JPH07258415A - Silane composition - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a novel silane coupling agent for producing a glass fiber product, and to provide a laminate excellent in heat resistance without causing measling, which is treated with the silane coupling agent. Provided is a glass fiber product capable of producing a board. [Structure] A silane coupling agent having at least two amino groups has a phenyl group-containing group bonded to the terminal nitrogen atom, and a styryl group-containing nitrogen atom other than the terminal nitrogen atom. A novel silane coupling agent having a bonded silane, a glass fiber product treated with the silane coupling agent, and a glass fiber reinforced resin laminate using the glass fiber product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a silane coupling agent composition used as a coupling agent between an inorganic support and an organic polymer compound. More specifically, the present invention provides an organosilicon compound having a specific functional group capable of significantly improving the adhesion of a certain resin to a siliceous surface, particularly a glass surface, and imparting a high stress relaxation ability to the adhesive interface. The present invention relates to a silane coupling agent composition as a main component and a glass fiber product treated with the silane coupling agent composition.

[0002]

2. Description of the Related Art In recent years, a wide variety of silane coupling agents have been developed and widely used in order to improve the miscibility and adhesiveness between an inorganic material and an organic polymer compound. The silane coupling agent usually contains an organic chain portion for providing an affinity and a binding property with an organic polymer compound and, when treated on the surface of the inorganic material, between the silicon and the inorganic material via an oxygen atom. And a part having a hydroxyl group or an alkoxy group for forming a chemical bond. By the way, in a composite material of an inorganic filler or an inorganic fiber material and an organic polymer compound, in particular, a thermosetting resin such as an epoxy resin or a polyimide resin, the function of the coupling agent plays an important role in manifesting its physical properties. Known to fulfill. When a mechanical shock is applied to this composite material from the outside, the mechanical stress concentrates on the interface with different elastic modulus.
If the adhesive force at the interface is not sufficient or if the stress relaxation ability of the interface is not sufficient, then the interface will be destroyed. Also, when a thermal shock is applied, the material expands and contracts, but the thermal stress due to the difference in the expansion coefficient between the base material and the resin concentrates on the interface, so that the adhesive force at the interface is not sufficient or the stress relaxation capability of the interface. If not enough, the interface is broken. Therefore, if the interface has a high adhesive force and the interface has a high stress relaxation ability, it is possible to prevent such breakage or increase the critical stress and the critical strain.

In recent years, many printed boards using a glass fabric as a strengthening agent and a thermosetting resin as a matrix resin have a high density packaging and a thin multilayer structure. In these substrates, a measling defect is a problem. The measling here is also called crazing, and is a phenomenon that occurs remarkably at the intersection of the weaving of glass woven fabric, and in the manufacturing process of the printed circuit board, the thermal shock and mechanical shock more severe than before This is a phenomenon in which peeling occurs at the interface due to insufficient adhesion at the interface between the glass woven fabric and the resin or insufficient stress relaxation capability due to exposure. Conventionally, silane coupling agents used for thermosetting resins such as epoxy resins and polyimide resins have a linear structure such as Formula III, Formula IV, and Formula V.

[0004]

[Chemical 3]

A silane coupling agent represented by the following formula is known. However, when a glass fabric is treated with these silane coupling agents and a printed circuit board is made with an epoxy resin, a polyimide resin, etc., according to the experiments of the present inventors, results that are sufficiently satisfactory in terms of measling resistance are obtained. Was not obtained. In other words, the performance of these existing silane coupling agents is not sufficient to meet the high level of physical properties required for glass fiber reinforced resins in recent years. I can't.

