JP3427465B2 - Modifier for composite material, method for producing the same, and composite material - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite material suitable for improving the characteristics of a composite material obtained by treating an inorganic reinforcing material such as a glass fiber product and a mica product with an organic resin, particularly solder heat resistance and heat shock characteristics. The present invention relates to a modifier, a method for producing the same, and a composite material.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Inorganic reinforcing materials such as glass cloth, glass tape, glass mat, glass paper, and other glass fiber products and mica products treated with epoxy resins, phenol resins, polyimide resins, unsaturated polyester resins and other organic resins are used in various applications. Widely used.

Laminates made from such composite materials have various physical properties such as mechanical strength, electrical properties,
In order to improve water resistance to boiling and resistance to chemicals, the inorganic reinforcing material is γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane,
A method has been proposed in which the adhesion between the inorganic reinforcing material and the resin is improved by pretreatment with a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane and then treatment with an organic resin.

On the other hand, a laminated board for a printed circuit board, which uses an epoxy resin or a polyimide resin as an organic resin among the composite materials, is immersed in molten solder during the wiring process, and recently, a laminated board for a printed circuit board is thin. Stratification is also increasing. Therefore, a silane coupling agent having stronger heat resistance is required for the pretreatment of the inorganic reinforcing material.

However, the treatment with the above-mentioned conventionally known silane coupling agent has a drawback that the heat resistance of the solder is poor because a large curing strain occurs 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 (4) or an aniline-substituted silane (Japanese Patent Publication Nos. 48-20609 and 57-4177).
No. 1) or treatment with a silane compound represented by the following formula (5) (see Japanese Patent Laid-Open No. 1-48832) is proposed, but a laminate pretreated with these compounds is also thinned. In that case, the blister prevention effect was still insufficient.

[0007]

[Chemical 6] (However, in the formula, R ¹⁰ is a methyl group or an ethyl group, R ¹¹ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 4 to 8.)

Further, regarding the conventional printed circuit board laminated plate, it is based on the difference in the coefficient of thermal expansion between the reinforcing plate and the resin when immersed in the molten solder, and further the copper foil for circuit wiring adhered to the surface. The disadvantage is that their bond is broken by the stress difference, which is why these products are also required to have improved heat shock properties in addition to solder heat resistance.

The present invention has been made to solve the above-mentioned problems, and when the inorganic reinforcing material of the composite material is pretreated, it is improved for the composite material, which is excellent in improving the heat resistance of solder and the heat shock property. An object is to provide a substance, a method for producing the same, and a composite material.

[0010]

Means and Actions for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that in a composite material obtained by treating an inorganic resin with an organic resin, the following general formula (2) is used. The amino group-containing silane compound represented by the following general formula (1) obtained by reacting the silane compound represented by the following with the silane compound represented by the following general formula (3) and benzyl halide and / or vinylbenzyl halide. Or by pre-treating the inorganic reinforcing material with a composite material modifier containing the halogenate as a main agent, the inorganic reinforcing material and the organic resin can be firmly bonded without curing strain, Therefore, it is possible to improve the solder heat resistance and the heat shock resistance at the same time, and it is possible to obtain very good characteristics even when the composite material is made into a thin layer to produce a laminated board. And it found that is, the present invention has been accomplished.

[0011]

[Chemical 7] [Wherein R ¹ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is 2 carbon atoms
To 8 are divalent hydrocarbon groups, X is a monovalent alkoxy group having 1 or 2 carbon atoms, and m and n are 0, 1 or 2, respectively. )

[0012]

[Chemical 8] [Wherein R ⁷ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ⁹ is a divalent hydrocarbon group which may contain an oxygen atom, Y
Is a monovalent alkoxy group having 1 or 2 carbon atoms, p is 0,
1 or 2. )

[0013]

[Chemical 9] [Wherein R ¹ , R ² , R ³ , X, m and n are the same as defined above, R ⁴ , R ⁵ and R ⁶ are hydrogen atoms,
Benzyl group, vinylbenzyl group or

[0014]

[Chemical 10] Is a hydroxy group-containing group (R ⁷ , Y and p are the same as defined above, and R ⁸ is a divalent hydrocarbon group optionally having an oxygen atom having a hydroxy group),
At least one of R ⁴ , R ⁵ and R ⁶ is

[0015]

[Chemical 11] And at least one is a benzyl group or a vinylbenzyl group.

