curable resin. As the component (A), specifically, phenol resin,
Formaldehyde resin, xylene resin, xylene-formaldehyde resin, ketone-formaldehyde resin, furan resin, urea resin, imide resin, melamine resin, alkyd resin, unsaturated polyester resin, aniline resin,
Examples thereof include sulfone-amide resins, silicone resins, epoxy resins, and copolymer resins thereof, and the curable resins exemplified above can be used in combination of two or more kinds. Among these curable resins, the component (A) is preferably a curable resin selected from the group consisting of epoxy resins, phenol resins, imide resins and silicone resins. The curing means for the component (A) is not particularly limited, and examples thereof include a curable resin that is cured by heat, a curable resin that is cured by high energy rays such as ultraviolet rays or radiation, and a curable resin that is cured by moisture. . Further, the component (A) may be a curable resin in a liquid or solid state at room temperature, and may contain an organic solvent or the like.

As the component (A), in addition to the above-mentioned curable resin, a curing agent, a curing accelerator, a filler, a photosensitizer, a higher fatty acid metal salt, an ester wax, a plasticizer and the like are blended. can do. Specific examples of the curing agent that can be added to the component (A) include organic acids such as carboxylic acids and sulfonic acids and their anhydrides, organic hydroxy compounds,
Examples thereof include an organosilicon compound having a silanol group, an alkoxy group, a halogeno group, and the like, and a primary or secondary amino compound, and two or more kinds of them can be used in combination. Specific examples of the curing accelerator that can be added to the component (A) include tertiary amine compounds, organometallic compounds such as aluminum and zirconium, organic phosphorus compounds such as phosphine, heterocyclic amine compounds, and boron complex compounds. Examples thereof include compounds, organic ammonium salts, organic sulfonium salts, organic peroxides and the like. Also, (A)
Specifically as a filler that can be blended with the components,
Fibers such as glass fiber, asbestos, alumina fiber, ceramic fiber containing alumina and silica, boron fiber, zirconia fiber, silicon carbide fiber, metal fiber, polyester fiber, aramid fiber, nylon fiber, phenol fiber, natural animal and plant fiber Filler, fused silica, precipitated silica,
Fumed silica, calcined silica, zinc oxide, calcined clay, carbon black, glass beads, alumina, talc, calcium carbonate, clay, aluminum hydroxide, barium sulfate, titanium dioxide, aluminum nitride, silicon carbide, magnesium oxide, beryllium oxide, Kaolin,
Examples thereof include granular fillers such as mica and zirconia, and mixtures thereof.

The organopolysiloxane (B) improves the fluidity of the curable resin composition of the present invention, improves the flexibility of the cured resin obtained by curing the curable resin composition, and improves the flexibility of the cured resin composition. It is a component for improving the adhesiveness to the body and has the general formula:

[Chemical 3] It is an organopolysiloxane represented by. In the above formula, R
¹ is a lower alkyl group having 5 or less carbon atoms or a phenyl group, and specific examples of the lower alkyl group having 5 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Further, in the above formula, R ² is a group selected from the group consisting of a lower alkyl group having 5 or less carbon atoms, a phenyl group and a hydrogen atom. Specifically, as the lower alkyl group having 5 or less carbon atoms of R ² , , Methyl group, ethyl group,
Examples include a propyl group, a butyl group, and a pentyl group. In the above formula, R ³ is a group selected from the group consisting of epoxy group-containing organic group, alkoxysilyl group and alkyl group having 6 or more carbon atoms, specifically as an epoxy group-containing organic group of R ³ Is a 2-glycidoxyethyl group,
3-glycidoxypropyl group, 4-glycidoxybutyl group, 5-glycidoxypentyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group, A 4- (3,4-epoxycyclohexyl) butyl group is exemplified, and specific examples of the alkoxysilylalkyl group of R ³ include trimethoxysilylethyl group, trimethoxysilylpropyl group, trimethoxysilylbutyl group, trimethoxysilyl group. Examples include pentyl group, triethoxysilylethyl group, triethoxysilylpropyl group, triethoxysilylbutyl group, methyldimethoxysilylethyl group, methyldimethoxysilylpropyl group, dimethylmethoxysilylethyl group, dimethylmethoxysilylpropyl group, R ³ As an alkyl group having 6 or more carbon atoms Specifically, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group are exemplified, and n-hexyl group, n-heptyl group, n
-Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n The -octadecyl group is preferred. In the component (B), the alkyl group of R ³ needs to have 6 or more carbon atoms, and the upper limit thereof is not particularly limited. However, when this is blended with the component (A), it is The compatibility with the component B) is good, and the flexibility and adhesiveness of the resin after curing the resulting cured resin composition are good, so that the alkyl group of R ³ has 6 to 30 carbon atoms. It is preferably in the range.

