JP3448902B2 - Silane coupling agent and method for producing silane coupling agent - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silane coupling agent and a method for producing the silane coupling agent.

[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 laminate used for a printed wiring board, high solder heat resistance is especially required, and further improvement in this respect is required. For this reason, efforts have been made to develop silane coupling agents as well as to improve resins.

[0004]

The object of the present invention is to facilitate the surface treatment of glass fiber because of its good water dispersibility.
An object of the present invention is to provide a method for producing a silane coupling agent that imparts excellent solder heat resistance to a glass fiber reinforced epoxy resin laminate.

[0005]

As a result of intensive studies to solve the above problems, the present inventor introduced a structure similar to that of a matrix resin into an alkoxy compound having an amino group, and then added di (hydroxyalkyl) thereto. ) It was found that by adding amine also, a silane coupling agent having excellent solder heat resistance to a glass fiber reinforced epoxy resin laminate and having excellent water dispersibility per se can be obtained, thus completing the present invention. Let

That is, the present invention is represented by the following general formula (I).

[0007]

[Chemical 5]

[However, the above chemical structure A is represented by the following general formula (II),

[0009]

[Chemical 6]

The above chemical structure B is represented by the following general formula (II
I),

[0011]

[Chemical 7]

The above chemical structure C is represented by the following general formula (IV)
Is represented by

[0013]

[Chemical 8]

N in the general formula (II) is an integer of 1 to 3, R ₁ in the general formula (IV) is hydrogen, a methyl group, an ethyl group or a phenyl group,
R ₂ is an alkyl group, an alkyl group having a nitrogen atom,
R ₃ is a methyl group, an ethyl group or a propyl group. ] The first summary of silane compounds,

(1) Di (hydroxyalkyl) amine is subjected to an addition reaction with a compound having two or more epoxy ring structures, and (2) a reaction product having at least one epoxy ring structure produced in the above reaction (1). And an addition reaction of at least one or more alkoxy compound having a primary or secondary amino group

A second aspect of the present invention is a method for producing a silane coupling agent characterized by the above. The present invention will be described in detail below.

The compound of the general formula (I) which is the first gist of the present invention is represented by the compounds of the following general formula (V) shown in the examples.

[0018]

[Chemical 9]

The compound of the general formula (I) is a di (hydroxyalkyl) amine represented by the following general formula (VI) [where n is an integer of 1 to 3] and a bisphenol of the following structural formula (VII). And an alkoxy compound having an amino group of the following general formula (VIII) [wherein R ₁ is hydrogen, methyl group, ethyl group or phenyl group, R ₂ is alkyl group, nitrogen] An alkyl group having atoms, R ₃ is obtained by adding a methyl group, an ethyl group or a propyl group]. Structural formula (V
As the bisphenol type diepoxy monomer of II),
For example, Epicoat 8 manufactured by Yuka Shell Epoxy Co., Ltd.
28 can be given. The compound of the general formula (VIII) undergoes an addition reaction in the following general formula (IX) [wherein n is 1 to 3].
Is an integer] of the reaction product.

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12]

[0023]

[Chemical 13]

Specific examples of the di (hydroxyalkyl) amine represented by the general formula (VI) [where n is an integer of 1 to 3] include dimethanolamine, diethanolamine and di-n-propanolamine. .

The alkoxy compound having an amino group of the general formula (VIII) is, for example, N-β-.
(Aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-
Phenyl-γ-aminopropyltrimethoxysilane, N
-Phenyl-γ-aminopropyltriethoxysilane,
Examples thereof include N-phenyl-β- (aminoethyl) -γ-aminopropyltrimethoxysilane.

The method for producing a silane coupling agent, which is the second aspect of the present invention, is carried out even at room temperature.
It is preferable to react in the temperature range of 0 ° C to 100 ° C. Further, the raw materials may be directly mixed and stirred, but may be carried out in a suitable organic solvent such as 2-methoxyethanol.

