JPH06172369A - Silane coupling agent and its production - Google Patents

Abstract

PURPOSE:To produce a compound excellent in heat resistance, water absorption and adhesivity and useful for a glass fiber-reinforced epoxy resin laminate, etc., without generation of a by product by blending a specified compound with benzylamine, etc., and allowing an addition reaction to take place. CONSTITUTION:A compound of formula I (R4 is methylene, ethylene or trimethylene; R5 is methyl, ethyl, n-propyl or i-propyl) is blended with benzylamine or aniline and an addition reaction is allowed to take place, thus producing the objective compound of formula II (R1 is a covalent bond or methylene; R2 is R4; R3 is R5).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organosilicon compound used for enhancing the adhesion between a polymeric material such as resin and an inorganic reinforcing material such as glass fiber, that is, a so-called silane coupling agent and a method for producing the same.

[0002]

2. Description of the Related Art Glass fibers used in the production of glass fiber reinforced resin laminates are generally surface-treated with a silane coupling agent, and especially in the production of laminates with epoxy resin, 3-aminopropyltriethoxysilane, A silane coupling agent such as 3-glycidoxypropyltrimethoxysilane or 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride is used.

In the case of a glass fiber reinforced epoxy resin laminated board used for a printed wiring board, both high heat resistance and low water absorption are required, and in order to meet these requirements, up to now, a silane compound has been used together with the improvement of the epoxy resin. Efforts have been made to develop silane coupling agents so as to obtain the above-mentioned desired properties by introducing an aryl group, particularly a benzene ring.

When synthesizing the silane coupling agent having an aryl group, a silane compound having an aminoalkyl group or a haloalkyl group is used as a reaction starting material, and an aryl group is added thereto by an acid-base reaction. .

It is well known that by using a silane coupling agent in which an aryl group is added to a silane compound, the heat resistance and water absorption characteristics of the glass fiber reinforced epoxy resin laminate can be improved to suit the purpose. However, in the above-mentioned acid-base reaction, the product becomes a mixture of a secondary amine compound and a tertiary amine compound, and a pure product of only the secondary amine compound or the tertiary amine compound is obtained. In addition, it is difficult to purify only one of them with high purity. The fact that it can only be obtained as this mixture destabilizes the performance of the silane coupling agent, leaving a problem in the heat resistance and water absorption characteristics of the glass fiber reinforced epoxy resin laminate.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to produce a silane coupling agent that imparts excellent heat resistance and water absorption characteristics to a glass fiber reinforced epoxy resin laminate and a silane coupling agent that does not show by-products. To provide a method.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventor has found that an aryl group can be easily converted to an aryl group by addition reaction of benzylamine or aniline with an isocyanate type silane compound. It was found that a silane coupling agent having a substituent and imparting excellent heat resistance and water absorption characteristics to a glass fiber reinforced epoxy resin laminate can be obtained without by-products, and the present invention was completed.

That is, the present invention provides the following general formula (I):

[Chemical 3] (In the formula, R1 is a covalent bond or a methylene group [=-
CH2--, R2 is a methylene group, an ethylene group [=-
(CH2) 2-] or trimethylene group [=-(CH2
) 3-], and R3 is a methyl group [= -CH3], an ethyl group [= -CH2CH3], an n-propyl group [=-
(CH2) 2 CH3] or i-propyl group [= -C
H (CH3) 2] is shown. ) Is a compound represented by the first gist,

The following general formula (II):

[Chemical 4] (Wherein R4 represents a methylene group, an ethylene group or a trimethylene group, and R5 represents a methyl group, an ethyl group, an n-propyl group or an i-propyl group) and benzylamine or aniline. The second gist is a method for producing the above compound obtained by an addition reaction.

The present invention will be described in detail below.

As described above, the silane coupling agent of the present invention can be obtained simply by stirring and mixing the triacylsilane compound having an isocyanate group and benzylamine or aniline in a suitable container.

The reaction proceeds even at room temperature, but at 50 ° C to 1
It is preferable to react in the temperature range of 00 ° C. Also,
The raw materials may be directly mixed and stirred, but may be carried out in an appropriate organic solvent such as dimethylformamide or 1,2-dimethoxyethane. Mixing of the raw materials is preferably carried out by dropping benzylamine or aniline into the triacylsilane compound having an isocyanate group little by little while paying attention to excessive heat generation.

If the compound of the general formula (II) and benzylamine or aniline are charged in equimolar amounts, the silane coupling agent of the present invention of the general formula (I) can be obtained without by-products. When one of the raw materials is excessive, the excess raw material remains after the reaction, and a mixture of the silane coupling agent of the present invention and the excess raw material is obtained. By-products are not synthesized.

The obtained silane coupling agent of the present invention of the general formula (I) is a solution of methanol, ethanol, n-propanol and i-propanol in a suitable concentration of an appropriate alcohol corresponding to the alkoxy group. Then it is convenient for storage. When used for the surface treatment of glass fiber or the like, the alcohol solution may be diluted with water by further adjusting the pH.

[0015]

The present invention will be described in more detail with reference to the following examples. Of course, the present invention is not limited to the description below.