[0006]

Under the above circumstances, the present invention remarkably improves the adhesiveness of thermosetting resins such as epoxy resins and polyimide resins to silicate surfaces, especially glass surfaces, Further, the present invention has been made for the purpose of providing a silane coupling composition having excellent characteristics capable of imparting a high stress relaxation ability to an adhesive surface. The present invention also provides a glass fiber product such as a glass woven fabric which is treated with the silane coupling agent composition and is useful as a reinforcing material for a printed circuit board having more excellent resistance to measling.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to develop a silane coupling agent composition having the above-mentioned excellent characteristics, and as a result, are represented by the formula II in the general formula I. The present inventors have found that a composition containing a group and having a bulky organic chain portion as a main component of a polyfunctionalized organosilicon compound can meet the purpose, and completed the present invention. . That is, the present invention provides (a) the general formula I

[0008]

[Chemical 4]

[Wherein Q _n is the formula II

[0010]

[Chemical 5]

A group represented by or hydrogen, k =
When 1 is a group represented by the formula II, when k = 2, at least one is a group represented by the formula II. Also, k is 1
Or 2. In the formula, R ¹ , R ² and R ⁶ are divalent aliphatic hydrocarbon groups having 6 or less carbon atoms, and R ³ has 1 carbon atom.
0 or less divalent aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic ring,, R ⁴ is an alkyl or cycloalkyl group or a phenyl group, the following six carbon number, R ⁵ Is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, and a is 0 or 1. ] The silane coupling agent composition which consists of the silane compound represented by these, or its acid salt, and the water-soluble organic solvent which can melt | dissolve (ii) and (ii), and the glass fiber processed with the said silane coupling agent composition. The gist of the present invention is a product and a glass fiber reinforced resin laminated plate having the glass fiber product as a reinforcing material. Hereinafter, the present invention will be described in detail.

The main component of the silane compound in the silane composition of the present invention is represented by the general formula I

[0013]

[Chemical 6]

An aminosilane represented by the formula [Q _n , R ^{1 to} R ⁵ , and a and k have the same meanings as described above].
A phenyl group at one end, R ¹ bonded to nitrogen at the other end and R ² bonded to a nitrogen atom at both ends are divalent aliphatic hydrocarbon groups having 6 or less carbon atoms. The number of carbon atoms of R ¹ and R ² may be 7 or more, but it is convenient to treat the final compound on the surface of the inorganic material in an aqueous solution state,
From the necessity of having solubility in water, an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl and isopropyl is preferable. For the same reason, the number of carbon atoms of R ³ , which is a divalent aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic ring, which is directly bonded to a silicon atom and bonded to a nitrogen atom at the other end, is 10 or less. desirable.
Examples of R ³ are methylene, ethylene, propylene,
Alkylene groups such as butylene and hexylene, phenylene groups,

[0015]

[Chemical 7]

And the like.

R ⁴ is an alkyl group having 6 or less carbon atoms or a cycloalkyl group, or a phenyl group, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and isopropyl, and cyclobutyl. , Cycloalkyl groups such as cyclohexyl,
And phenyl groups, etc., but having a large number of carbons adversely affects the adhesion between the silane compound and the surface of the inorganic material.
Preferred are methyl and ethyl groups. R ⁵ is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, for example methoxy, ethoxy,
An alkoxy group such as propoxy, isopropoxy, butoxy, t-butoxy, 2-methoxyepoxy, and 2-methoxypropoxy, and an aryloxy group such as phenoxy and naphthoxy are preferable because of their good hydrolyzability. It is 1 to 4 lower alkoxy groups.

Formula II

[0019]

[Chemical 8]

The vinyl group in the group represented by may be in the ortho position, the meta position or the para position. One or more groups represented by the general formula II must be contained in the molecule in order to firmly adhere to the matrix resin and to impart the stress relaxation ability at the interface between the matrix resin and the glass. R ⁶ is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms. It is possible to set the carbon number to 7 or more, but it is convenient to process the final compound on the surface of the inorganic material in the state of an aqueous solution, and it is 6 or less from the necessity of having solubility in water. desirable. k is 1 or 2. If the number of k is excessively increased, the solubility of the compound in water remarkably decreases, which is not preferable.