The compound having two or more epoxy ring structures used as a raw material in the present invention is, for example, Epicoat 10
01 (produced by Yuka Shell Epoxy Co., Ltd.) and Araldite 8011 (produced by Nippon Ciba Geigy Co., Ltd.).

In the raw materials used in this manufacturing method,
As the di (hydroxyalkyl) amine, the di (hydroxyalkyl) amine represented by the above-mentioned general formula (VI) [where n is an integer of 1 to 3], and the above-mentioned general as the compound having two or more epoxy ring structures A bisphenol diepoxy monomer of the formula (VII), an alkoxy compound having an amino group of the above general formula (VIII) is selected as the alkoxy compound having at least one or more primary or secondary amino groups. It is represented by the following general formula (I) which is the first gist.

[0029]

[Chemical 14]

[However, the above chemical structure A is represented by the following general formula (II),

[0031]

[Chemical 15]

The above chemical structure B is represented by the following general formula (II
I),

[0033]

[Chemical 16]

The above chemical structure C is represented by the following general formula (IV)
Is represented by

[0035]

[Chemical 17]

N in the general formula (II) is an integer of 1 to 3, R ₁ in the general formula (IV) is hydrogen, a methyl group, an ethyl group or a phenyl group,
R ₂ is an alkyl group, an alkyl group having a nitrogen atom,
R ₃ is a methyl group, an ethyl group or a propyl group. ] A silane compound is obtained.

When the silane coupling agent of the present invention is used for surface treatment of glass fiber or the like, it may be diluted with water by adjusting the pH.

[0038]

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 Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. was used as a GPC column Megapak manufactured by JASCO Corporation.
A product having a molecular weight of 340 (Sample A) was collected using GEL201. The preparative conditions are as follows.

A 5% by weight chloroform solution of Epikote 828 was prepared, and this was used as a sample to add chloroform to 3.
Liquid chromatography was performed through the column at a flow rate of 0 ml / min. The equipment used was a TRI R pump.
OTAR-V, UV detector is UVIDEC-100-V
I. The measurement wavelength is 254 nm.

A GPC chart is shown in FIG. The peak of sample A is indicated by an arrow.

1 g of the sample A collected and 2,2'-iminodiethanol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 10 g of 2-methoxyethanol solvent (CH ₃ OC ₂ H ₄ OH) were mixed. The mixture was heated to 80 ° C. and reacted for 6 hours with stirring. The mixing molar ratio of sample A and 2,2'-iminodiethanol is 1: 1.

The reaction product (sample B) obtained in the above reaction was subjected to F
When measured by T-IR (JIR-3510, manufactured by JEOL Ltd.), the amine peaks (1545 cm ⁻¹ and 3275 cm ⁻¹ ) of 2,2′-iminodiethanol disappeared and the reaction was confirmed.

Further, 0.65 g of N-β-aminoethyl-γ-aminopropyltrimethoxysilane (A-1122 manufactured by Nippon Unicar Co., Ltd.) was mixed with this reaction product, heated to 80 ° C. and stirred for 6 hours. While reacting.
The mixing molar ratio of Sample A, 2,2′-iminodiethanol and N-β-aminoethyl-γ-aminopropyltrimethoxysilane was 1: 1: 1.

While heating and proceeding the reaction, the reaction product was taken once an hour, and a part of the reaction product was developed with TLC (Kiesel gel 60 F ₂₅₄ manufactured by Merck Co.) with a benzene solvent, and the sample B disappeared. It was confirmed. Then, the reaction was terminated to obtain a sample C (target compound).

The IR chart of Sample A is shown in FIG.
-The IR chart of iminodiethanol is shown in FIG.
FIG. 4 shows an IR chart of N-β-aminoethyl-γ-
An IR chart of aminopropyltrimethoxysilane is shown in FIG. 5, and an IR chart of sample C is shown in FIG.