Therefore, the present invention is a modifier for a composite material, characterized by containing an amino group-containing silane compound represented by the above general formula (1) or a halogenate thereof as a main agent, and the above general formula. The silane compound represented by the formula (2) is reacted with the silane compound represented by the following general formula (3) with benzyl halide and / or vinylbenzyl halide, or the amino group-containing silane compound represented by the general formula (1) or a compound thereof. A method for producing a modifier for a composite material for obtaining a halogenate,
And a composite material obtained by treating an inorganic reinforcing material with an organic resin, wherein the inorganic reinforcing material is pretreated with the modifier for a composite material.

The present invention will be described in more detail below. The modifier for a composite material of the present invention is a glass fiber such as alkali glass, non-alkali glass, low dielectric glass, high elasticity glass, and E glass for electrical use. Strands (glass bundles) of spun glass filaments, non-woven glass mats, glass paper, and glass fiber products such as woven glass cloth and glass tape, and soft or hard bundles made from mica flakes. Using a mica product such as mica sheet as an inorganic reinforcing material, in the composite material obtained by treating the inorganic reinforcing material with an organic resin such as epoxy resin, polyimide resin, unsaturated polyester resin,
It is used for pretreatment of 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 halogenate thereof.

[0018]

[Chemical 12] [Wherein R ¹ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is 2 carbon atoms
~ 8 divalent hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom, a benzyl group, a vinylbenzyl group or

[0019]

[Chemical 13] A hydroxy group-containing group (R⁷Has 1 or 2 carbon atoms
Monovalent hydrocarbon group of R⁸Is an oxygen source having a hydroxy group
A divalent hydrocarbon group which may contain a child, Y has 1 or more carbon atoms
Is a monovalent alkoxy group of 2 and p is 0, 1 or 2. )
And R^Four, R^Five , R⁶At least one of

[0020]

[Chemical 14] A hydroxy group-containing group represented by and at least one is
A benzyl group or a vinylbenzyl group. Also, X is charcoal
It is a monovalent alkoxy group having a prime number of 1 or 2, and m and n are
0, 1 or 2 respectively. ) Where R¹Is for example CH₃
-, CH₃CH ₂− And R²Is an alkylene group, ant
Examples of the alkylene group include an arylene group and an arylene group
For example,

[0021]

[Chemical 15] Is. Examples of R ³ include an alkylene group, an arylene group, and an alkylene group in which an arylene group is present.

[0022]

[Chemical 16] Is. R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom,

[0023]

[Chemical 17] A vinylbenzyl group represented by or

[0024]

[Chemical 18] A hydroxy group-containing group represented by (R ⁷ is, for example, CH ₃ —,
CH ₃ CH ₂ -, R ⁸ preferably has 4 to 14 carbon atoms, especially 6 to 10, e.g.

[0025]

[Chemical 19] Y is CH ₃ O-, CH ₃ CH ₂ are O-, p is 0, 1 or 2. ). At least one of R ⁴ , R ⁵ and R ⁶ is

[0026]

[Chemical 20] And at least one is a benzyl group or a vinylbenzyl group. Further, X is a monovalent alkoxy group having 1 or 2 carbon atoms, and m and n are 0, 1 or 2, respectively.

Examples of the halogen salt of the amino group-containing silane compound represented by the above formula (1) include hydrochloride, hydrobromide, and iodine salt, and the hydrochloride is preferred.

Specific examples of the amino group-containing silane compound of the above formula (1) or its halogen salt thereof include the following compounds.

[0029]

[Chemical 21]

[0030]

[Chemical formula 22]

[0031]

[Chemical formula 23]

[0032]

[Chemical formula 24]

The amino group-containing silane compound of the above formula (1) or its halogenate is a silane compound represented by the following general formula (2), a silane compound represented by the following general formula (3), a benzyl halide, and And / or vinylbenzyl halide.

[0034]

[Chemical 25] [However, in the formula, R ¹ , R ² , R ³ , R ⁷ , X, Y, p, m, n
Are the same as above, respectively, and R ⁹ is a divalent hydrocarbon group which may contain an oxygen atom, preferably having 2 to 1 carbon atoms.
2, especially 4-8, for example

[0035]

[Chemical formula 26] Is. )

Specific examples of the silane compound of the above formula (2) and the silane compound of the above formula (3) include the following compounds.

