JP3047725B2 - Composite material modifier and composite material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material obtained by treating an inorganic reinforcing material such as glass fiber product and mica product with an organic resin, especially for a composite material suitable for improving solder heat resistance and heat shock characteristics. It relates to a modifier and a composite material.

[0002]

2. Description of the Related Art
Composite materials obtained by treating glass fiber products such as glass cloth, glass tape, glass mat, glass paper and mica products with inorganic resins such as epoxy resin, phenol resin, polyimide resin and unsaturated polyester resin as inorganic reinforcing materials for various uses. Widely used.

[0003] Laminates made from such composite materials have various physical properties, such as mechanical strength, electrical properties, and the like.
In order to improve water resistance, boiling resistance and chemical resistance, the above-mentioned inorganic reinforcing material is used as γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane,
There has been proposed a method of improving the adhesion between an inorganic reinforcing material and a resin by performing a preliminary treatment with a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane and then treating with an organic resin.

On the other hand, a laminate for a printed circuit board using an epoxy resin or a polyimide resin as an organic resin in a composite material is immersed in molten solder during a wiring process. The stratification is also increasing. For this reason, a silane coupling agent having stronger heat resistance is required for pretreatment of the inorganic reinforcing material.

[0005] However, the above-mentioned treatment with the conventionally known silane coupling agent has a disadvantage that the solder heat resistance is poor because a large curing strain is generated at the interface between the inorganic reinforcing material and the resin.

Further, a method of treating with a hydrochloride of a compound represented by the following formula (a) or aniline-substituted silane (JP-B-48-20609, JP-B-57-4177)
No. 1) and a treatment with a silane compound represented by the following formula (b) (see Japanese Patent Application Laid-Open No. 1-48832) have been proposed. In that case, the blister prevention effect was still insufficient.

[0007]

Embedded image (However, in the formula, R ⁹ is a methyl group or an ethyl group, R ¹⁰ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and q is an integer of 4 to 8.)

Further, the conventional printed circuit board laminate is based on the difference in the coefficient of thermal expansion between the reinforcing plate and the resin when immersed in molten solder, and furthermore between the copper foil for circuit wiring adhered to the surface. The disadvantage is that these bonds are broken by stress differences, and for these products,
It has been required to improve heat shock characteristics in addition to solder heat resistance.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and when a pretreatment is performed on an inorganic reinforcing material of a composite material, a modification for a composite material having excellent effects of improving solder heat resistance and heat shock characteristics. It is intended to provide a filler and a composite material.

[0010]

The present inventors have made intensive studies to achieve the above object, and as a result, obtained a composite material obtained by treating an inorganic reinforcing material with an organic resin by the following general formula (1). By pre-treating the inorganic reinforcing material with a modifier for a composite material containing the amino group-containing silane compound or its halide shown as a main agent, the inorganic reinforcing material and the organic resin have no curing strain. , So that solder heat resistance and heat shock resistance can be improved at the same time, and very good properties can be obtained even when such a composite material is made into a thin-layer laminate. This has led to the achievement of the present invention.

[0011]

Embedded image (Wherein, R ¹ and R ⁵ each represent a monovalent hydrocarbon group having 1 or 2 carbon atoms, R ² and R ⁴ each represent a divalent hydrocarbon group containing 1 to 10 carbon atoms and not containing a hydroxy group, R ³ Is carbon number 2
To 8 divalent hydrocarbon groups, R ⁶ and R ⁷ are each a hydrogen atom,
A benzyl group or a vinylbenzyl group, and at least one of R ⁶ and R ⁷ is a benzyl group or a vinylbenzyl group; X and Y are each a monovalent alkoxy group having 1 or 2 carbon atoms, and m, n and p are each 0, 1 or 2. )

Accordingly, the present invention is a composite material modifier for treating the surface of the inorganic reinforcing material in a composite material obtained by bonding an inorganic reinforcing material and an organic resin,
A modifier for a composite material comprising an amino group-containing silane compound represented by the general formula (1) or a halide thereof as a main agent, and an inorganic reinforcing material and an organic resin bonded to each other. A composite material, wherein the surface of the inorganic reinforcing material is treated in advance with the composite material modifier.

