JPH0547551B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a silane composition used as a coupling agent between an inorganic support and an organic resin.
More specifically, the present invention relates to a silane composition whose main component is an organosilicon compound having a specific functional group that significantly improves the adhesion of a resin to a siliceous surface, particularly a glass surface. [Prior Art] In recent years, a wide variety of silane coupling agents have been developed and widely used to improve the miscibility and adhesion between inorganic agents and unsaturated polymers. The silane coupling agent usually contains an organic chain moiety for providing affinity and bonding properties with the unsaturated polymer;
It consists of a moiety having a hydroxyl group or an alkoxy group for forming a chemical bond between silicon and the inorganic material via oxygen atoms when the surface of the inorganic material is treated. By the way, in a composite material of an inorganic filler or an inorganic fiber material and an unsaturated polymer compound, it can be said that the function of the coupling agent plays an important role in the expression of its physical properties. In other words, when a mechanical shock is applied to this composite material from the outside, the mechanical stress is concentrated at the interface where the elastic modulus differs, so if the adhesive force at the interface is insufficient, the interface will break. When a thermal shock is applied, the material expands and contracts, but thermal stress due to the difference in expansion coefficients between the base material and resin is concentrated at the interface, so if the adhesive force at the interface is insufficient, destruction of the interface will still occur. It's put away. Therefore, if the adhesive force at the interface is increased by the coupling agent, it will be possible to prevent such destruction. In recent years, many printed wiring boards using unsaturated polyester resin have been manufactured, but these boards also have problems with measling defects similar to glass-epoxy boards. There is. Measling here is also called crazing, and is a phenomenon that occurs noticeably at the intersections of glass fiber weaves, and when thermal shock or mechanical shock is applied during the manufacturing process of the substrate, If the adhesion between the glass fiber and the resin is not sufficient, separation will occur at this interface. On the other hand, most of the silane coupling agents commonly used for unsaturated polymer resins have a linear structure with an unsaturated group at the end, such as an acrylic group, a methacrylic group, or a styryl group as an organic functional group. For example, the formula and A silane coupling agent represented by is known. According to experiments conducted by the present inventors, when a glass fabric is treated with the silane coupling agent and a printed wiring board is made from an unsaturated polyester resin, sufficiently satisfactory results in measling resistance are not obtained. Nakatsuta. In other words, the performance of existing silane coupling agents cannot meet the advanced physical properties required of recent glass-reinforced resins, and cannot meet the demands of the rapidly becoming more sophisticated electronics industry. It is starting to disappear. [Problems to be Solved by the Invention] Under these circumstances, the present invention makes it possible to significantly improve the adhesion of unsaturated polymers, such as unsaturated polyester resins, to silicic surfaces, especially glass surfaces. The purpose of this invention is to provide a silane composition that can The present invention also provides a silane coupling agent composition for surface treatment of glass fabric, which is useful as a reinforcing material for printed wiring boards and has excellent measling resistance. [Means for Solving the Problems] As a result of intensive studies to develop a silane composition having the above-mentioned excellent characteristics, the present inventors have found that the silane composition has a plurality of groups represented by the formula in its molecule. ,
The present inventors have discovered that a composition containing a polyfunctionalized organosilicon compound as a main component is suitable for this purpose, and have completed the present invention based on this finding. That is, the present invention relates to (a) general formula [Q ¹ , Q ² , Q ³ in the formula are A group or hydrogen represented by n=0
When n = ¹ or ² , at least two of Q ¹ , Q ² and Q ³ are groups represented by the formula.
R ¹ is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms, and R ² is a divalent aliphatic hydrocarbon group having 10 or less carbon atoms, or a hydrocarbon group containing an aromatic ring. , R ³ is an alkyl group or cycloalkyl group having 6 or less carbon atoms, or a phenyl group, R ⁴ is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, and R ⁵ is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms. n is 0 or an integer of 1 or 2, and a is an integer of 0 to 2. The present invention provides a silane composition comprising a silane compound or an acid salt thereof represented by the following formula and a water-soluble organic solvent capable of dissolving (b) and (a). The present invention will be explained in detail below. Main components of the silane composition of the present invention, general formula (In the formula, ^Q1 to ^Q3 are the formulas R1 to R5, and n and a have the same meanings as above.) It is an aminosilane represented by the following formula. Although it is theoretically possible to make the number of carbon atoms of R ¹ , which is a divalent aliphatic hydrocarbon group with 6 or less carbon atoms bonded to nitrogen atoms at both ends, to 7 or more, it is possible to make the final compound inorganic. When treating the surface, it is convenient to use the form of an aqueous solution, and because of the need for solubility in water, it is desirable that the number is 6 or less. For the same reason, the number of carbon atoms in ^R2 , which is a divalent aliphatic hydrocarbon group directly bonded to a silicon atom and bonded to a nitrogen atom at the other end or a hydrocarbon group containing an aromatic ring, is 10 or less. desirable. Examples of ^R2 include alkylene groups such as methylene, ethylene, propylene, butylene, and hexylene, phenylene groups,

【formula】

[Operation and effect of the invention]