The -NH peak (1545c) of the IR chart of 2,2'-iminodiethanol existing in FIG.
m ⁻¹ and 3275 cm ⁻¹ ) have disappeared in the IR chart of sample B in FIG. Similarly, the -NH peak (15 in the IR chart of N-β-aminoethyl-γ-aminopropyltrimethoxysilane present in FIG.
76 cm ⁻¹ ) disappears in the IR chart of sample C in FIG.

Sample C has the above structural formula (V).

[0049]

[Chemical 18]

Example 2 In a 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel, and a thermometer, 450 g of epoxy resin Epicoat 1001 (Yukaka Shell Epoxy Co., Ltd.) (epoxy equivalent 450-500), After charging 815.49 g of 2-methoxyethanol and heating at 80 ° C., 52.57 g (0.5 mol) of 2,2′-iminodiethanol, 105.14 of 2-methoxyethanol.
Gram of the mixed solution was slowly added dropwise, and the mixture was reacted under heating and refluxing at 80 to 85 ° C. for 6 hours to obtain a water-soluble epoxy resin of 35% by weight of 2-methoxyethanol.

Then, in a 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel, and a thermometer,
111.18 grams of N-β-aminoethyl-γ-aminopropyltrimethoxysilane (diaminosilane) (0.
(5 mol), and after heating to 80 ° C., 1423.2 g of a 2-methoxyethanol solution of the above water-soluble epoxy resin is added dropwise, and the mixture is reacted at 80 to 85 ° C. for 6 hours under heating and refluxing to give 60% by weight. A 2-methoxyethanol solution of a water-soluble epoxy resin-diaminosilane compound was obtained.

Example 3 In a 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel and a thermometer, 455 g of epoxy resin Araldite 8011 (Nippon Ciba-Geigy Co., Ltd.) (epoxy equivalent 445-520), 2- 807.99 g of methoxyethanol was charged and after heating at 80 ° C., 52.57 g (0.5 mol) of 2,2′-iminodiethanol, 105.14 of 2-methoxyethanol.
Gram of the mixed solution was slowly added dropwise, and the mixture was reacted under heating and refluxing at 80 to 85 ° C. for 6 hours to obtain a water-soluble epoxy resin of 35% by weight of 2-methoxyethanol.

Then, in a 2 liter separable flask equipped with a condenser, a stirrer, a dropping funnel, and a thermometer,
111.18 grams of N-β-aminoethyl-γ-aminopropyltrimethoxysilane (diaminosilane) (0.
(5 mol), and after heating to 80 ° C., 1423.2 g of a 2-methoxyethanol solution of the above water-soluble epoxy resin is added dropwise, and the mixture is reacted at 80 to 85 ° C. for 6 hours under heating and refluxing to give 60% by weight. A 2-methoxyethanol solution of a water-soluble epoxy resin-diaminosilane compound was obtained.

Example 4 (Measurement of Performance of Silane Coupling Agent of Example 1) A test for measuring the performance of the silane coupling agent of Example 1 was conducted as follows. First, 0.5 parts by weight of acetic acid and 0.4 parts by weight of the sample C of Example 1 were diluted with distilled water to obtain a total of 10 parts.
A glass cloth treatment liquid was prepared so as to be 0 part by weight.
This glass cloth treatment liquid was transparent. Glass cloth WE18W105 (Nitto Boseki Co., Ltd.)
After being impregnated with the product, the product was squeezed with a mangle 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 resin 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 sides, and heated at 170 ° C. for 90 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 has a copper foil of 4 cm
A test piece was cut out in four directions. The solder heat resistance and the water absorption rate of the laminated plate thus prepared were 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 to put the laminated plate in the pressure cooker is 120 minutes, 135 minutes, 1
50 minutes. The number of samples was 3 for each time. The delamination status is shown in Table 1 as "○" means "no blistering", "△" means "one small blistering", and "×".
Means "there are two or more blisters". Here, the "small blisters" are those that are barely visible to the naked eye.

Further, the water absorption of the laminated plate put in the pressure cooker set at 133 ° C. for 135 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 before water absorption) × 100 The results are shown in Table 1.

