JPH0228228A - Silane composition - Google Patents

Abstract

PURPOSE:To obtain the title composition suitable for surface treatment of woven fabric of glass useful as a reinforcing material of printed circuit board consisting essentially of a silane compound containing plural specific functional groups prepared by reacting an aminosilane compound with a styrene derivative. CONSTITUTION:(A) (i) An aminosilane compound such as N-beta-(N- vinylbenzylaminoethyl)-gamma-aminopropyltrimethoxysilane and (ii) a halogen- containing styrene derivative such as vinylbenzyl chloride are dissolved in (B) a water-soluble solvent such as methanol and reacted e.g., at 60-120 deg.C to give the aimed composition as a silane compound shown by formula I [Q<1>-Q<3> are group shown by formula II (R<5> is <=6C aliphatic); R<1> is <=6C aliphatic; R<2> is <=10C aliphatic; R<3> is <=6C alkyl; R<4> is alkoxy, etc.; n is 0-2; a is 0-2].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] 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.

[Conventional technology]

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 has an organic chain moiety to provide affinity and bonding properties with unsaturated polymers, and when treated on the surface of an inorganic material, it forms a bond between silicon and the inorganic material through oxygen atoms. It consists of a hydroxyl group or a moiety covering an alkoxy group to form a chemical bond.

By the way, in a composite material of an inorganic filler or an inorganic fiber material and an unsaturated polymer compound, the function of a coupling agent plays an important role in expressing its physical properties. 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. In addition, when a thermal shock is applied, the material expands and contracts, but the thermal stress due to the difference in expansion coefficient between the base material and the resin is concentrated at the interface, so if the adhesive force at the interface is not sufficient, the interface may also be destroyed. arise. Therefore, if the contact between the interfaces is high, it is possible to prevent such failure.

In recent years, many printed wiring boards using unsaturated polyester resins have been manufactured, and even in these boards, measling defects similar to glass-epoxy boards have become a problem. The measling referred to here is also called crazing, and is a phenomenon that occurs noticeably at the intersection of the weaves of glass fabric, and is a phenomenon that occurs when thermal shock or mechanical shock is applied during the manufacturing process of the substrate. If the adhesion between the glass fabric and the resin does not last for 1 minute, peeling will occur at this interface.

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 styrene group as an organic functional group. For example, 2 and 1v NH ((] 12 > 3 3! (QC) - 13) 3
A silane coupling agent represented by HC,Q-IV 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 created using an unsaturated polyester resin, sufficiently satisfactory results with Measling resistance H can be obtained. I couldn't.

In other words, the performance of these existing silane coupling agents has not been able to achieve sufficient results in response to the advanced physical conditions required of recent glass-reinforced resins. I've become unable to cope.

[Invention or problem to be solved]

Under these circumstances, the present invention provides a silane composition that makes it possible to significantly improve the adhesion of unsaturated polymers, such as unsaturated polyester resins, to silicic surfaces, especially glass surfaces. This was done as a first step.

The present invention also provides puddings 1 to 1 with better measling resistance.
The present invention provides a silane coupling agent composition for surface treatment of 1" glass fabric as a reinforcing material for wiring boards.

[Means for Solving the Problems] The present inventors have conducted intensive studies to develop a silane composition having the above-mentioned excellent characteristics, and as a result, the present inventors have found that the formula
The present inventors have discovered that a composition containing a plurality of groups represented by the formula and whose main component is a polyfunctionalized organosilicon compound is suitable for the purpose, and based on this knowledge, the present invention has been completed. It's arrived.

That is, the present invention provides (a) general formula 1 (in the formula, ol, Q2, and Q3 are necessarily groups represented by the formula (■) or hydrogen, and when n=o, Q and Q2 are represented by the formula (■). When n-1 or 2, at least two of ol, o2, and Q3 are groups represented by the group of formula (1). R1 is a divalent aliphatic hydrocarbon having 6 or more carbon atoms. group, and R2 has 10 carbon atoms.
a divalent aliphatic hydrocarbon group or a hydrocarbon group containing an aromatic ring, R3 is an alkyl group or cycloalkyl group with carbon number or 6 F, or a phenyl group, R4
is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, and R5 is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms. n is O or an integer of 1 or 2, and a is an integer of O to 2. ] or an acid salt thereof; and a water-soluble organic solvent capable of dissolving ([]) (a).