[0037]

[Chemical 27]

[0038]

[Chemical 28]

In this case, in the above reaction, after reacting the silane compound of the above formula (2) and the silane compound of the above formula (3), a benzyl halide and / or a vinylbenzyl halide is reacted ( After the reaction 1) or the silane compound of the above formula (2) is reacted with benzyl halide and / or vinylbenzyl halide, the silane compound of the above formula (3) can be reacted (reaction 2).

The amount of each compound used in the above reaction 1 is 1 mol of the silane compound of the above formula (2) when the compound of the above formula (3) is 0 in the formula (2). 1 mol, 1-2 mol when n is 1, 1-3 when n is 2
It is preferable to use a molar amount of benzyl halide and / or vinylbenzyl halide so that the number of hydrogen atoms on the nitrogen atom remaining in the above reaction is not more than the number of moles. Further, in the above Reaction 2, for 1 mol of the silane compound of the above formula (2), benzyl halide and //
Alternatively, vinylbenzyl halide is used in the formula (2) in an amount of 1 mol when n is 0, 1 to 2 mol when n is 1, and 1 to 3 mol when n is 2, and the formula (3) above. It is preferable to use the compound (1) such that the number of moles of hydrogen atoms on the nitrogen atom remaining in the above reaction is not more than the number of moles.

Further, during or after the reaction, a tertiary amine compound such as triethylamine or pyridine or a metal alcoholate such as sodium methylate or sodium ethylate is used as a tertiary amine halogenate or a metal halide. It is also possible to remove the halogen acid by filtering.

When reacting benzyl halide or vinyl benzyl 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 either compound may be reacted first and then both compounds 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 can be used.

The reaction conditions are not particularly limited, but are 60 to 12
0 ° C., the formula (3) for the silane compound of the formula (2)
The reaction of the silane compound is preferably for 2 to 15 hours, and the reaction of the benzyl halide and vinylbenzyl halide is preferably for 2 to 100 hours.

Pretreatment of inorganic reinforcing materials for composite materials such as glass fiber products and mica products using the modifier for composite materials containing the amino group-containing silane compound of the above formula (1) of the present invention as a main component. In this case, it is preferable to dilute the composite material modifier with an appropriate solvent to prepare a treatment liquid. In this case, the solvent is preferably water or an acetic acid aqueous solution having a concentration of about 0.5 to 3% by weight, and alcohols such as methanol and ethanol may be added.
In this treatment liquid, the compounding amount of the amino group-containing silane compound of the above formula (1) is preferably 0.1 to 3% (% by weight, the same hereinafter) of the whole, particularly preferably 0.5 to 1%.
If it is less than 0.1%, a satisfactory modifying effect may not be obtained, and if it exceeds 3%, the treatment effect is not improved and it is disadvantageous in terms of cost.

The composite material modifier of the present invention may contain other additives, other than dyes, pigments, antistatic agents, lubricants and amino group-containing silane compounds of the above formula (1), if necessary. The silane compound and the like can be added within a range that does not impair the effects of the present invention.

As a method of treating the inorganic reinforcing material with the composite material modifying agent, the reinforcing material may be dipped in a treatment liquid in which the composite material modifying agent is diluted. At this time, depending on the case, the solvent retention rate of the treatment liquid may be made constant by using a squeeze roll or the like, or the treatment liquid may be spray-coated on the mica sheet or the like. Further, after the treatment, the solvent is removed by drying at 60 to 120 ° C. for about 1 minute to 1 hour, and at the same time, the surface of the inorganic reinforcing material and the amino group-containing silane compound of the above formula (1) in the modifier for composite material are removed. It is preferable to carry out a chemical reaction.

[0048]

Industrial Applicability The modifier for composite materials of the present invention is an inorganic reinforcing material such as glass fiber products and mica products, and an epoxy resin,
When pretreatment is applied to the inorganic reinforcing material of the composite material consisting of polyimide resin and organic resin such as unsaturated polyester resin, the inorganic reinforcing material and the organic resin are firmly adhered to each other without curing strain, and the adhesion surface is A composite material that is flexible and has good water resistance, and has a thin layer and is excellent in solder heat resistance and heat shock characteristics even as a laminated plate.

[0049]

EXAMPLES The present invention will be specifically described below by showing 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 (0.5) of β-aminoethyl-γ-aminopropyltrimethoxysilane represented by the following formula (6). Mol), and at 1350 g, γ-glycidyloxypropyltrimethoxysilane represented by the following formula (7) 118.0 g (0.5
Mol) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at 140 ° C. for 4 hours, and when the disappearance of γ-glycidyloxypropyltrimethoxysilane was confirmed by gas chromatographic analysis, the reaction was regarded as the end point.

