JPH08325439A - Silane coupling agent for manufacturing glass fiber reinforced epoxy resin moldings - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a silane coupling agent for producing a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance and impregnation property. [Structure] Silane coupling consisting of N-γ-{(p-tolylmethyl) amino} propyltriethoxysilane hydrochloride or N-β- {N- (p-tolylmethyl) aminoethyl} -γ-aminopropyltrimethoxysilane A glass fiber-reinforced epoxy resin molded article can be produced by surface-treating glass fibers with an agent and impregnating the resulting surface-treated glass fibers with an epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silane coupling agent for producing a glass fiber reinforced epoxy resin molded article, a glass fiber surface-treated with the silane coupling agent, a glass fiber reinforced epoxy resin molded article, and a molding thereof. The present invention relates to a method of manufacturing a product. More specifically, the present invention relates to a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance, a silane coupling agent for producing the molded article, and a surface-treated glass fiber.

[0002]

2. Description of the Related Art Glass fiber reinforced epoxy resin molded products are
It is used for electronic parts such as printed circuit boards, high-voltage insulators, industrial pipes, and corrosion resistant tanks. When such a molded article is manufactured, the glass fiber is surface-treated with a silane coupling agent, and the obtained surface-treated glass fiber is impregnated with an epoxy resin. Conventionally, N-β has been used as the silane coupling agent from the viewpoint of affinity for glass and resin.
-{N- (vinylbenzyl) aminoethyl} -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, a special aminosilane having two or more benzene rings described in JP-A-4-178432, etc. Has been used.

However, when the former two silane coupling agents are used, the resulting glass fiber reinforced epoxy resin molded product has insufficient solder heat resistance and impregnation property, and as a result, the molded product is printed circuit board or high voltage insulation. In the case of a product, there is a problem that it may cause an electrical defect such as a short circuit or a dielectric breakdown, and when the molded product is an industrial pipe or a corrosion resistant tank, it may cause a liquid leak. In addition, 2 benzene rings
Since a silane coupling agent consisting of more than one special aminosilane has poor water solubility, it takes a long time to produce a surface treatment liquid when used in the production of glass fiber reinforced epoxy resin molded products, resulting in extremely poor productivity. There was a problem.

Therefore, it has been desired to develop a water-soluble silane coupling agent which gives a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance and heat resistance.

[0005]

DISCLOSURE OF THE INVENTION The objects of the present invention are: i) Silane coupling for glass fiber, which is easily soluble in water, for producing a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance in a short time. Agent, ii) glass fiber surface-treated with the silane coupling agent, and iii) a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance, and iv) a method for producing the above i to iii) is there.

[0006]

The present inventors have made diligent efforts to develop a method for producing a glass fiber reinforced epoxy resin molded article having excellent solder heat resistance in a short time. As a result, surprisingly, when a certain kind of aminosilane compound was used as a silane coupling agent to surface-treat glass fiber and the resulting surface-treated glass fiber was impregnated with epoxy resin, the desired glass fiber-reinforced epoxy resin was obtained. It has been found that a molded article can be manufactured. The present invention has been achieved based on such findings. The present invention has the general formula

[0007]

Embedded image (In the formula, R ¹ represents a hydrogen atom, a substituent selected from a methyl group or an ethyl group, m represents an integer of 0 to 3, and n
Represents an integer of 1 to 6 and R ² represents an alkyl group having 1 to 10 carbon atoms) and is a silane coupling agent for producing a glass fiber reinforced epoxy resin molded article, which comprises an aminosilane compound or a salt thereof.

In this case, for the purpose of the present invention, R ¹ is preferably a methyl group such as p-methyl, and m is 0 or 1.
Is preferred, n is preferably 3, and R ² is preferably methyl, ethyl, propyl or the like.

The glass fiber reinforced epoxy resin molded article of the present invention can be produced by surface-treating the glass fiber with the silane coupling agent of the present invention and impregnating the resulting surface-treated glass fiber with an epoxy resin.

The surface-treated glass fiber of the present invention is obtained by surface-treating the glass fiber with the silane coupling agent of the present invention.