A detailed description of the present invention is provided below.

The main component of the silane composition of the present invention is represented by the formula (Q1 in the formula
-Q3 are aminosilanes represented by formulas R1 to R5 and "1.a has the same meaning as above."

Although it is theoretically possible to make the number of carbon atoms of R1, which is a divalent aliphatic hydrocarbon group having 6 or more carbon atoms bonded to nitrogen atoms at both ends, to 7 or more, it is possible to When processing, it is convenient to use the form of an aqueous solution, and from the necessity of controlling the 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.

R? Examples include alkylenes such as meblene, ethylene, propylene, butylene, and hexylene.

R3 is a 7/ruyl group or a cycloalul group having 6 or less carbon atoms, or a phenyl group, examples of which include methyl, T-tyl, methyl, butyl, pentyl, Alkyl groups such as hexyl and isopropyl; Schiff [1 alkyl groups such as cyclobutyl and cycloCat\xyl;
and phenyl groups.

If the number of carbon atoms is large, it will adversely affect the adhesion between the silane compound and the surface of the inorganic material, so methyl and nibble groups are preferred.

R4 is a hydrolyzable group selected from the group consisting of alkoxy and aryloxy groups, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy,
t-butoxy, 2-methoxy 1 toxy, 2-methoxy 1
These include alkoxy groups such as toxy, and aryloxy groups such as phenoxy and naphthoxy. Due to its good hydrolyzability,
Preferably it is a lower alkoxy group having 1 to 4 carbon atoms.

The vinyl group in the group represented by the formula (1) may be at any of the ortho, meta, and para positions.

Further, R5 is a divalent aliphatic hydrocarbon group having 6 or less carbon atoms. Although it is theoretically possible to increase the number of carbon atoms to 7 or more, it is convenient to treat the final compound on an inorganic surface in the form of an aqueous solution, and it is necessary to have solubility in water. The following is desirable.

r'>(, is an integer of 2 from to. If the number of n is increased unnecessarily, the number of secondary amines in the molecule will increase, which will have an adverse effect on the bond between the group represented by formula (■) and the unsaturated resin. effect.

In order to avoid this, it is theoretically possible to introduce a group represented by the formula (2) to all amines, but this is not preferred since the solubility of the compound in water is significantly reduced.

The solvent used in the silane composition of the present invention is not particularly limited as long as it is an organic solvent that dissolves the silane compound as a reaction product and is water-soluble.
It is convenient and desirable to prepare the composition by dissolving each raw material used in producing the silane compound. Such water-soluble ↑ (l solvents include, for example, alcohols such as methanol, ethanol, propatool, diethyl ether, 1,4-dioxane, 1,3-dioquiline, tetrahydrofuran, needles such as ethylene glycol monomethyl ether, and acetone. , methyl S [ketones such as pulketone, etc.].

These solvents may be used alone or in combination of two or more. Further, there is no particular restriction on the content of the solvent in the composition, as long as it is sufficient to dissolve the silane compound as a reaction product.

An example of a method for producing the silane composition of the present invention is shown below.

The aminosilane compound, such as N
-β-(N-vinylbenzylamino nibble)-γ-aminopropyltrimethoxysilane and a halogen-containing styrene derivative, such as vinylbenzyl chloride, preferably in an inert gas atmosphere such as argon or nitrogen, usually under normal pressure. The desired product can be obtained by carrying out the reaction under reflux at 60°C to 120°C.

When the kinematic viscosity of the composition thus obtained was measured using an Ubbelohde viscosity tube, the kinematic viscosity was 0.5 to 5.
0 centes 1 hex, specific gravity 0.78・-2,0',
j/cm3 of liquid.

The composition of the present invention contains a compound represented by the above general formula 21 and/or an acid salt thereof as a main component, and the following compound (in the formula (Q, R, R-, R, R', a, n have the same meanings as above).