The solvent used in the silane composition of the present invention is not particularly limited as long as it dissolves the silane compound of the reaction product and is a water-soluble solvent, but the silane compound is produced. What can dissolve each of the raw materials used in the preparation is convenient and desirable for preparing the composition. Examples of such a water-soluble solvent include alcohols such as methanol, ethanol and propanol, diethyl ether, 1,4-dioxane, 1,3-dioxane, tetrahydrofuran, ethers such as ethylene glycol monomethyl ether, acetone and methyl ethyl ketone. Such as ketones. These solvents may be used alone or in combination of two or more. The content of the solvent in the composition is not particularly limited as long as it is an amount sufficient to dissolve the silane compound as the reaction product.

An example of the method for producing the silane coupling agent composition of the present invention is shown below. Aminosilane compound such as N-β- (N-benzylaminoethyl) -γ-aminopropyltrimethoxysilane and halogen-containing styryl in a suitable solvent such as at least one solvent selected from the above solvents. The desired product can be obtained by reacting a derivative, for example, vinylbenzyl chloride, preferably under an atmosphere of an inert gas such as argon or nitrogen under reflux at 40 ° C to 120 ° C under normal pressure. The composition of the present invention contains, as a main component, the compound represented by the general formula I or an acid salt thereof, and the following compound which is conveniently used in the production of the composition.

[0023]

[Chemical 9]

(Wherein R ¹ , R ² , R ³ , R ⁴ , a and k have the same meanings as described above) may be included.

In order to prevent the vinyl group from being polymerized when the silane coupling agent composition of the present invention is stored, a polymerization inhibitor such as p-benzoquinone, t-butylcatechol, nitrobenzene or the like is contained in an amount of 1% or less by weight. It is also possible to add. As a method of treating a glass fiber product with the silane coupling agent composition of the present invention, a conventionally known dipping method, spraying method or the like can be applied. As a glass fiber product to which the silane coupling agent composition of the present invention can be applied, glass filaments obtained by spinning conventionally known alkali glass, non-alkali glass, low dielectric glass, high elasticity glass, E glass for electrical use, etc. are bundled. Glass thread,
Examples of the cloth include glass cloth woven with glass thread, glass tape, non-woven glass mat, and glass paper. In addition, the glass fiber product treated with the silane coupling agent composition of the present invention is particularly preferably used as a reinforcing agent for a resin laminated board for a printed circuit board.

[0026]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, each physical property was calculated | required as follows.

(1) Impregnation of Resin The prepreg was observed visually and by an optical microscope to judge whether the impregnation of the resin was good or bad. ◎: Very good ○: Good Δ: Normal ×: Poor (2) Solder heat resistance after boiling According to JIS-C-6481 solder heat resistance, a pressure cooker (PCT) at 120 ° C for 3 hours,
After moist heat treatment for 3.5 hours and 4 hours, the presence or absence of floating blisters was examined in a solder bath at 260 ° C. for 1 minute. ◎: No blisters ○: Slight spots blisters △: Spots blisters ×: Overall blisters (3) Measling property after boiling water treatment After boiling water treatment for 2 hours, 3 hours, 4 hours It was immersed in a solder bath at 260 ° C. for 20 seconds and examined for the occurrence of measling. ◎: No occurrence ○: Slightly spot-like generation △: Spot-like generation ×: Overall generation (4) Potentiometric titration Toa Denpa Kogyo HM-5A PH meter,
The hydrolyzable chlorine ion was titrated with a sodium methylate solution in methanol. Titration was performed at room temperature. (5) NMR The measurement was performed using the NMR spectrometer of JNM-PMX60SI of JEOL Ltd. (6) IR Measurement was performed using an infrared spectroscope of FTIR-4100 manufactured by Shimadzu Corporation.

