JPH0733785A - Silane coupling agent and method for producing the same - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] To provide a silane coupling agent that imparts excellent solder heat resistance to a glass fiber reinforced epoxy resin laminate and a method for producing the same. [Structure] The following general formula obtained by the addition reaction of hydroxybenzylamine or hydroxyaniline with a silane compound having a halogen functional group or a glycidyl group (However, in the formula, R ₁ is —NH—, —CH ₂ —NH—, —
_{NH-CH 2 -CH (OH)} -CH 2 -O -, - CH 2
_{-NH-CH 2 -CH (OH)} -CH 2 -O- are shown,
R ₂ is a methyl group [= -CH ₃ ] or an ethyl group [= -CH ₂ ].
CH _3], n-propyl group _{[= - (CH 2) 2} CH 3]
Or i- propyl indicates _{[= -CH (CH 3) 2} ], n represents 1, 2 or 3. The manufacturing method of the silane coupling agent represented by these.

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 in the production of laminates with epoxy resins, especially γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β- (N-
A silane coupling agent such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride is used.

In the case of glass fiber reinforced epoxy resin laminates used for printed wiring boards, high soldering heat resistance is especially required, and in order to meet this requirement, up to now, along with improvement of epoxy resins, aryl groups have been added to silane compounds. In particular, efforts have been made to develop silane coupling agents so that the above-mentioned desired properties can be obtained by introducing a benzene ring.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silane coupling agent which imparts excellent solder heat resistance to a glass fiber reinforced epoxy resin laminate and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a silane compound having a halogen functional group or a glycidyl group is subjected to an addition reaction with hydroxybenzylamine or hydroxyaniline. As a result, it was found that a silane coupling agent which gives excellent solder heat resistance to a glass fiber reinforced epoxy resin laminate can be easily obtained, and the present invention has been completed.

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

[Chemical 5] (In the formula, R ₁ is —NH—, —CH ₂ —NH—, —
_{NH-CH 2 -CH (OH)} -CH 2 -O -, - CH 2
_{-NH-CH 2 -CH (OH)} -CH 2 -O- are shown,
R ₂ is a methyl group [= -CH _3], ethyl [= -C
H ₂ CH _3], n- propyl group _{[= - (CH 2) 2} C
H _3] or i- propyl group [= -CH (C
H ₃ ) ₂ ] and n is 1, 2 or 3. ) And a compound represented by

The following general formula (II) or (III)

[Chemical 6] (In the formula, X represents F, Cl, Br or I, R ₂ represents a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and n represents 1, 2 or 3.)

[0008]

[Chemical 7] (In the formula, R ₂ represents a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and n represents 1, 2 or 3.)

A compound represented by the following formula (IV)
I.e.

[Chemical 8] The gist is a method for producing a compound of the general formula (I) by mixing with a compound represented by (m represents 0 or 1) and carrying out an addition reaction. The present invention will be described in detail below.

As described above, a silane coupling agent which is a compound of the present invention can be obtained simply by stirring and mixing a silane compound having a halogen functional group or a glycidyl group and hydroxybenzylamine or hydroxyaniline in a suitable container. You can

The reaction is preferably carried out in the temperature range of 60 ° C to 140 ° C. Further, the raw materials may be directly mixed and stirred, but may be carried out in an appropriate organic solvent depending on the kind of the functional group of the silane compound. Mixing the raw materials
It is preferable to employ a method in which the silane compound is added dropwise to hydroxybenzylamine or hydroxyaniline little by little while paying attention to excessive heat generation.

The obtained silane coupling agent of the present invention of the general formula (I) is convenient for storage if it is prepared as a solution of alcohol such as methanol, ethanol, n-propanol and i-propanol in an appropriate concentration. 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.

[0013]

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 30 equipped with a condenser, a stirrer, a dropping funnel and a thermometer
42 ml of m-aminophenol (molecular weight 109.13; melting point 122 ° C.) was placed in a 0 ml separable flask.
54 grams (0.39 moles) of ethanol 42.54
After the gram was charged, this was heated to 80 ° C. to completely dissolve m-aminophenol, and finally 77.46 g (0.39) of γ-chloropropyltrimethoxysilane (molecular weight 198.72) was added from a dropping funnel. Mol), and the mixture is reacted by heating under reflux at 80 to 85 ° C. for 6 hours to give m-hydroxyphenylimino-n-propyltrimethoxysilane hydrochloride (molecular weight: 307.85).
) Got. After completion of the reaction, add 13 ethanol to the flask.
7.46 grams was poured to prepare a 40% by weight diluent.
The diluted solution was developed by TLC (thin layer chromatography) to confirm the addition of m-aminophenol. In addition, T
LC plate is Kieselgel 60 manufactured by Merck
F ₂₅₄ was used and ethanol was used as a developing solvent.

FIG. 1 shows the reaction product of Example 1, and FIG. 2 shows m.
-Aminophenol, and Fig. 3 shows an IR chart of γ-chloropropyltrimethoxysilane. In the IR chart of the reaction product of FIG. 1, a peak of 1490.7 nm showing the presence of the aromatic secondary amine appears.