When the glass fiber is surface-treated with the silane coupling agent of the present invention, first, the silane coupling agent can be dissolved in a solution containing an acid to produce a surface treatment solution. This surface treatment liquid has little cloudiness or is transparent. Examples of the liquid containing acid include acetic acid aqueous solution, formic acid aqueous solution, and hydrochloric acid aqueous solution. The surface treatment liquid is p
It is preferable to use H3 to H5. This coupling agent has good solubility in an acidic solution, and the glass fiber can be treated with the silane coupling agent quickly. In addition, this surface treatment liquid is extremely stable, and
Easy to handle because it is stable even if left unattended.

When the glass fiber is glass cloth, the surface treatment liquid is particularly required to be an aqueous solution, so that the present invention is particularly effective when glass cloth is used as the glass fiber. The glass is not particularly limited, and E
-Glass, T-glass, D-glass, etc. can be used.

When producing the surface-treated glass fiber of the present invention, the glass fiber is immersed in this surface-treatment liquid and then dried. It is preferable to dry at 100 to 120 ° C. When the glass fiber is glass cloth, the pickup amount can be adjusted by squeezing it with a mangle or the like after the immersion. If the drying temperature is too low, the drying will be insufficient.

By impregnating the surface-treated glass fiber of the present invention with an epoxy resin, the glass fiber-reinforced epoxy resin molded product of the present invention can be obtained.

An example of the effective use of the silane coupling agent of the present invention in the production of molded articles is the production of glass fiber reinforced epoxy resin laminates as molded articles. In this case, the glass cloth may be treated with the silane coupling agent of the present invention, and the surface-treated glass cloth obtained may be impregnated with an epoxy resin to produce a glass fiber reinforced epoxy resin laminate. When the surface-treated glass cloth is impregnated with the epoxy resin, it is preferable in operation that the prepreg is formed by using the surface-treated glass glass cloth and the epoxy resin, a plurality of the prepregs are laminated, and the prepreg is pressed under heating. . In this case, a copper-clad laminate suitable for printed circuit board production can be manufactured by applying copper foils on both sides.

In the present invention, examples of the epoxy resin include bisphenol A type epoxy resin, novolac type epoxy resin, and cycloaliphatic epoxy resin. It is preferable to use a brominated epoxy resin of bisphenol A type epoxy resin as the epoxy resin because the molded article produced is less likely to burn. A mixture of plural kinds of epoxy resins may be used depending on the use and purpose of the molded product to be manufactured.

When the surface-treated glass fiber of the present invention is impregnated into these epoxy resins, the epoxy resin can be dissolved in a solvent before use. As the solvent, an organic solvent such as diethyl ketone, dimethylformamide, acetone, methyl cellosolve, or a mixed solvent thereof can be used. An amine-based or acid anhydride-based curing agent may be added to the solution. Examples of amine curing agents include diethylenetriamine and dicyandiamide. Examples of the acid anhydride-based curing agent include phthalic anhydride and maleic anhydride.
Further, a catalyst such as 2-ethyl-4-methylimidazole can be added to the solution and used.

[0018]

When the silane coupling agent for the glass fiber reinforced epoxy resin molded article of the present invention is used, the molded article produced has excellent solder heat resistance. The coupling agent is characterized by having i) an alkoxysilane structure and ii) a structure such as methylbenzylamino. When a glass fiber reinforced epoxy resin molded article is produced using the present coupling agent, the silane portion is bonded to the glass and the methylbenzylamino portion is bonded to the epoxy resin, whereby the epoxy resin is impregnated with the glass fiber. It is considered possible. At this time, it is considered that the three-dimensional structure of methylbenzyl is involved in solder heat resistance.

[0019]

【Example】

Example 1 221.4 g (1.0 mol) of γ-aminopropyltriethoxysilane was charged as a raw material aminosilane into a 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel and a thermometer. After heating this to 60 to 80 ° C., 140.5 g (1.0 mol) of α-chloroparaxylene as a halide was slowly added dropwise from a dropping funnel.