Now, the present invention will be described in further detail. The modifier for a composite material according to the present invention may be a glass fiber such as an alkali glass, a non-alkali glass, a low dielectric glass, a high elastic glass, an E glass for electricity, and the like. Strands (glass bundles) obtained by bundling glass filaments, non-woven glass mats, glass papers, glass fibers woven with yarns, glass tapes and other glass fiber products, and soft or hard bundles made from mica flakes Mica products such as mica sheets are used as inorganic reinforcing materials, and in the case of composite materials in which this inorganic reinforcing material is treated with an organic resin such as an epoxy resin, a polyimide resin, and an unsaturated polyester resin,
It is used for pre-treating the inorganic reinforcing material of this composite material, and is mainly composed of an amino group-containing silane compound represented by the following general formula (1) or a halide thereof.

[0014]

Embedded image (Wherein, R ¹ and R ⁵ each represent a monovalent hydrocarbon group having 1 or 2 carbon atoms, R ² and R ⁴ each represent a divalent hydrocarbon group containing 1 to 10 carbon atoms and not containing a hydroxy group, R ³ Is carbon number 2
To 8 divalent hydrocarbon groups, R ⁶ and R ⁷ are each a hydrogen atom,
A benzyl group or a vinylbenzyl group, and at least one of R ⁶ and R ⁷ is a benzyl group or a vinylbenzyl group; X and Y are each a monovalent alkoxy group having 1 or 2 carbon atoms, and m, n and p are each 0, 1 or 2
It is. )

[0015]

Embedded image

The halogen salt of the amino group-containing silane compound of the above formula (1) includes, for example, hydrochloride, bromate and the like, and hydrochloride is preferred.

Specific examples of the amino group-containing silane compound of the above formula (1) include the following compounds.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

The amino group-containing silane compound of the above formula (1) or a salt thereof is a silane compound represented by the following formula (2), a silane compound represented by the following formula (3) and a silane compound represented by the following formula (4) ) And / or methyl styrene halide.

[0022]

Embedded image (Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, Y, m,
n and p are respectively the same as above, R ⁸ is a hydrogen atom or a vinyl group, A is a halogen atom, and a chlorine atom or a bromine atom is preferable. )

In this case, the amount of each compound used is determined by the formula (2)
Is preferably reacted with the compound of the formula (3) and the compound of the formula (4) in a reaction molar ratio of 1: 1: 1-1: 1: (1 + m). Note that m has the same meaning as described above.

During or after the reaction, a tertiary amine compound such as triethylamine or pyridine or an alkali metal alcoholate such as sodium methylate or sodium ethylate is used to form a tertiary amine halide or a metal halide. To remove the halogen acid.

When reacting a benzyl halide or a methyl styrene halide, either one of the two compounds may be reacted or both compounds may be used in combination. When both compounds are used in combination, both compounds may be mixed and reacted, or one may be reacted first and then the other may be reacted.

In any of the above methods, the use of a solvent is optional. For example, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, hexane, heptane and nonane And aliphatic hydrocarbons such as decane.

The reaction conditions are not particularly limited, but may be 50 to 1
The reaction of the silane compound of the formula (3) with the silane compound of the formula (2) is carried out for 2 to 15 hours at 50 ° C.
The reaction between the benzyl halide and the methyl styrene halide is preferably performed for 2 to 15 hours.

Pretreatment of an inorganic reinforcing material for a composite material such as a glass fiber product and a mica product using a modifier for a composite material containing the amino group-containing silane compound of the formula (1) of the present invention as a main component. In this case, it is desirable to dilute the above composite material modifier with an appropriate solvent to prepare a treatment liquid. In this case, the solvent is preferably water or an aqueous acetic acid solution having a concentration of about 0.5 to 2% by weight, and alcohols such as methanol and ethanol may be further added.
In this treatment liquid, the compounding amount of the amino group-containing silane compound of the above formula (1) is preferably 0.2 to 3% (wt%, the same applies hereinafter), particularly preferably 0.5 to 1% of the whole,
If it is less than 0.2%, a satisfactory modifying effect may not be obtained, and if it exceeds 3%, the treatment effect may not be improved and the cost may be increased.