Example 1 300 g of a 40% silane methanol solution of N-β- (N-benzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride was stirred at room temperature while stirring sodium methylate 28% methanol. After adding 66.5 g of the solution and allowing it to stand at room temperature for a whole day and night, the precipitate was removed by filtration. After adding 40.7 g of vinylbenzyl chloride to 267 g of the silane solution, the mixture was reacted at 40 ° C. for 5 hours under reflux. After completion of the reaction, the reaction product was developed by thin layer chromatography (TLC) to confirm that the addition of vinylbenzyl chloride was carried out, and then the chloride ion generated during the reaction was quantified by potentiometric titration.
Since 90% or more of benzyl chloride had reacted,
H-NMR spectrum analysis of the obtained reaction composition, IR
Spectral analysis is performed

[0029]

[Chemical 10]

It was confirmed that

Next, the silane compound of the reaction composition of 0.
A 5% by weight aqueous solution was prepared, and acetic acid was added to these to obtain PH4.
Was adjusted to (treatment liquid). Thickness of this processing liquid is 0.19 mm
The glass cloth (7628, manufactured by Asahi Shabel Co., Ltd.) was immersed in the glass cloth, and then the liquid was removed so that the treatment liquid retention rate was about 30% by weight with respect to the glass cloth, followed by drying with hot air at 120 ° C. Also, brominated bisphenol A type epoxy resin DER514 [manufactured by Dow Chemical Japan Co., Ltd.] 85 parts by weight (solid), cresol novolac type epoxy resin N
690 [Dainippon Chemical Industry Co., Ltd.] 15 parts by weight (solid), N, N′-dimethylformamide 10 parts by weight, methoxyethanol 10 parts by weight, dicyanamide 2.4 parts by weight, 2-ethyl-4-methylimidazole. An epoxy varnish was prepared by blending 0.2 part by weight. The varnish was impregnated into a glass cloth treated with the reaction composition and dried to prepare a prepreg having a resin content of 43%. Next, eight of the prepregs were stacked, a copper foil having a thickness of 35 μm was stacked on both surface layers thereof, and heated at 175 ° C. for 60 minutes to be integrally molded to obtain a copper-clad laminate having a thickness of 1.6 mm. Further, the copper foil was entirely etched out with an etching solution, washed with water and air-dried to obtain a solder heat resistance test laminate.

A prepreg having a resin content of 46% was prepared in the same manner using a glass cloth [216 manufactured by Asahi Shabel Co., Ltd.] having a thickness of 0.10 mm. The prepreg was laminated on both surface layers of a 0.2 mm-thick glass cloth / epoxy resin printed wiring board (manufactured by Daiwa Kogyo Co., Ltd., blackened product), and 35 μm copper foil was further laminated on both surface layers of the prepreg. Then, heat at 175 ° C for 60 minutes to integrally mold,
A copper clad laminate having a thickness of 0.45 mm was obtained. Further, the copper foil was entirely etched out with an etching solution, washed with water and air-dried to obtain a laminate for a measling characteristic test. Using these prepregs and laminated plates, the resin impregnability, solder heat resistance, and measling characteristics were measured. The results are shown in Table 1.

Example 2 35.0 g of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane was dissolved in 70 g of methanol, 18.7 g of benzyl chloride was added, and the mixture was reacted at 50 ° C. for 3 hours. Thereafter, in the same manner as in Example 1, 28.5 g of a methanol solution containing 28% sodium methylate was added to remove the precipitate. Further, 17.4 g of vinylbenzyl chloride was added to the silane reaction product, and the mixture was reacted under reflux at 50 ° C. for 4 hours. Chlorine ion generated during the reaction was quantified by potentiometric titration, and it was found that 88% vinylbenzyl chloride and benzyl chloride were reacting with each other.

[0034]

[Chemical 11]

Was obtained. The obtained reaction product was treated with glass cloth in the same manner as in Example 1 to form a laminated plate, and the characteristics were measured. The results are shown in Table 1.