As a characteristic structure, the silane composition according to the present invention contains as a main component a compound having a plurality of groups represented by the formula that crosslinks with the matrix resin in the molecule. Generally, in a silane coupling agent, a silicon atom is bonded to an inorganic material via oxygen and bonded to a matrix resin via an organic functional group, but when the silane composition according to the present invention is used, the group represented by the formula Since there are multiple silane molecules in the matrix resin, it is presumed that the silane molecules cross-link with the matrix resin at high density, forming a strong bond between the matrix resin and the inorganic material. Furthermore, since the vinylbenzyl group contained in the molecule of the silane compound has a reactivity equivalent to that of styrene, it has good copolymerizability and miscibility with unsaturated resins, such as acrylic-modified epoxy resins and various unsaturated polyester resins. Are better. The most preferred example of the application of the silane composition of the present invention is as a silane coupling agent for surface treatment of glass fabric useful as a reinforcing material for printed wiring boards. It shows a remarkable effect on improvement. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, each physical property was calculated|required as follows. (1) Resin impregnability The impregnability of the resin was determined visually. ◎: Very good, 〇: Good, △: Average, ×: Poor (2) Soldering heat resistance Immersed in a solder bath at 260℃ for 10 seconds, 20 seconds, and 30 seconds respectively, with blisters (×) and without (〇 ) was investigated. (3) Measling characteristics A soldering iron with a diameter of 5 mm heated to 240°C, 260°C, and 280°C was pressed for 10 seconds with a load of 100 g to determine whether measling occurred (x) or not (〇). I looked into it. (4) Potentiometric titration Hydrolyzable chloride ions were titrated with a methanol solution of sodium methylate using a PH meter manufactured by Toa Denpa Kogyo Co., Ltd. HM-5A. Measurements were performed at room temperature. (5) Kinematic viscosity Using an Ubbelohde type viscosity tube, in a constant temperature water bath, 25
Kinematic viscosity measurements were carried out at °C. (6) NMR Measurements were performed using an NMR spectrometer manufactured by JEOL Ltd. JNM-PMX60SI. (7) IR Measurement was performed using an infrared spectrometer of Shimadzu Corporation FTIR-4100. Example 1 N-β-(N-vinylbenzylaminoethyl)-
While stirring 300 g of a 40% silane methanol solution of γ-aminopropyltrimethoxysilane/hydrochloride, 618 g of a 28% sodium methylate methanol solution was added, and the mixture was stirred at room temperature for 2 hours. After stopping the stirring and leaving the mixture at room temperature overnight, the precipitate was removed by filtration. After adding 36.7 g of vinylbenzyl chloride to 267 g of the silane solution, the mixture was reacted under reflux for 3 hours. After the reaction was completed, the reaction product was developed by thin layer chromatography (TLC), and it was confirmed that vinylbenzyl chloride had been added. Furthermore, when the chlorine ions produced during the reaction were quantified by potentiometric titration, it was confirmed that more than 90% of vinylbenzyl chloride had reacted. In the composition, in addition to unreacted N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane and/or its hydrochloride, N-β-(N-vinylbenzylaminoethyl)-N-γ-(vinylbenzyl)-γ-aminopropyltrimethoxysilane and/or its hydrochloride, N-β-(N-di(vinylbenzyl)
(aminoethyl)-γ-aminopropyltrimethoxysilane and/or its hydrochloride, N-β-(N-di(vinylbenzyl)
aminoethyl)-N-γ-(vinylbenzyl)-γ
products such as -aminopropyltrimethoxysilane and/or its hydrochloride. The solution thus obtained was a brown to reddish brown liquid with a kinematic viscosity of 1.16 centiTokes, a specific gravity of 0.85 g/cm ³ , and a chloride ion concentration of 2.1 wt%. The IF chart of the composition is shown in Figure 1, and
The NMR chart is shown in Figure 2. Then 0.5% by weight of the silane compound in the reaction composition
Aqueous solutions were prepared, and acetic acid was added to them to adjust the pH to 4 (treatment liquid). A glass cloth with a thickness of 0.19 mm (7628 manufactured by Asahi Schwebel Co., Ltd.) was immersed in this treatment solution, and then the liquid was removed so that the treatment solution retention rate was approximately 30% by weight relative to the glass cloth. Dry with hot air. Further, an unsaturated polyester varnish was prepared by blending 100 parts by weight of an unsaturated polyester resin, 40 parts by weight of polymerized monomer styrene, and 1 part by weight of kyumene hydroperoxide. A glass cloth treated with the reaction composition was impregnated with the varnish. Layer two sheets of the cloth, layer copper foil with a thickness of 35 μm on both surfaces, degas for 2 minutes, heat at 130℃ for 120 minutes, mold into one piece, and
A 0.4 mm copper clad laminate was obtained. Further, the entire surface of the copper foil was etched out using an etching solution, washed with water, and air-dried to obtain a laminate for physical property testing. Regarding this laminate, resin impregnation properties, solder heat resistance, and measling resistance were measured. Results first
Shown in the table. Example 2 In place of N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride in Example 1, N-vinylbenzyl-γ-aminopropyltriethoxysilane.