The modifier for a composite material of the present invention may further contain other additives other than a dye, a pigment, an antistatic agent, a lubricant and the amino group-containing silane compound of the above formula (1), if necessary. Can be added in a range that does not impair the effects of the present invention.

Further, the method of treating the composite material modifier into the inorganic reinforcing material may be performed by immersing the reinforcing material in a treatment liquid obtained by diluting the composite material modifier. In this case, depending on the case, the solution holding ratio of the processing liquid may be made constant using a squeeze roll or the like, or the processing liquid may be spray applied to a mica sheet or the like. Further, after the treatment, the resultant is dried at 60 to 120 ° C. for about 5 minutes to 2 hours, and simultaneously with the removal of the solvent, the surface of the inorganic reinforcing material and the amino group-containing silane compound of the above formula (1) in the composite material modifier are combined. Preferably, a chemical reaction is performed.

[0031]

Industrial Applicability The modifier for a composite material of the present invention comprises an inorganic reinforcing material such as a glass fiber product and a mica product and an epoxy resin,
When the inorganic reinforcing material of a composite material composed of an organic resin such as a polyimide resin and an unsaturated polyester resin is pre-treated, the inorganic reinforcing material and the organic resin are firmly bonded without curing distortion, and the bonding surface is A composite material that is flexible and has good water resistance and is excellent in solder heat resistance and heat shock characteristics even as a laminated plate when thinned.

[0032]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

[Synthesis Example 1] A thermometer, a cooler, and a dropping funnel were attached to a 1-liter separable flask, and 111.0 g of β-aminoethyl-γ-aminopropyltrimethoxysilane represented by the following formula (5) was added. 0.5 mol) at 120 ° C., and γ-
99.3 g of chloropropyltrimethoxysilane (0.5
Mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 10 hours, and the amount of chlorine was measured to confirm that the reaction was completed.

[0034]

Embedded image

Thereafter, the mixture was cooled and 111.0 g of methanol was added.
And 76.2 g of chloromethylstyrene at 70 ° C.
(0.5 mol) was slowly added dropwise. After dropping, 70
Stirring was continued at 10 ° C. for 10 hours, and it was confirmed that the reaction was completed by measuring the amount of hydrochloric acid in this solution. When this solution was further diluted with methanol, a 50% methanol solution of the silane compound (I) represented by the following formula (7) was obtained.

[0036]

Embedded image

[Synthesis Example 2] A thermometer, a cooler, and a dropping funnel were attached to a 1-liter separable flask, and 90.0 g (0.5 mol) of γ-aminopropyltrimethoxysilane represented by the following formula (8) was attached. At 120 ° C
Then, 99.3 g (0.5 mol) of γ-chloropropyltrimethoxysilane represented by the above formula (6) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 10 hours, and the amount of chlorine was measured to confirm that the reaction was completed.

[0038]

Embedded image

After cooling to 60 ° C., 96.5 g of a 28% methanol solution of sodium methylate was slowly added dropwise. After completion of dropping, stirring was continued at 70 ° C. for 2 hours.
The salt formed is filtered off, the product is again charged into the flask,
At 70 ° C., 63.2 g (0.5 mol) of benzyl chloride was slowly added dropwise. After the completion of the dropwise addition, stirring was continued at 70 ° C. for 10 hours, and it was confirmed that the reaction was completed by measuring the amount of hydrochloric acid in this solution. When this solution was further diluted with methanol, the silane compound (I) represented by the following formula (9) was obtained.
A 50% methanol solution of I) was obtained.

[0040]

Embedded image

[Synthesis Example 3] A thermometer, a cooler and a dropping funnel were attached to a 1-liter separable flask, and γ- (aminomethylphenylmethyl) -aminopropyltrimethoxysilane 149. 0g
(0.5 mol), and 99.2 g (0.5 mol) of γ-chloropropyltrimethoxysilane represented by the above formula (6) was slowly dropped at 120 ° C. After completion of the dropwise addition, the mixture was stirred at 120 ° C. for 10 hours, and the amount of chlorine was measured to confirm that the reaction was completed.