In the above formula, a is 0 or a positive number which represents the number of monofunctional siloxane units (M units) having no epoxy group-containing organic group, alkoxysilylalkyl group or alkyl group having 6 or more carbon atoms. Yes, b is an epoxy group-containing organic group, an alkoxysilylalkyl group or 6 carbon atoms
Monofunctional siloxane unit (M
Unit), c is a positive number indicating the number of tetrafunctional siloxane units (Q units), and the ratio of each is
a / c is a number in the range of 0-4, and b / c is 0.05-
Is a number in the range of 4 and (a + b) / c is 0.2 to 4
Is the number of ranges. This is because one tetrafunctional siloxane unit (Q unit) is added to one monofunctional siloxane unit (M
Unit) cannot exceed 4, and when the number of monofunctional siloxane units (M units) is less than 0.2, the
This is because the compatibility of the component (B) decreases. Further, in the curable resin composition of the present invention, in order to have excellent compatibility between the component (A) and the component (B), an epoxy group-containing organic group, an alkoxysilylalkyl group or a carbon number of 6 in the component (B) is required. Monofunctional siloxane unit (M unit) having the above alkyl groups
Is necessary to be at least 0.05 per 1 tetrafunctional siloxane unit (Q unit). The component (B) is liquid or solid at room temperature, and its molecular weight is not particularly limited, but it is preferably in the range of 500 to 500,000 because it has good compatibility with the component (A).

In the curable resin composition of the present invention, (B)
Since the component has an alkoxysilylalkyl group and an alkyl group having 6 or more carbon atoms, the flexibility of the obtained cured resin is improved by being incorporated into the resin matrix of the component (A), Further, since the component (B) is composed of SiO ₂ units (Q units), it has the advantage of excellent flexibility and adhesiveness.

The component (B) is represented by the general formula: in the presence of a catalyst for hydrosilylation reaction:

[Chemical 4] {In the formula, R ¹ is a lower alkyl group having 5 or less carbon atoms or a phenyl group. Further, d is 0 or a positive number, e is a positive number, f is a positive number, d / f is a number from 0 to 4, and e / f is a number from 0.05 to 4. , And (d + e)
/ F is a number from 0.2 to 4. } The organopolysiloxane represented by the formula (1) can be prepared by subjecting an alkoxysilyl alkene, an alkene having 6 or more carbon atoms, and, if necessary, an organic compound having an epoxy group and an aliphatic unsaturated bond.

In the curable resin composition of the present invention, (B)
The compounding amount of the component is 0.1 with respect to 100 parts by weight of the component (A).
To 500 parts by weight, preferably 0.5 to 100 parts by weight. This is because the amount of component (B) is 100 parts of component (A).
This is because if the amount is less than 0.1 parts by weight with respect to parts by weight, the flexibility of the obtained cured resin is not improved.
This is because if the amount exceeds 100 parts by weight, the mechanical strength of the obtained cured resin is significantly reduced.

The curable resin composition of the present invention comprises the component (A)
It can be prepared by uniformly mixing the component (B). The method of mixing the component (A) and the component (B) is not particularly limited, and specifically, a method of directly blending the component (B) with the component (A), and the component (B) when preparing the component (A). After blending and premixing, a method of blending an additive such as a filler into the component (A), (B)
Examples of the method include sequentially adding various additives to the component (A). The mixing device for mixing the component (A) and the component (B) is not particularly limited, and the mixing device is selected according to various forms such as the component (A) or the component (B) being liquid, solid, powdery, or the like. Specific examples include a single-screw or twin-screw continuous mixer, a two-roll mill, a loss mixer, and a kneader mixer.

Since the curable resin composition of the present invention is excellent in fluidity before curing, transfer mold, injection mold, potting, casting,
It can be used by methods such as powder coating, dip coating, and dropping. Further, since the curable resin composition of the present invention becomes a cured resin having excellent flexibility and adhesiveness after curing, it can be used as a curable resin composition for encapsulating electric / electronic elements, an adhesive, etc. Can be used.

[0019]

EXAMPLES The curable resin composition of the present invention will be described in detail with reference to Examples. In addition, in the examples, the value of viscosity is a value measured at 25 ° C., and various properties of the curable resin composition and the cured resin were measured by the following methods.