A reaction composition was obtained in the same manner as in Example 1 using the hydrochloride. This was treated with glass cloth in the same manner as in Example 1 to form a laminate, and its properties were then measured.
The results are shown in Table 1. Example 3 N-β-(N-vinylbenzylaminoethyl)-
After adding 4.07 g of vinylbenzyl chloride to 50.0 g of a 40% silane methanol solution of γ-aminopropyltrimethoxysilane hydrochloride, the mixture was reacted under reflux for 3 hours. When the chlorine ion generated during the reaction was quantified by potentiometric titration, it was found to be 92%.
It was confirmed that vinylbenzyl chloride had reacted. The obtained reaction composition was treated with glass cloth in the same manner as in Example 1 to form a laminate, and then its properties were measured. The results are shown in Table 1. Example 4 In place of N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride in Example 3, N-vinylbenzyl-γ-aminopropyltriethoxysilane.
A reaction composition was obtained in the same manner as in Example 3 using the hydrochloride. This was treated with glass cloth in the same manner as in Example 1 to form a laminate, and its properties were then measured.
The results are shown in Table 1. Example 5 First, 1-trimethoxysilylpropyl-
The hydrolyzable chloride concentration of a methanol solution containing 40 wt% of 7-vinylbenzyldiethylenetriamine hydrochloride was determined in the same manner as in Example 1, and was confirmed to be 3.2 wt%. Next, 50.00 g of the solution was added to a 300 ml tube equipped with a reflux tube.
The mixture was placed in a separable flask, and while stirring using a magnetic stirrer, 8.32 g of a methanol solution containing 28 wt% of sodium methylate was added dropwise using a dropping funnel over 5 minutes. The liquid state changed to a yellow-white suspension due to the produced sodium chloride. Next, the flask was heated in an oil bath to raise the temperature, stirred and refluxed for 10 minutes at reflux temperature, and then 6.57 g of vinylbenzyl chloride was added dropwise from the dropping funnel over 3 minutes, followed by reflux reaction for 3 hours under a nitrogen atmosphere. After that, the mixture was cooled to room temperature and stirring was stopped. Further, after being left at room temperature for 2 hours, the white precipitate was removed by decantation to obtain the desired composition. Further, the resulting white precipitate was washed with 100 g of chloroform, filtered, and dried to obtain 2.4 g of sodium chloride. The solution thus obtained was a yellow-brown liquid with a kinematic viscosity of 5.32 cst and a specific gravity of 0.932 g/cm ³ chloro ion concentration of 3.0 wt%. IR of the composition
The chart is shown in Figure 3, and the NMR chart is shown in Figure 4. The resulting composition was treated with glass cloth to form a laminate in the same manner as in Example 1, and various properties were measured. Table 1 shows the results. In the composition, In addition to the unreacted compound and/or its hydrochloride represented by and/or products such as its hydrochloride. Comparative Example 1 N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride was used as a comparative drug. Using this chemical, glass cloth was treated in the same manner as in Example 1 to form a laminate, and the properties were then measured. The results are shown in Table 1. Comparative Example 2 γ-methacryloxypropyltrimethoxysilane was used as a comparative drug. Example 1
After processing the glass cloth in the same manner as above to form a laminate, its properties were measured. The results are shown in Table 1. Comparative Example 3 γ-methacryloxypropyldimethoxymethylsilane was used as a comparative drug. The drug was treated with glass cloth in the same manner as in Example 1 to form a laminate, and its properties were then measured. The results are shown in Table 1. Comparative Example 4 γ-acryloxymethyltrimethoxysilane was used as a comparative drug. The drug was treated with glass cloth in the same manner as in Example 1 to form a laminate, and then
Characteristics were measured. The results are shown in Table 1. Comparative Example 5 N-vinylbenzyl-γ-aminopropyltriethoxysilane was used as a comparative drug. The drug was treated with glass cloth in the same manner as in Example 1,
After forming a laminate, its properties were measured. The results are shown in Table 1.

【table】 [Brief explanation of the drawing]

FIG. 1 is an IR spectrum after the solvent was removed by volatilization from the silane composition of the present invention (Example 1),
FIG. 2 is an NMR spectrum of the composition. Moreover, FIG. 3 is an IR spectrum obtained by removing the solvent by volatilization from the composition of Example 5, and FIG. 4 is an NMR spectrum of the composition.

Claims (1)

[Claims] 1 (a) General formula [Q ¹ , Q ² , Q ³ in the formula are A group or hydrogen represented by n=0
When n = ¹ or ² , at least two of Q ¹ , Q ² and Q ³ are groups represented by the formula.
R ¹ is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms, and R ² is a divalent aliphatic hydrocarbon group having 10 or less carbon atoms, or a hydrocarbon group containing an aromatic ring. , R ³ is an alkyl group or cycloalkyl group having 6 or less carbon atoms, or a phenyl group, R ⁴ is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, and R ⁵ is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms. n is 0 or an integer of 1 or 2, and a is 0 or an integer of 1 or 2. ] A silane composition comprising a silane compound or an acid salt thereof and (b) and a water-soluble organic solvent capable of dissolving (a).