In addition, in order to prevent polymerization of vinyl groups during storage of the silane composition of the present invention, it is also possible to add 1% or less of a polymerization inhibitor such as P-benzoquinone, ↑-butylcatheter, nitrobenpine, etc. during polymerization. It is.

[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 bases represented by the formula H that crosslink with the matrix 4't4 fat in the molecule.

In general, in a silane coupling agent, a silane coupling agent binds to an inorganic material via oxygen and also binds to a matrix resin with an organic functional group. However, when the silane composition of the present invention is used, Since there are multiple silane molecules in the molecule, 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, the hynylbenzyl group that the silane compound has in its molecule has a reactivity equivalent to that of styrene.
Therefore, it has excellent copolymerizability and miscibility with unsaturated resins such as acrylic mono-decorated epoxy resins and various unsaturated poly-ester resins.

The most preferred application example of the silane composition of the present invention is:
It can be used as a silane coupling agent for surface treatment of pieces of glass fabric as a reinforcing material for printed wiring boards, and has a remarkable effect on improving soldering heat resistance, Miesling resistance, etc.

[Examples] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, each clothesline 1 was calculated|required as follows.

(1) Resin impregnability [ ] The quality of the impregnating property of the resin was determined by visual inspection.

◎: Extremely good, ○: Good, Δ: Good, ×: Poor (2) A11i4 Immersed in a thermal 260 °C semi-FB bath for 1 () seconds, 20 seconds, and 3 () seconds, and no blistering occurred. We investigated whether there was a dip (x) or no (○).

(3) Measling Koma tq 240'0. 11N at 260℃ and 280'C respectively
Heat a half-a1 iron with a diameter of 5Irun for 10 seconds.
Does it cause measling when pressing with g load? j(X
) and none (○).

(4) Potential-differential titration Using a pH meter manufactured by Tokyoku Denpa Kogyo ■Bun-5, titration was carried out with a methanol solution of hydrolyzable chloride ions and -lium meblate. Measurements were performed at room temperature.

(5) Kinematic viscosity The kinematic viscosity was measured at 25°C in a constant temperature water bath using an Ubbelohde type viscosity tube.

(6) NMR H book 1 f@JN) f-PHX60SI O) N
Measurements were performed using an MR spectrometer.

(7) IR Measurement was performed using an infrared spectrometer of Shimaoki Seisakusho ■FrIR-4100.

Example 1 While stirring 300 q of a 40% silane methanol solution of N-β-(N-vinylbenzylaminoethyl)-T-aminopropyl i-rimethoxysilane hydrochloride, 28% of No. 1 helium methylate was added. 618g methanol solution
was added and stirred at room temperature for 2 hours. Stirring was stopped and the mixture was allowed to stand at room temperature for a while, and then the precipitate was removed by filtration. 36.7 g of vinylbenzyl chloride is added to 267 g of the silane solution.
was added, and the mixture was reacted under reflux for 3 hours. After reaction route r, the reaction product was developed by thin layer chromatography (T'LC), and it was confirmed that vinylbenzyl chloride had been added. Furthermore, when the chlorine ions produced during the reaction were determined by potentiometric titration, it was confirmed that 90% or more of vinylbenzyl fluoride had reacted.

The solution obtained in this way is a child-colored to reddish-brown liquid with a kinematic viscosity of 1.16 centistokes and a specific gravity of 0.8.
5'J/cm3, ri [1 Louis A and 1 Noriyoshi is 2.1
It was wt%. FIG. 1 shows the IR block v-1 of the composition, and FIG. 2 shows the IR block 7-1 of the composition.

Next, a 0.5% by weight aqueous solution of the silane compound of the reaction composition was prepared, and acetic acid was added to it to adjust the pif/1. A cloth (7628 manufactured by Asahi Nibel Corporation) was immersed, and then the liquid was removed so that the retention rate of the treatment liquid was about 30% relative to the glass cloth, and then dried by heat K (K) at 110°C.

In addition, an unsaturated polyester Sonis was prepared by blending unsaturated polynispule resin 100 medium-early part, 40 parts by volume of polymerized monomer styrene, and 1 part cumene hydroveroxide.