[0050]

[Chemical 29]

Then, the mixture was cooled and charged with 50 g of methanol, and at 80 ° C., 76.2 g of chloromethylstyrene (0.
5 mol) was slowly added dropwise. After the dropping was completed, stirring was continued at 80 ° C. for 28 hours, and the amount of hydrochloric acid in this solution was measured to confirm that the reaction was completed. When this solution was further diluted with methanol, a 50% methanol solution of the silane compound (I) represented by the following formula (8) was obtained.

[0052]

[Chemical 30]

[Synthesis Example 2] Synthesis was carried out in the same manner as in Synthesis Example 1 and, after confirming that the reaction was completed, 91.7 g (0.48 mol) of a methanol solution of 28% sodium methylate was added at 60 ° C. It was dripped slowly. After dropping, 60
%, The resulting salt was filtered off and then diluted with methanol to obtain a 50% methanol solution of a silane compound (II) represented by the following formula (9).

[0054]

[Chemical 31]

[Synthesis Example 3] The reaction was performed in the same manner as in Synthesis Example 1 except that the amount of chloromethylstyrene dropped was 106.8 g (0.7 mol), and the silane compound (III) represented by the following formula (10) was used. A 50% methanol solution of () was obtained.

[0056]

[Chemical 32]

[Synthesis Example 4] 9,10-epoxydecyltrimethoxysilane 13 represented by the following formula (11) instead of γ-glycidyloxypropyltrimethoxysilane 13
The reaction was performed in the same manner as in Synthesis Example 1 except that 8.0 g (0.5 mol) was used to obtain a 50% methanol solution of the silane compound (IV) represented by the following formula (12).

[0058]

[Chemical 33]

[Synthesis Example 5] Instead of β-aminoethyl-γ-aminopropyltrimethoxysilane, the following formula (1)
3) β-aminoethyl-β-aminoethyl-
γ-aminopropyltrimethoxysilane 132.5 g
(0.5 mol) was used, and the reaction was performed in the same manner as in Synthesis Example 2 except that the amount of chloromethylstyrene added was 106.8 g (0.7 mol), and the silane compound represented by the following formula (14) was used. A 50% methanol solution of (V) was obtained.

[0060]

[Chemical 34]

[Synthesis Example 6] 89.5 g (0.5 mol) of γ-aminopropyltrimethoxysilane was used in place of β-aminoethyl-γ-aminopropyltrimethoxysilane, and the amount of chloromethylstyrene dropped was 61. 0.0 g
The reaction was performed in the same manner as in Synthesis Example 1 except that the amount was (0.4 mol), and the silane compound represented by the following formula (15) (V
5 of a mixture of I) and a compound represented by the following formula (16)
A 0% methanol solution was obtained.

[0062]

[Chemical 35]

[Synthesis Example 7] The reaction was carried out in the same manner as in Synthesis Example 3 except that 88.6 g (0.7 mol) of benzyl chloride was added dropwise instead of chloromethylstyrene, and the following formula (1)
A 50% methanol solution of the silane compound (VII) represented by 7) was obtained.

[0064]

[Chemical 36]

[Synthesis Example 8] ω-aminohexyl-γ-aminopropyltrimethoxysilane 13 instead of β-aminoethyl-γ-aminopropyltrimethoxysilane 13
The reaction was carried out in the same manner as in Synthesis Example 1 except that 9.0 g (0.5 mol) was used and 63.3 g (0.5 mol) of benzyl chloride was added dropwise instead of chloromethylstyrene. ) 50 of the silane compound (VIII)
% Methanol solution was obtained.

[0066]

[Chemical 37]

[Example 1] A surface of the silane compound (I) obtained in Synthesis Example 1 was heat-cleaned in a treatment solution prepared by dissolving 50% methanol solution of silane compound (I) in 1% by weight of acetic acid solution at a concentration of 10 g / 1. Cleaned glass cloth WE18
K105B (manufactured by Nitto Boseki Co., Ltd.) was dipped, squeezed with a squeeze roll, and dried at 110 ° C. for 15 minutes.