○ Spiral flow: Measured by a method according to the EMMI standard. Molding shrinkage rate: Measured by a method according to JIS-K-6911. Thermal expansion coefficient: A cured resin molded into 5 mm × 5 mm × 16 mm was measured using a thermal expansion meter (DL-7000 manufactured by Vacuum Riko Co., Ltd.). The value of the coefficient of thermal expansion is the value from room temperature to the glass transition point. Glass transition point (Tg): Measured by measuring the coefficient of thermal expansion. Bending elastic modulus: Measured by a method according to JIS-K-6911. ○ Water absorption rate: 2 inches x 0.5 inches x 0.2
Cured resin molded into 5 inches has a temperature of 121 ° C and a humidity of 10
It was determined by measuring the weight increase of the cured resin after making it 0% and humidifying for 20 hours. ○ Burr: The burr length was measured using a groove having a depth of 20 μm. ○ Adhesiveness: The curable resin composition was sandwiched between a 42 alloy plate and a copper plate and cured, and the adhesiveness when the cured resin was peeled off was judged by ○ (good) and × (poor). ○ Thermal shock resistance: Molded 20 resin-sealed semiconductor elements with a chip size of 36 mm ² and a package thickness of 2.0 mm,
This is subjected to a heat cycle test at a cycle of 1 minute at -196 ° C ← → + 150 ° C. After 150 cycles, the surface of the sealing resin is observed with a stereoscopic microscope, and the number of molded products with cracks on the surface is 5 or less. When the number was 6, the case was 6 to 10, and when the number was 11 or more, the degree was x. ○ Soldering heat resistance: Mold 20 resin-sealed semiconductor elements with a chip size of 36 mm ² and a package thickness of 2.0 mm,
After leaving this for 72 hours at 85 ° C. and 85% RH,
Immediately, it was immersed in a solder bath at 240 ° C. for 1 hour, and the surface of the sealing resin was observed with a stereoscopic microscope. When the number of molded products having cracks on the surface was 5 or less, it was evaluated as ◯, when 6 to 10 was evaluated as Δ, and when it was 11 or more, it was evaluated as x.

[0021]

Reference Example 1 Tetrakis (dimethylsiloxy) silane was reacted with allyltrimethoxysilane and 1-octadenene in toluene in the presence of chloroplatinic acid in a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer. As a result, a yellowish brown transparent organopolysiloxane was prepared. The viscosity of this organopolysiloxane was 24 centipoise and the refractive index was 1.4358. This organopolysiloxane was analyzed by ¹ H-nuclear magnetic resonance spectroscopy (hereinafter referred to as NM
When analyzed by R), ¹³ C-NMR and ²⁹ Si-NMR, it was confirmed to be represented by the following structural formula.

[0022]

[Chemical 5]

[0023]

[Reference Example 2] A four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with the formula:

[Chemical 6] The organopolysiloxane represented by the formula (viscosity 46 centipoise, content of hydrogen atoms bonded to silicon atoms 0.92% by weight) is reacted with 1-octadecene and vinyltrimethoxysilane in the presence of a chloroplatinic acid catalyst. hand,
A colorless transparent organopolysiloxane was prepared. The viscosity of this organopolysiloxane was 97 centipoise and the refractive index was 1.4386. This organopolysiloxane was analyzed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si.
-By NMR analysis, it was confirmed to be represented by the following structural formula.

[0024]

[Chemical 7]

[0025]

[Reference Example 3] A four-necked flask equipped with a stirrer, a reflux condenser and a thermometer was charged with the formula:

[Chemical 8] The presence of a chloroplatinic acid catalyst containing 1-dodecene, vinyltrimethoxysilane and allylglycidyl ether in organotoluene represented by the formula (viscosity 46 centipoise, content of hydrogen atoms bonded to silicon atoms: 0.92% by weight) in toluene. The reaction was carried out below to prepare a brown transparent organopolysiloxane. The viscosity of this organopolysiloxane was 142 centipoise and the refractive index was 1.4475. This organopolysiloxane was analyzed by ¹ H-NMR, ¹³
Analysis by C-NMR and ²⁹ Si-NMR confirmed that the compound was represented by the following structural formula.

[0026]

[Chemical 9]

[0027]

[Reference Example 4] A four-necked flask equipped with a stirrer, a reflux condenser and a thermometer had the formula:

[Chemical 10] The organopolysiloxane represented by the formula (viscosity 46 centipoise, content of hydrogen atoms bonded to silicon atoms: 0.92% by weight) is reacted with 1-octadecene and vinyltrimethoxysilane in the presence of chloroplatinic acid. A colorless transparent organopolysiloxane was prepared. This organopolysiloxane had a viscosity of 97 centipoise and a refractive index of 1.4386. This organopolysiloxane was analyzed by ¹ H-NMR, ¹³ C-NMR and ²⁹ Si-NM.
When analyzed by R, it was confirmed to be represented by the following structural formula.