Example 1 A 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel, and a thermometer has a structural formula of OCN (CH
2) 3 Si (OC2 H5) 3 isocyanate silane (Y-9030; manufactured by Nippon Unicar Co., Ltd.) was charged in an amount of 247 g (1.0 mol), heated to 50 ° C., and then added with benzylamine from a dropping funnel. Was slowly added dropwise to the final weight of 107 g (1.0 mol), and 5
The reaction was carried out at 0-60 ° C. for 2 hours under heating under reflux to obtain a highly crystalline product. After the reaction was completed, 531 g of ethanol was poured into the flask to prepare a 40% by weight diluted solution. The diluted solution was developed by TLC (thin layer chromatography) to confirm the disappearance of benzylamine. Kieselgel 60F254 manufactured by Merck was used as the TLC plate, and benzene was used as the developing solvent.

FIG. 1 shows an IR chart of a sample obtained by removing ethanol from the above ethanol solution under reduced pressure. The model of FT-IR used is JIR-35, JEOL Ltd.
It is 10. In addition, the IR chart of isocyanate silane is shown in FIG. 2, and the IR chart of benzylamine is shown in FIG.
Shown in.

FIG. 1 shows the presence of secondary amines from the wave number 3350 peak and the presence of amide bonds from the wave number 1630 peak. Similarly, in FIG. 1, the peak of the isocyanate group having the wave number 2240 existing in FIG. 2 and the peak of the primary amines having the wave numbers 3400, 3300, 1620, and 900 existing in FIG. 3 disappear.

Reference Example 1 A 40% by weight ethanol solution of benzylureylenepropyltriethoxysilane obtained in Example 1 above was used to prepare a laminate having the following formulation, and its laminate characteristics were measured. The measurement results are shown in Table 1 below.

The test for measuring the performance was conducted as follows. First, a 40% by weight ethanol solution of the above benzylureylenepropyltriethoxysilane was diluted 50 times with water, and the pH was adjusted to 3 with acetic acid to prepare a glass cloth treatment liquid. Glass cloth WEA-18 was added to this treatment liquid.
After impregnating with W (manufactured by Nitto Boseki Co., Ltd.), it was squeezed with a squeeze roll so that the pickup was 28% by weight, and dried at 110 ° C. for 5 minutes.

The dried treated glass cloth was treated with the following N
It was impregnated with an epoxy varnish of FR-4 composition conforming to the EMA standard and dried at 130 ° C for 6 minutes to obtain a prepreg.
Eight prepregs were laminated, copper foil having a thickness of 18 μm was applied to both surfaces, and heated at 170 ° C. for 60 minutes under a load of 30 kgf / cm 2 to prepare a copper clad laminate having a thickness of 1.5 mm. The copper clad laminate was removed by etching to remove the copper foil, and 4c.
A test piece was cut out into m squares. The solder heat resistance of the laminated plate thus prepared was measured.

Specific composition of 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 Methyl ethyl ketone 15 parts by weight Dimethylformamide 30 parts by weight

The solder heat resistance was measured as follows. The test piece of the laminated plate was put 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 (delamination). In addition, the time for putting the laminated plate in the pressure cooker is 90 minutes, 105 minutes, 12
It was set to 0 minutes. The number of samples was 3 for each time. Regarding the delamination state, in Table 1, "○" means "no blister", "△" means "one small blister", and "x" means "two or more blisters". Here, the "small blisters" are those that are barely visible to the naked eye.

Comparative Reference Examples 1-3 Epoxysilane (A18 as a silane coupling agent
7; Nippon Unicar Co., Ltd.) [= Comparative Reference Example 1], aminosilane (A1100; Nippon Unicar Co., Ltd.) [= Comparative Reference Example 2] and Weed Silane (A1160; Nippon Unicar Co., Ltd.) [= Comparative Reference Example 3] was used to treat a glass cloth to prepare an epoxy resin laminate, and its solder heat resistance was examined. The results are shown in Table 1 together with Reference Example 1.

The above-mentioned glass cloth treatment liquids of the three types of silane coupling agents were prepared as follows. Distilled water was previously adjusted to pH 4 with acetic acid and diluted with this to prepare a glass cloth treatment liquid in which the solid content of the silane coupling agent was 0.5% by weight for each of epoxysilane, aminosilane, and weed silane. Other operations were carried out in the same manner as in Reference Example 1, whether the surface treatment of the glass cloth, the production of the laminated plate, or the measurement of solder heat resistance.

[0026]

[Table 1]

[0027]

The silane coupling agent of the present invention described above can impart excellent heat resistance to the obtained glass fiber reinforced resin when the glass fiber is treated therewith. Further, the above-mentioned silane coupling agent can be easily obtained without by-products by the production method of the present invention.

[Brief description of drawings]

FIG. 1 is an IR of the silane coupling agent of the present invention.
It is a chart.

FIG. 2 is an IR chart of isocyanate silane.

FIG. 3 is an IR chart of benzylamine.

Claims (2)

[Claims] 1. The following general formula (I), namely: (In the formula, R1 is a covalent bond or a methylene group [=-
CH2--, R2 is a methylene group, an ethylene group [=-
(CH2) 2-] or trimethylene group [=-(CH2
) 3-], and R3 is a methyl group [= -CH3], an ethyl group [= -CH2CH3], an n-propyl group [=-
(CH2) 2 CH3] or i-propyl group [= -C
H (CH3) 2] is shown. ) The compound represented by. 2. The following general formula (II), namely: (Wherein R4 represents a methylene group, an ethylene group or a trimethylene group, and R5 represents a methyl group, an ethyl group, an n-propyl group or an i-propyl group) and benzylamine or aniline. The method for producing the compound according to claim 1, wherein the compound is subjected to an addition reaction.