As a silane coupling agent of the comparative example, SZ-6 from Toray Dow Corning Silicone Co., Ltd.
A glass cloth was treated with a 40% by weight methanol solution of N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride sold as 032. The solder heat resistance was examined. The preparation of the laminated plate including the preparation of the diluting solution for using the silane coupling agent in the glass cloth treatment and the measurement operation of the solder heat resistance were performed in the same manner as the sample C of Example 1. The results are shown in Table 1 as Comparative Example 1 together with Example 1.

[0060]

[Table 1]

As can be seen from Table 1, the silane coupling agent prepared by the method of the present invention is N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxy known as cationic silane. Compared with silane hydrochloride, it is possible to give the laminated board excellent solder heat resistance.

Example 5 (Measurement of Performance of Silane Coupling Agents of Examples 2 to 3) The silane coupling agents of Examples 2 and 3 were each added with p.
It was dissolved in distilled water adjusted to H4 to prepare a 0.7% by weight glass cloth treatment liquid. This glass cloth treatment liquid was transparent. Glass cloth WEA-18 was added to this treatment liquid.
After being impregnated with W (manufactured by Nitto Boseki Co., Ltd.), it was squeezed with a squeeze roll to squeeze the pick-up to 28% by weight, and then at 110 ° C.
Dry for minutes.

The dried treated glass cloth was treated with the following N
It was impregnated with an epoxy resin 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 sides, 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 has a copper foil of 4 cm
A test piece was cut out in four directions. The solder heat resistance and the water absorption rate of the laminated plate thus prepared were 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 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 before water absorption) × 100 The results are shown in Table 2.

As a silane coupling agent of the comparative example, SZ-6 from Toray Dow Corning Silicone Co., Ltd.
A glass cloth was treated with a 40% by weight methanol solution of N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride sold as 032. The solder heat resistance was examined. Preparation of a laminated plate including preparation of a diluting solution for using a silane coupling agent for glass cloth treatment and operation for measuring solder heat resistance were performed in the same manner as in Examples 2 and 3. The results are shown in Table 2 as Comparative Example 2 together with Examples 2 and 3.

[0068]

[Table 2]

As is apparent from Table 2, the silane coupling agent prepared by the method of the present invention is the N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxy known as cationic silane. Compared with silane hydrochloride, it is possible to give the laminated board excellent solder heat resistance.

[0070]

The silane coupling agent obtained according to the present invention described above has high water dispersibility, and when the glass fiber is treated therewith, the obtained glass fiber reinforced resin has excellent solder heat resistance. Can be given. 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 is a GPC chart of the epoxy monomer of Example 1.

FIG. 2 is an IR chart of the epoxy monomer of Example 1.

FIG. 3 is an IR chart of 2,2′-iminodiethanol.

FIG. 4 is an IR chart of Sample B which is a reaction product of the epoxy monomer of Example 1 and 2,2′-iminodiethanol.

FIG. 5: N-β- (N-vinylbenzylaminoethyl)
IR of -γ-aminopropyltrimethoxysilane hydrochloride
chart.

FIG. 6 is an IR chart of sample B which is a reaction product of sample B and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride.

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (I): [However, the above chemical structure A is represented by the following general formula (II): The above chemical structure B is represented by the following general formula (III): The above chemical structure C is represented by the following general formula (IV): N in the general formula (II) is an integer of 1 to 3, the general formula (I
R ₁ in V) is hydrogen, a methyl group, an ethyl group or a phenyl group, R ₂ is an alkyl group, an alkyl group having a nitrogen atom,
R ₃ is a methyl group, an ethyl group or a propyl group. ] Silane compounds. 2. A reaction having (1) di (hydroxyalkyl) amine and a compound having two or more epoxy ring structures, and (2) a reaction having at least one epoxy ring structure produced in the reaction of the above (1). A method for producing a silane coupling agent, which comprises subjecting a product to an addition reaction of an alkoxy compound having at least one primary or secondary amino group.