[0028]

[Chemical 11]

[0029]

Example 1 Phenol novolac resin (softening point 80
C., hydroxyl equivalent 100) 100 parts by weight, organopolysiloxane 8.9 parts by weight prepared in Reference Example 1, fused silica powder 185.7 parts by weight, hexamethylenetetramine 11.
4 parts by weight, 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane and 2.9 parts by weight of carnauba wax were evenly mixed, and this was further kneaded with a heating roll at 90 ° C. and then cooled to obtain the present invention. A curable resin composition was prepared. Then, this was crushed and transfer molded under conditions of 175 ° C. and 70 kg / cm ² for 3 minutes. Then, the cured resin 15
Post-cure was performed at 0 ° C. for 2 hours. Various properties of the obtained cured resin are shown in Table 1.

[0030]

Comparative Example 1 A curable resin composition was prepared in the same manner as in Example 1 except that the organopolysiloxane represented by the following formula was used in place of the organopolysiloxane prepared in Reference Example 1. did. This was cured in the same manner as in Example 1. Various properties of the obtained cured resin are shown in Table 1.

[0031]

[Chemical 12]

[0032]

Comparative Example 2 A curable resin composition was prepared in the same manner as in Example 1 except that the organopolysiloxane prepared in Reference Example 1 was not used. This is Example 1
It was cured in the same manner. Various properties of the obtained cured resin are shown in Table 1.

[0033]

[Table 1]

[0034]

Example 2 CH ₃ SiO _3/2 unit 40 mol%, C ₆ H
₅ (CH ₃ ) SiO _2/2 unit 10 mol%, C ₆ H ₅ SiO _3/2
Unit 40 consists mole% and _{(C 6 H 5) 2 SiO} 2/2 units 10 mole%, the silicone resin 50 parts by weight of cresol novolak epoxy resins containing silicon-bonded hydroxyl 5 wt% (softening point 80 ° C., epoxy Equivalent 220) 50
100 parts by weight of silicone-epoxy resin, 8.0 parts of organopolysiloxane prepared in Reference Example 2
Parts by weight, 284.6 parts by weight of fused silica powder, 3.5 parts by weight of aluminum acetylacetonate, 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane and 3.8 parts by weight of carnauba wax. And this is 9
The curable resin composition of the present invention was prepared by further kneading with a heating roll at 0 ° C. and then cooling. It is then crushed and
Transfer molding was performed for 2 minutes at 5 ° C. and 70 kg / cm ² . Then, this cured resin was post-cured at 180 ° C. for 12 hours. Various properties of the obtained cured resin are shown in Table 2.

[0035]

Example 3 A curable resin composition was prepared in the same manner as in Example 2 except that the organopolysiloxane prepared in Reference Example 3 was used instead of the organopolysiloxane prepared in Reference Example 2. Prepared. Example 2
It was cured in the same manner. Various properties of the obtained cured resin are shown in Table 2.

[0036]

Example 4 A curable resin composition was prepared in the same manner as in Example 2 except that the organopolysiloxane prepared in Reference Example 4 was used instead of the organopolysiloxane prepared in Reference Example 2. Prepared. Example 2
It was cured in the same manner. Various properties of the obtained cured resin are shown in Table 2.

[0037]

Comparative Example 3 A curable resin composition was prepared in the same manner as in Example 2 except that the organopolysiloxane prepared in Reference Example 2 was replaced by the organopolysiloxane represented by the following structural formula. Was prepared. This was cured as in Example 2. Various properties of the obtained cured resin are shown in Table 2.

[0038]

[Chemical 13]

[0039]

Comparative Example 4 A curable resin composition was prepared in the same manner as in Example 2 except that the organopolysiloxane prepared in Reference Example 2 was not added. Example 2
It was cured in the same manner. Various properties of the obtained cured resin are shown in Table 2.

[0040]

[Table 2]

[0041]

Example 5 100 parts by weight of a bismaleimide-triazine type thermosetting polyimide resin, 12 parts by weight of the organopolysiloxane prepared in Reference Example 3, fused silica powder 185.
7 parts by weight, 2.9 parts by weight of carnauba wax and 0.9 parts by weight of aluminum benzoate were uniformly mixed, and this was further kneaded with a heating roll at 90 ° C. and then cooled to obtain the curable resin composition of the present invention. Was prepared. Then, this was crushed and transfer-molded for 4 minutes at 220 ° C. and 70 kg / cm ² . Then, the cured resin is heated to 230 ° C.
I did post cure for 3 hours. Various properties of the obtained cured resin are shown in Table 3.