[0042]

Embedded image

After cooling, 149.0 g of methanol was added.
Was further charged, and 63.2 g of benzyl chloride was added at 70 ° C.
(0.5 mol) was slowly added dropwise. After dropping, 70
Stirred at 150C for 15 hours. It was confirmed that the reaction was completed by measuring the chlorine content of this product. Then, 183.3 g of a 28% methanol solution of sodium methylate
(0.95 mol) was slowly added dropwise. After dropping, 7
After stirring at 0 ° C. for 1 hour, the generated salt was filtered off,
Further dilution with methanol gave a 50% methanol solution of the silane compound (III) represented by the following formula (11).

[0044]

Embedded image

Synthesis Example 4 As an amino group-containing silane compound, 1.0 mol of a compound represented by the following formula (12), γ-
The reaction was carried out in the same manner as in Synthesis Example 1 except that 1.0 mol of the compound represented by the following formula (13) was used instead of chloropropyltrimethoxysilane, and 1.0 mol of benzyl chloride was used instead of chloromethylstyrene. The following equation (14)
To give a 50% methanol solution of the silane compound (IV).

[0046]

Embedded image

[Synthesis Example 5] As the amino group-containing silane compound, 1.0 mol of the compound represented by the above formula (5) was used instead of γ-chloropropyltrimethoxysilane.
The reaction was carried out in the same manner as in Synthesis Example 2 except that 1.0 mol of the compound represented by 5) and 2.0 mol of chloromethylstyrene were used instead of benzyl chloride, and a silane compound represented by the following formula (16) ( A 50% methanol solution of V) was obtained.

[0048]

Embedded image

Synthesis Example 6 As an amino group-containing silane compound, 1.0 mol of a compound represented by the following formula (17):
The reaction was carried out in the same manner as in Synthesis Example 1 except that 1.0 mol of the compound represented by the following formula (18) was used instead of chloropropyltrimethoxysilane, and 1.0 mol of benzyl chloride was used instead of chloromethylstyrene. The following equation (19)
To obtain a 50% methanol solution of the silane compound (VI).

[0050]

Embedded image

[Synthesis Example 7] As an amino group-containing silane compound, 1.0 mol of a compound represented by the following formula (20):
The reaction was carried out in the same manner as in Synthesis Example 3 except that 1.0 mol of the compound represented by the following formula (21) was used instead of chloropropyltrimethoxysilane, and 1.0 mol of chloromethylstyrene was used instead of benzyl chloride. The following equation (22)
To obtain a 50% methanol solution of the silane compound (VII).

[0052]

Embedded image

Example 1 A 50% methanol solution of the silane compound (I) obtained in Synthesis Example 1 was dissolved in a 1% by weight aqueous acetic acid solution to a concentration of 10 g / l in a treatment solution, and the surface was subjected to heat cleaning. Glass cloth WE18
K105B (manufactured by Nitto Boseki Co., Ltd.) was immersed, squeezed with a squeeze roll, and dried at 110 ° C. for 15 minutes.

Next, a bisphenol type epoxy resin (Epicoat 100) was used according to the NEMA standard G-10 prescription.
1, 80 parts of Yuka Shell Epoxy), 20 parts of novolak type epoxy resin (Epicoat 154, 20 parts of Yuka Shell Epoxy), 4.0 parts of dicyandiamide, 0.2 part of benzyldimethylamine, 20 parts of methyl ethyl ketone and methyl cellosolve After impregnating the silane-treated glass cloth in a resin varnish mixed with 45 parts,
Precuring was performed under the condition of minutes to prepare a B-stage prepreg. A copper foil was laid on top and bottom of the eight prepregs, and press-molded under the conditions of 170 ° C. × 35 kg / cm ² × 60 minutes to produce a double-sided copper-clad laminate.

Examples 2 to 4, Comparative Examples 1 to 3 As shown in Table 1, 50% of the silane compounds (II) to (IV) obtained in Synthesis Examples 2 to 4 in place of the silane compound (I). Methanol solution, 5 of the following silane compounds (VIII) to (X)
A silane-treated glass cloth and a copper-clad laminate were prepared in the same manner as in Example 1 except that a 0% methanol solution was used. Since the silane compound (VIII) was soluble in pure water, pure water was used instead of acetic acid water.