A glass cloth treated with the reaction composition was impregnated with the varnish. Take two pieces of the cloth and apply a thickness of 35cm on both surfaces.
After stacking μm copper foil and degassing for 2 minutes, 130'C''
r Heated for 120 minutes and molded into one piece, 19mm x 0.4m
A copper-clad laminate with a diameter of m 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, semi-[[1 heat resistance,
The measling resistance was measured. The results are shown in Table 1.

Example 2 In place of N-β-(N-vinylbenzyl 7minoethyl)-γ-aminopropyltrimethoxysilane hydrochloride in Example 1, N-vinylbenzyl-γ-aminopropyltriethoxysilane hydrochloride was used. The reaction composition was prepared in the same manner as in Example 1 using i9. This was subjected to the lath cross treatment 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-vinylbenzylamino 1 tyl>-r-7
After adding 4.075j of vinylbenzyl chloride to 50.09 g of a 40% silane methanol solution of xysilane hydrochloride, 4.075 j of vinylbenzyl chloride was reacted under reflux for 3 hours. When the chlorine ions produced during the reaction were quantitatively determined by potentiometric titration, it was confirmed that 92% of 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 the 1-h property was measured. The results are shown in Table 1.

Example 4 N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyl trime 1-xysilane in Example 3
A reaction composition was obtained in the same manner as in Example 3 except that N-vinylbenzyl-γ-aminopropyl 1-ethoxysilane hydrochloride was used instead of the hydrochloride. This was treated with a 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 26.5 J of trime] - xysilylprobyl di-T ethylene] - riamine was dissolved in 60 g of methanol (and after adding 15.3 V of vinylbenzyl fluoride, it was reacted for 3 hours. Furthermore, vinylbenzyl chloride was added 15,39 was added and reacted under reflux for 3 hours.The chlorine ion generated during the reaction was determined by potentiometric titration with J and ω, and it was found that 86
It was confirmed that % vinylbensilic [1 ride] reacted. The 1q reaction composition was treated with glass cloth in the same manner as in Example 1 to form a laminate, and its properties were measured.

The results are shown in Table 1.

Comparative Example 1 As a comparative drug, N-β-(N-vinylbenzylaminoethyl)-di-aminopropyl trime 1-xysilane.
Hydrochloride was used. The obtained reaction composition was subjected to a glass coating treatment 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.

Comparative Example 2 γ-methacryloxypropyltrimethoxysilane was used as a comparative drug. The obtained reaction composition was treated with crow cloth in the same manner as in Example 1 to form a laminate, and then
The sex was measured. The results are shown in Table 1.

Comparative Example 3 As a comparative drug, T = methacrylic [bilayer xip]:1 pyrudimethoxymethylsilane was used. The resulting reaction composition was treated with glass cloth in the same manner as in Example 1 to form a laminate, and then the specificity and P[ were measured. Enter the results in Table 1.
.

Comparative Example 4 γ-7Clyloxyprobyltrimethoxysilane was used as a comparative drug. The 1″:1 Radar reaction composition was treated with crow cloth in the same manner as in Example 1 to form a laminate, and then
Characteristics were measured. Bob's results are shown in Table 1.

Comparative Example 5 N-hinylbenzyl-r-7minopropyltriethoxysilane was used as a comparative drug. The resulting reaction composition 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. (more space)

[Brief explanation of the drawing]

FIG. 1 is an IR chart of the silane composition of the present invention (Example 1), and FIG. 2 is an NMR chart thereof.

Claims (1)

[Claims] 1. (A) General formula I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... I (Q^1, Q^2, Q^3 in the formula are formula II ▲ Numerical formulas, chemical formulas, etc.) , tables, etc. ▼...II When n=0, Q^1 and Q^2 are groups expressed by formula II, and n=1
Or if 2, at least 2 of Q^1, Q^2, Q^3
is a group represented by a group of formula II. 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 carbide containing an aromatic ring. It is a hydrogen group, R^3 is an alkyl group or cycloalkyl group having 6 or less carbon atoms, or a phenyl group, and 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 a water-soluble organic solvent capable of dissolving (b) and (a).