After completion of the dropping, the raw materials in the separable flask are heated more gently while stirring, and the heating temperature is set to 60-80.
The reaction was continued for 16 hours while maintaining the temperature at ℃. The contents of the separable flask were taken every hour, and a part of the contents was developed by TLC (thin layer chromatography) to confirm the disappearance of α-chloroparaxylene. The TLC plate is kiesel manufactured by Merk.
gel 160 F254 was used, and benzene was used as a developing solvent.
About the obtained N- (p-tolylmethyl) -γ-aminopropyltriethoxysilane hydrochloride, 542.9 g of methanol was added and used as a 40% by weight methanol solution. FIG.
An IR chart of the reaction product obtained by removing methanol is shown in FIG.

Example 2 222.1 g (1.0%) of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane was used as the starting aminosilane.
Mol), α-chloroparaxylene as a halide 14
N-β- {N- (p-tolylmethyl) aminoethyl} -γ-aminopropyltrimethoxylane was treated in the same manner as in Example 1 except that 0.5 g (1.0 mol) was used.
_{p-CH 3 -C 6 H 4} CH 2 NHCH 2 CH 2 NH (CH
_{2) 3 -Si (OCH 3)} 3 was obtained 40 wt% methanol solution of hydrochloride.

Example 3 222.1 g (1.0 mol) of N-β- (aminoethyl) -γ-aminopropyltrimethosisilane was heated to 60 to 80 ° C., and then 140.5 g of α-chloroparaxylene was added from a dropping funnel ( 1.0 mol) was slowly added dropwise.

After the completion of dropping, the raw materials in the separable flask are heated more gently while stirring to raise the heating temperature to 60-80.
The reaction was continued for 16 hours while maintaining the temperature at ℃. After cooling, the obtained p-
_{CH 3 -C 6 H 4 -CH 2} NHCH 2 CH 2 NH (CH
₂ ) 28% by weight sodium methylate methanol solution for dehydrochlorination of _3- Si (OCH ₃ ) ₃ hydrochloride 192.
9 grams (1.0 mol) was added with slow stirring. After standing for 12 hours, the precipitated sodium chloride was separated by filtration, and methanol was added so that the weight percentage of the dehydrochlorinated compound was 40%.

Example 4 The same procedure as in Example 1 was carried out except that 221.4 g (1.0 mol) of γ-aminopropyltriethoxysilane was used as the starting aminosilane and 126.5 g (1.0 mol) of benzyl chloride was used as the halide. A 40 wt% methanol solution of N-benzyl-γ-aminopropyltriethoxysilane hydrochloride was prepared.

Example 5 The same procedure as in Example 1 was carried out except that 179.2 g (1.0 mol) of γ-aminopropyltrimethoxysilane was used as the starting aminosilane and 126.5 g (1.0 mol) of benzyl chloride was used as the halide. A 40 wt% solution of N-benzyl-γ-aminopropyltrimethoxylane hydrochloride in methanol was prepared.

Example 6 The compounds prepared in Examples 1 to 5 and N-β- {N- (Comparative Example 1
Vinylbenzyl) aminoethyl} -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane of Comparative Example 2, the formula C ₆ H ₅ — of Comparative Example 3.
_{CH 2 -NH (CH 2) 2} N (C 6 H 5) (CH 2) 3
A silane coupling agent selected from silane compounds represented by Si (OCH ₃ ) ₃ is used to produce a laminate from an epoxy resin and a glass fiber woven fabric as follows,
The solder heat resistance and impregnation property, and the water solubility of the silane coupling agent were examined.

0.7 parts by weight of a silane coupling agent and acetic acid
0.5 parts by weight was diluted with water and mixed to make a total of 100 parts by weight. The resulting mixture was stirred for 1 hour at room temperature to prepare a surface treatment agent solution. This surface treatment agent solution was impregnated with glass cloth WEA 18W 105 (manufactured by Nitto Boseki Co., Ltd.), squeezed with a squeeze roller to a pick-up of 28% by weight, and dried at 110 ° C. for 5 minutes. Epoxy resin of FR-4 composition that complies with the following NEMA standards is used as a prepreg, and eight prepregs are laminated and copper foil with a thickness of 18 μm is applied to both sides and heated at 170 ° C for 90 minutes, at 30 Kgf / cm ² Pressurize,
It was a copper clad laminate with a thickness of 1.5 mm.