[0056]

Embedded image

Examples 5 to 7, Comparative Examples 4 to 7 Instead of the silane compound (I), as shown in Table 1, 50% of the silane compounds (V) to (VII) obtained in Synthesis Examples 5 to 7 Methanol solution, 5 of the above silane compounds (VIII) to (X)
A silane-treated glass cloth was prepared in the same manner as in Example 1 except that a 0% methanol solution was used.

Next, according to NEMA standard FR-4 processing method, brominated epoxy resin Epicoat 5046-B-8
100 parts (manufactured by Yuka Shell Epoxy), 20 parts of novolak type epoxy resin Epicoat 154, 4 parts of dicyandiamide, 2-ethyl-4-methylimidazole 0.1 part.
A resin varnish obtained by mixing 2 parts, 15 parts of methyl ethyl ketone and 30 parts of dimethylformamide was impregnated with these silane-treated glass cloths, and treated in the same manner as in Example 1 to produce a double-sided copper-clad laminate.

The obtained copper-clad laminate was subjected to boiling water absorption, solder heat resistance and heat shock tests by the following methods. The results are shown in Tables 1 and 2. Boiling water absorption: 50 × in which copper foil was removed from a copper-clad laminate by etching according to the test method of JIS-C-6481.
A 50 mm test plate was cut out and the water absorption after boiling for 4 to 14 hours was measured. Solder heat resistance: The test plate after measuring the boiling water absorption was 26
The area of the part where blisters occurred on the test plate when it was floated on a solder bath at 0 ° C. for 30 seconds was shown as a fracture area (%). Heat shock test: The copper-clad laminate was immersed in liquid nitrogen for 1 minute, immediately immersed in a solder bath at 290 ° C. for 30 seconds, and then inspected for damage on the test plate from which the copper foil was removed by etching. Decided. ：: Good ：: Slight spot defect generated △: Spot defect generated ×: Destruction occurred entirely (laminated plate peeled off) From the results in Tables 1 and 2, treatment with the composite material modifier of the present invention was performed. It was confirmed that the obtained copper-clad laminate was excellent in boiling water absorption, solder heat resistance and heat shock characteristics.

[0060]

[Table 1]

[0061]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C03C 25/02 Z (56) References JP-A-7-228587 (JP, A) JP-A 5-156080 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 25/00-25/02 D06M 13/50-13/517

Claims (6)

(57) [Claims] 1. A composite material modifier for treating the surface of an inorganic reinforcing material in a composite material obtained by bonding an inorganic reinforcing material and an organic resin, wherein the modifying agent has the following general formula (1):
A modifier for a composite material comprising, as a main agent, an amino group-containing silane compound represented by the formula (1) or a salt thereof. Embedded image (Wherein, R ¹ and R ⁵ each represent a monovalent hydrocarbon group having 1 or 2 carbon atoms, R ² and R ⁴ each represent a divalent hydrocarbon group containing 1 to 10 carbon atoms and not containing a hydroxy group, R ³ Is carbon number 2
To 8 divalent hydrocarbon groups, R ⁶ and R ⁷ are each a hydrogen atom,
A benzyl group or a vinylbenzyl group, and at least one of R ⁶ and R ⁷ is a benzyl group or a vinylbenzyl group; X and Y are each a monovalent alkoxy group having 1 or 2 carbon atoms, and m, n and p are each 0, 1 or 2
It is. ) 2. The compound of the formula (1) is represented by the following general formula (2)
And a silane compound represented by the following general formula (3) and a benzyl halide and / or a halogenated methyl styrene represented by the following general formula (4) in a molar ratio of 1: 1: 1-1: 1: The modifier according to claim 1, which is obtained by reacting at 1: 1: (1 + m). Embedded image (Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, Y, m,
n and p have the same meanings as described in claim 1,
R ⁸ is a hydrogen atom or a vinyl group, and A is a halogen atom. ) 3. The composite material modifier according to claim 1, wherein the inorganic reinforcing material is a glass fiber product or a mica product. 4. A composite material comprising an inorganic reinforcing material and an organic resin bonded to each other, wherein the surface of the inorganic reinforcing material is previously treated with the composite material modifier according to claim 1 or 2. A composite material characterized by the above. 5. The composite material according to claim 4, wherein the inorganic reinforcing material is a glass fiber product or a mica product. 6. The composite material according to claim 4, wherein the composite material is a laminate for a printed circuit board.