Example 2 30 equipped with a condenser, a stirrer, a dropping funnel, and a thermometer
M-Aminophenol (molecular weight 109.13; melting point 122 ° C.) 37.
93 grams (0.35 mol), ethanol 37.93
After the gram was charged and heated to 80 ° C. to completely dissolve m-aminophenol, γ-glycidoxypropyltrimethoxysilane (molecular weight 236.
1) was slowly added dropwise so that the final weight was 82.07 g (0.35 mol), and the mixture was reacted under heating under reflux at 80 to 85 ° C. for 6 hours. After the reaction was completed, 142.07 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 addition of m-aminophenol. The molecular weight of the reaction product was 345.23. The TLC plate is a Kieselge manufactured by Merck.
160F ₂₅₄ was used, and ethanol was used as a developing solvent.

FIG. 4 shows the reaction product of Example 2, and FIG.
-Shows an IR chart of glycidoxypropyltrimethoxysilane. In the IR chart of the reaction product of FIG. 4, it is shown that the presence of aromatic secondary amine is 1500.4 nm.
Peak has appeared. On the other hand, in the IR chart of FIG. 4, C of the epoxy ring structure seen in the IR chart of γ-glycidoxypropyltrimethoxysilane in FIG.
The peak at 1255.4 nm, which indicates the presence of a stretch bond between —O, does not appear.

Reference Examples 1 and 2 Silane Coupling Agent 4 of Examples 1 and 2 above
A laminated plate was prepared with the following formulation using a 0 wt% ethanol solution, and its laminating characteristics were measured. The measurement results are shown in Table 1 below.

The test for measuring the performance was conducted as follows. First, the 40 wt% ethanol solution of the silane coupling agent of Examples 1 and 2 above was diluted with distilled water whose pH was adjusted to 3 with acetic acid to prepare a glass cloth treatment liquid having a solid content of 0.7 wt%. . This treatment liquid was impregnated with glass cloth WEA-18W (manufactured by Nitto Boseki Co., Ltd.), squeezed with a squeeze roll so that the pickup would be 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 175 ° C. for 60 minutes under a load of 30 kgf / cm ² to prepare a copper clad laminate. The copper clad laminate was removed from the copper foil by etching, and cut into 4 cm squares to give test pieces. About the laminated board created in this way,
Solder heat resistance 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.

Further, the water absorption rate of the laminated plate put in the pressure cooker set at 133 ° C. for 105 minutes was also measured. The water absorption rate was calculated by the following formula. Water absorption rate (%) = {(weight after water absorption)-(weight before water absorption)} / (weight after water absorption) × 100

Comparative Reference Examples 1 to 3 γ-aminopropyltriethoxysilane [= Comparative Reference Example 1], γ-glycidoxypropyltriethoxysilane [= Comparative Reference Example 2] and N as silane coupling agents.
A glass cloth was treated with -β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride [= Comparative Reference Example 3] to prepare an epoxy resin laminate, and its solder heat resistance was evaluated. Examined. The results are shown in Table 1 together with the reference example.

The above-mentioned glass cloth treatment liquids of the three types of silane coupling agents were prepared as follows. Preliminarily distilled water with acetic acid, pH 4 for N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, pH 3 for other silanes.
And the solid content of the silane coupling agent is 0.7% by weight for N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride by diluting with With respect to the silane, a 0.4% by weight glass cloth treatment liquid was prepared. Other operations are surface treatment of glass cloth, creation of laminated board,
The solder heat resistance and the water absorption were measured in the same manner as in the reference example.

[0026]

[Table 1]

[0027]

The silane coupling agent of the present invention described above can impart excellent solder 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 by the production method of the present invention.

[Brief description of drawings]

FIG. 1 shows m-aminophenol obtained in Example 1 and γ.
3 is an IR chart of a reaction product with -chloropropyltrimethoxysilane.

FIG. 2 is an IR chart of m-aminophenol.

FIG. 3 IR of γ-chloropropyltrimethoxysilane
It is a chart.

FIG. 4 shows m-aminophenol and γ obtained in Example 2.
-IR chart of the reaction product with glycidoxypropyltrimethoxysilane.

FIG. 5 is an IR chart of γ-glycidoxypropyltrimethoxysilane.

Claims (2)

[Claims] 1. The following general formula (I), namely: (In the formula, R ₁ is —NH—, —CH ₂ —NH—, —NH—CH ₂ —CH (OH) —CH ₂ —O—, —CH ₂ —NH—CH ₂ —CH (OH) — CH ₂ -O-
Are shown, R ₂ is a methyl group [= -CH _3], ethyl [= -C
H ₂ CH _3], n- propyl group _{[= - (CH 2) 2} CH 3] or i
- propyl indicates _{[= -CH (CH 3) 2} ], n represents 1, 2 or 3. ) The compound represented by. 2. The following general formula (II) or (III):
That is, (In the formula, X is F, Cl, Br or I, and R ₂ is a methyl group, an ethyl group, an n-propyl group or i-
A propyl group is shown, and n is 1, 2 or 3. ) [Chemical 3] (Wherein R ₂ represents a methyl group, an ethyl group, an n-propyl group or an i-propyl group, and n represents 1, 2 or 3) and a compound represented by the following general formula (IV): [Chemical 4] The method for producing the compound according to claim 1, wherein the compound represented by (m represents 0 or 1) is mixed and an addition reaction is carried out.