[0042]

Comparative Example 5 A curable resin composition was prepared in the same manner as in Example 5 except that the organopolysiloxane prepared in Reference Example 3 was not used. This is Example 5
And cured in the same manner. Various properties of this cured resin are shown in Table 3.

[0043]

[Table 3]

[0044]

Example 6 75 parts by weight of orthocresol novolac epoxy resin (softening point 80 ° C., epoxy equivalent 220), 260 parts by weight fused silica, 1 part by weight carnauba wax,
35 parts by weight of phenol novolac resin, 0.6 parts by weight of triphenylphosphine, 13 parts by weight of organopolysiloxane prepared in Reference Example 4 and 1.0 part by weight of 3-glycidoxypropyltrimethoxysilane were uniformly mixed,
This was further kneaded with a heating roll at 90 ° C. and then cooled to prepare the curable resin composition of the present invention. Then, this was crushed and transfer-molded for 3 minutes under the conditions of 150 ° C. and 70 kg / cm ² . After that, the cured resin is heated to 180 ° C.
I did post cure for 4 hours. Various properties of the obtained cured resin are shown in Table 4.

[0045]

Comparative Example 6 A curable resin composition was prepared in the same manner as in Example 6 except that the organopolysiloxane prepared in Reference Example 4 was not used. Example 6
It was cured in the same manner. Various properties of the obtained cured resin are shown in Table 4.

[0046]

[Table 4]

[0047]

Example 7 3,4-epoxycyclohexyl-3,4
-Epoxycyclohexanecarboxylate 100 parts by weight, 3 or 4-methylhexahydrophthalic anhydride 120.5 parts by weight, tin octylate 1.4 parts by weight and 24 parts by weight of the organopolysiloxane prepared in Reference Example 2 are uniformly added. The curable resin composition of the present invention was prepared by mixing. It is sandwiched between 1mm thick nickel plates and
After heating at 0 ° C. for 2 hours, it was further heated at 150 ° C. for 3 hours to cure the resin. The adhesive strength of the cured resin to the nickel plate was measured. The results are shown in Table 5.

[0048]

Example 8 A curable resin composition is prepared in the same manner as in Example 7 except that the organopolysiloxane prepared in Reference Example 4 is used instead of the organopolysiloxane prepared in Reference Example 2. did. This was cured as in Example 7. The adhesive strength of the obtained cured resin to the nickel plate was measured. The results are shown in Table 5.

[0049]

Comparative Example 7 A curable resin was prepared in the same manner as in Example 7, except that the organopolysiloxane prepared in Reference Example 2 was not used. This was cured as in Example 7. The adhesive strength of the obtained cured resin to the nickel plate was measured. The results are shown in Table 5.

[0050]

[Table 5]

[0051]

The curable resin composition of the present invention comprises, as the component (B), an organopolysiloxane having at least one alkoxysilylalkyl group and at least one alkyl group having 6 or more carbon atoms in one molecule. Therefore, there is a feature that a cured resin having excellent fluidity before curing and excellent flexibility and adhesiveness after curing can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location C08L 79/08 LRC 101/00 LTA (72) Inventor Takashi Tachibana 2-2 Chikusaigan, Ichihara, Chiba Prefecture Toray Dow Corning Silicone Co., Ltd.

Claims (3)

[Claims] 1. A curable resin (A) 1
00 parts by weight and (B) general formula: {In the formula, R ¹ is a lower alkyl group having 5 or less carbon atoms or a phenyl group, R ² is a group selected from the group consisting of a lower alkyl group having 5 or less carbon atoms, a phenyl group and a hydrogen atom; ³ is a group selected from the group consisting of an epoxy group-containing organic group, an alkoxysilylalkyl group and an alkyl group having 6 or more carbon atoms. Also, a is 0 or a positive number, b is a positive number, c is a positive number, a / c is a number from 0 to 4, b / c is a number from 0.05 to 4. ,
And (a + b) / c is a number of 0.2-4. } And has an alkoxysilylalkyl group and 6 carbon atoms in one molecule.
A curable resin composition comprising 0.1 to 500 parts by weight of an organopolysiloxane having at least one of each of the above alkyl groups. 2. The curable resin composition according to claim 1, wherein the component (A) is a curable resin selected from the group consisting of epoxy resins, phenol resins, imide resins and silicone resins. 3. The component (B) is an organopolysiloxane having at least one organic group containing an epoxy group, an alkoxysilylalkyl group and an alkyl group having 6 or more carbon atoms in one molecule. Item 1. The curable resin composition according to item 1.