The specific composition of the epoxy resin (FR-
4) is as follows. Brominated epoxy resin (Epicoat 5046-B-8, manufactured by Yuka Shell Epoxy Co., Ltd.) 100 parts by weight Novolac type epoxy resin (Epicoat 154, manufactured by Yuka Shell Epoxy Co., Ltd.) 20 parts by weight Dicyandiamide 4 parts by weight 2-Ethyl 4-Methylimidazole 0.2 parts by weight Methylethylketone 15 parts by weight Dimethylformamide 30 parts by weight Next, the copper foil is removed from the copper-clad laminate by etching and cut into 4 cm squares. The resin impregnability and solder heat resistance are as follows. I investigated the sex.

Evaluation method (1) Resin impregnating property The impregnating property of the epoxy resin into the glass cloth was visually evaluated. Very good ones were marked with ⊚, good ones with ○, ordinary ones with Δ, and bad ones. Displayed as x.

(2) Solder heat resistance The laminated plate was placed in a pressure cooker set at 133 ° C. and then immersed in a solder melt at 260 ° C. for 20 seconds. After pulling up, the laminate was examined for delamination. The time taken to put the laminated plate in the pressure cooker was 150 minutes. The number of sheets examined was three. The delamination condition is based on the presence or absence of blistering: ◎ for excellent, ○ for good, △ for normal, and × for bad.
Displayed in.

(3) Solubility (water dispersibility) test When the surface treatment solution was prepared, the solubility was observed, and based on the transparency and the dissolution time of the treatment solution, a very good one was marked with ⊚, and a good one was marked with Good, bad things were shown by x, bad things were shown by x. The results of these evaluations are shown in Table 1.

[0032]

[Table 1]

[0033]

When the silane coupling agent of the present invention is used, the glass fiber reinforced epoxy resin molded article produced has excellent solder heat resistance. The silane coupling agent of the present invention has good solubility in water. Therefore, the surface treatment liquid can be manufactured in a short time. Therefore, a printed circuit board requiring soldering heat resistance can be manufactured in a short time.

[Brief description of drawings]

1 is an IR spectrum of the compound of Example 1. FIG. The vertical axis represents the transmittance (%) and the horizontal axis represents the wave number (cm ^-1 ). FIG.
There is no peak at the wavenumber 1280 position, indicating that there is no halide, and there is no peak at the 3450 and 3300 positions, indicating that the amino group is reacting. 32
Broad absorption at positions 00 to 2400 indicates that it is a hydrochloride.

Claims (7)

[Claims] 1. A compound of the general formula (In the formula, R ¹ represents a hydrogen atom, a substituent selected from a methyl group or an ethyl group, m represents an integer of 0 to 3, and n
Represents an integer of 1 to 6 and R ² represents an alkyl group having 1 to 10 carbon atoms), and a silane coupling agent for producing a glass fiber reinforced epoxy resin molded article, which comprises an aminosilane compound or a salt thereof. 2. The silane coupling agent for producing a glass fiber reinforced epoxy resin molded article according to claim 1, wherein R ¹ is a methyl group. 3. A glass fiber reinforced epoxy resin molded article produced by surface-treating glass fiber with the silane coupling agent according to claim 1 and impregnating the resulting surface-treated glass fiber with an epoxy resin for production. Production method. 4. The method according to claim 3, wherein the glass fiber reinforced epoxy resin molded product is a printed circuit board. 5. A surface-treated glass fiber surface-treated with the silane coupling agent according to claim 1. 6. A glass fiber reinforced epoxy resin molded article obtained by impregnating the surface-treated glass fiber according to claim 5 with an epoxy resin. 7. The molded product according to claim 6, wherein the glass fiber reinforced epoxy resin molded product is a printed circuit board.