Example 3 Trimethoxysilylpropyldiethylenetriamine 3
0.9 g was dissolved in 70 g of methanol, 13.9 g of benzyl chloride was added, and the mixture was reacted at 60 ° C. for 3 hours. Further, 18.0 g of vinylbenzyl chloride was added, and the mixture was reacted at 50 ° C. for 5 hours under reflux. Chlorine ions generated during the reaction were quantified by potentiometric titration, and as a result, 85% of vinylbenzyl chloride and benzyl chloride were reacted,

[0037]

[Chemical 12]

And

[0039]

[Chemical 13]

Was obtained. The obtained reaction composition was treated with glass cloth in the same manner as in Example 1 to prepare a laminated plate, and then the characteristics were measured. The results are shown in Table 1.

Comparative Example 1 As a comparative drug, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.hydrochloride [SZ manufactured by Toray Dow Corning Silicone Co., Ltd.
6032] was used, a glass cloth treatment was carried out in the same manner as in Example 1 to obtain a laminated plate, and then the characteristics were measured. The results are shown in Table 1. Comparative Example 2 In the same manner as in Example 1 except that N-β- (N-benzylaminoethyl) -γ-aminopropyltrimethoxysilane and hydrochloride [KBM6123 manufactured by Shin-Etsu Chemical Co., Ltd.] were used as comparative agents. After the glass cloth treatment was performed to obtain a laminated plate, the characteristics were measured. The results are shown in Table 1. Comparative Example 3 A glass cloth treatment was performed in the same manner as in Example 1 except that N-aminoethylaminopropyltrimethoxysilane [S320 manufactured by Chisso Corporation] was used as a comparative agent, and then the characteristics were measured. . The results are shown in Table 1.

[0042]

[Table 1]

[0043]

The silane composition according to the present invention has, as a characteristic structure, a compound having a group represented by the formula II in the side chain in the molecule and a bulky organic chain portion as a main component. In general, a silane coupling agent has a silicon atom bonded to an inorganic substrate through oxygen and an organic functional group and a matrix resin, but when the silane composition according to the present invention is used, a group represented by the formula II is used. Incorporation of the organic chain into a bulky structure improves the miscibility and affinity with the resin to form a tough bond with the resin, and the silane coupling agent is appropriately polymerized with each other. Suppressed, and forms a silane molecular layer with stress relaxation ability on the glass surface,
Form a bond with the tougher glass surface.

The silane coupling agent composition of the present invention is
Thermosetting resin for siliceous surface, especially glass surface,
For example, for printed circuit boards that can significantly improve the adhesiveness of epoxy resin, polyimide resin, etc., and can impart a high stress relaxation ability to the adhesive interface, especially excellent thermal shock resistance, solder resistance, and measling resistance. It is suitable as a surface treatment agent for glass fabric which is a reinforcing material.

Claims (3)

[Claims] 1. (a) General formula I: [In the formula, Q _n is the formula II: Is a group represented by or hydrogen, and when k = 1, the formula is
II is a group represented by II, and when k = 2, at least one is a group represented by Formula II. Also, k is 1 or 2. In the formula, R ¹ , R ² and R ⁶ are divalent aliphatic hydrocarbon groups having 6 or less carbon atoms, and R ³ is a divalent aliphatic hydrocarbon group having 10 or less carbon atoms, or It is a hydrocarbon group containing an aromatic ring, R ⁴ is an alkyl group or cycloalkyl group having 6 or less carbon atoms, or a phenyl group, and R ⁵ is a hydrolyzed group selected from the group consisting of alkoxy and aryloxy groups. It is a decomposable group, and a is 0 or 1. ] The silane coupling agent composition which consists of the silane compound or its acid salt represented by these, and the water-soluble organic solvent which can melt | dissolve (ii) and (ii). 2. A glass fiber product treated with the silane coupling agent composition according to claim 1. 3. A glass fiber reinforced resin laminate comprising the glass fiber product according to claim 2 as a reinforcing material.