Then, a bisphenol type epoxy resin (Epicoat 100 was used according to the NEMA standard G-10 prescription.
80 parts, Novolak type epoxy resin (Epicoat 154, manufactured by Yuka Shell Epoxy Co., Ltd.), 4.0 parts of dicyandiamide, 0.2 part of benzyldimethylamine, 20 parts of methyl ethyl ketone and methyl cellosolve. A resin varnish mixed with 45 parts was impregnated with the above-mentioned silane-treated glass cloth, then,
Pre-cured under the condition of 1 minute to make a prepreg in the B stage. A copper foil was laminated on the upper and lower sides of a stack of 8 sheets of this prepreg and press-molded under the conditions of 170 ° C. × 35 kg / cm ² × 60 minutes to prepare a double-sided copper-clad laminate.

Examples 2 to 8 A 50% methanol solution of the silane compounds (II) to (VIII) obtained in Synthesis Examples 2 to 8 as shown in Table 1 was used instead of the silane compound (I). A silane-treated glass cloth and a copper clad laminate were prepared in the same manner as in Example 1.

[Comparative Examples 1 to 3] Instead of the silane compound (I), as shown in Table 1, the following silane compounds (IX) to
A silane-treated glass cloth and a copper clad laminate were produced in the same manner as in Example 1 except that a 50% methanol solution of (XI) was used. Since the silane compound (IX) was soluble in pure water, pure water was used instead of acetic acid water.

[0071]

[Chemical 38]

With respect to the obtained copper-clad laminate, the glass content of the laminate, the boiling water absorption rate, the solder heat resistance, and the sheet shock test were conducted by the following methods. The results are shown in Table 1. Boiled water absorption: The copper foil was removed from the copper clad laminate by etching according to the test method of JIS-C-6481 50 ×
A 50 mm test plate was cut out and the water absorption after boiling for 4 to 16 hours was measured. Solder heat resistance: 26 test plates after the above boiling water absorption measurement
The area of the portion where the test plate blistered when floated in 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 the copper foil removed by etching was observed for damage. I judged it. ⊚: Good ○: Slight spot-like defect occurrence △: Spot-like defect occurrence ×: Overall breakage (lamination plate peeled)

[0073]

[Table 1]

From the results shown in Table 1, it was confirmed that the copper clad laminate treated with the composite material modifier of the present invention was excellent in boiling water absorption, solder resistance and heat shock characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-3-184985 (JP, A) US Patent 3621047 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07F 7 / 18 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. An amino group-containing compound represented by the following general formula (1):
Contains a silane compound or its halogenate as the main agent
A modifier for a composite material, characterized by comprising: [Chemical 1] [However, in the formula R¹Is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R²Is a divalent hydrocarbon group having 1 to 10 carbon atoms, R³Has 2 carbon atoms
~ 8 divalent hydrocarbon groups, R^Four, R^Five, R⁶Are each hydrogen
Atom, benzyl group, vinylbenzyl group or [Chemical 2] A hydroxy group-containing group (R⁷Has 1 or 2 carbon atoms
Monovalent hydrocarbon group of R⁸Is an oxygen source having a hydroxy group
A divalent hydrocarbon group which may contain a child, Y has 1 or more carbon atoms
Is a monovalent alkoxy group of 2 and p is 0, 1 or 2. )
And R^Four, R^Five , R⁶At least one of [Chemical 3] A hydroxy group-containing group represented by and at least one is
A benzyl group or a vinylbenzyl group. Also, X is charcoal
It is a monovalent alkoxy group having a prime number of 1 or 2, and m and n are
It is 0, 1 or 2, respectively. ) 2. The silane compound represented by the following general formula (2) is reacted with the silane compound represented by the following general formula (3) with benzyl halide and / or vinylbenzyl halide, and The method for producing a modifier for a composite material according to claim 1, wherein the amino group-containing silane compound represented by the general formula (1) or a halogenate thereof is obtained. [Chemical 4] [Wherein R ¹ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ² is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is 2 carbon atoms
To 8 are divalent hydrocarbon groups, X is a monovalent alkoxy group having 1 or 2 carbon atoms, and m and n are 0, 1 or 2, respectively. ) [Chemical 5] [Wherein R ⁷ is a monovalent hydrocarbon group having 1 or 2 carbon atoms,
R ⁹ is a divalent hydrocarbon group which may contain an oxygen atom, Y
Is a monovalent alkoxy group having 1 or 2 carbon atoms, p is 0,
1 or 2. ) 3. A composite material obtained by treating an inorganic reinforcing material with an organic resin, wherein the inorganic reinforcing material is pretreated with the modifier for a composite material according to claim 1.