JPH05147979A - Glass fiber base material and glass fiber reinforced resin laminated sheet using the same - Google Patents

Abstract

(57) [Summary] [Object] To provide a glass fiber base material having a high impregnation property and a high heat resistance, and a glass fiber reinforced resin laminated plate using the glass fiber base material as a reinforcing material. The glass fiber base material of the present invention is an amine having a vinylbenzyl group at one end and an alkoxysilane group at the other end, and having at least one benzyl group substituted on the nitrogen atom in the main chain. It is characterized in that the compound or its acid salt is attached to the surface. The glass fiber reinforced resin laminate of the present invention is characterized by using the glass fiber base material as a reinforcing material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber base material having a high impregnation property and a high heat resistance, and a glass fiber reinforced resin laminated plate using the glass fiber base material as a reinforcing material. The glass fiber base material and the glass fiber reinforced resin laminate of the present invention are particularly preferably used for a printed circuit board.

[0002]

2. Description of the Related Art Glass fibers have excellent dimensional stability,
It is widely used in the electronics field for reasons such as electrical characteristics, and in particular, glass cloth obtained by weaving glass raw yarn is in great demand as a material for printed circuit boards due to its excellent dimensional stability.

With the rapid technological progress in the electronics industry in recent years, the demand for its related materials is increasing. For example, in order to avoid the problem of increased heat generation due to high integration of ICs and the problem of smear when drilling a through hole plating drill (a phenomenon in which resin flows out due to frictional heat between a high-speed rotating drill and a substrate). However, even higher heat resistance of printed circuit boards has been required.
A printed circuit board having poor heat resistance has various drawbacks in the course of its processing steps such as etching, water washing, perforation, washing with an organic solvent, and soldering step. For example, when placed in a high-temperature environment in the solder fusing process, a material having poor heat resistance causes significant problems in practical use such as swelling or peeling on the surface or inside.

On the other hand, the heat resistance and other properties of the printed circuit board largely depend not only on the resin but also on the performance of the silane coupling agent used for the surface treatment of the glass cloth used as the material. Currently, various silane coupling agents are used in order to improve the miscibility, adhesiveness, etc. of the glass cloth and the resin, but these silane coupling agents are usually used for one silicon atom and usually one When it is treated on the surface of the glass cloth, the hydrolyzable group is decomposed and has a chemical bond between the silicon atom and the glass cloth via the oxygen atom. To generate. On the other hand, when the organic functional group is combined with the resin, it reacts with the functional group of the resin to form a chemical bond. The type of silane coupling agent and its performance are almost determined by the structure of this organic functional group, and those having a suitable structure are selected according to the type of resin used. For example, the organic functional group of the silane coupling agent used for the epoxy resin or polyimide resin used for the matrix is mostly a chain group having an amino group and having several to about 20 carbon atoms. ..

[0005]

At present, existing silane coupling agents have not been sufficiently improved in impregnability and heat resistance, and therefore, silane coupling agents having high impregnation property and high heat resistance. No agent-treated glass fiber substrate has been obtained either.

It is an object of the present invention to provide a glass fiber base material having a high impregnation property and a high heat resistance, and a glass fiber reinforced resin laminated board using the glass fiber base material as a reinforcing material.

[0007]

The present invention has been made to achieve the above object, and the glass fiber substrate of the present invention has the general formula I

[Chemical 3] [Q ¹ and Q ² in Formula I are Formula II

[Chemical 4] Is a group represented by or hydrogen, and when n = 0, Q
¹ is a group represented by the formula II, and when n = 1 or 2, Q
^At least one of ¹ , Q ² is a group represented by the group of formula II.

R ^{1 to} R ⁶ in the formulas I and II are as follows. R ¹ : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ² : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ³ : a divalent aliphatic hydrocarbon group having 10 or less carbon atoms group R ^4: 1 monovalent aliphatic having 6 or fewer carbon hydrocarbon group or an alicyclic hydrocarbon group or a phenyl group R ^5: an alkoxy group or an aryloxy group R ^6: 2-valent aliphatic or less 6 carbon atoms Group hydrocarbon group In addition, n is an integer of 0 or 1 or 2, and a is 0 or 1 or 2
Is an integer. ] It consists of the glass fiber which the compound shown by these or its acid salt adhered to the surface.

Further, the glass fiber reinforced resin laminate of the present invention is characterized by using the above glass fiber base material as a reinforcing material.

As the glass fibers used in the glass fiber base material of the present invention, glass fibers such as E glass, S glass and D glass which have been conventionally used as a reinforcing material for glass fiber reinforced resin laminates can be used. it can. The glass fibers may be long fibers or short fibers. Also,
The shape of the glass fiber base material of the present invention is preferably a sheet shape such as a glass fiber woven cloth, a glass fiber nonwoven cloth, and paper.

The glass fiber substrate of the present invention has the general formula I on the surface of the glass fiber as described above.

[Chemical 5] [Q ¹ and Q ² in Formula I are Formula II

[Chemical 6] Is a group represented by or hydrogen, and when n = 0, Q
¹ is a group represented by the formula II, and when n = 1 or 2, Q
^At least one of ¹ , Q ² is a group represented by the group of formula II.

R ^{1 to} R ⁶ in the formulas I and II are as follows. R ¹ : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ² : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ³ : a divalent aliphatic hydrocarbon group having 10 or less carbon atoms group R ^4: 1 monovalent aliphatic having 6 or fewer carbon hydrocarbon group or an alicyclic hydrocarbon group or a phenyl group R ^5: an alkoxy group or an aryloxy group R ^6: 2-valent aliphatic or less 6 carbon atoms Group hydrocarbon group In addition, n is an integer of 0 or 1 or 2, and a is 0 or 1 or 2
Is an integer. ] A compound represented by the following formula or an acid salt thereof is attached, and after the glass fiber as described above is treated with the silane compound as described above, it is processed into a desired substrate shape, for example, a sheet shape by a conventional method. Such a glass fiber is obtained by processing the glass fiber into a desired substrate shape, for example, a sheet by a conventional method, and then treating the glass fiber substrate with the above-mentioned silane compound.

Specific examples of the silane compound represented by the above general formula I include the following. N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminopropyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzylaminoethyl) -N-benzyl-γ-aminopropyltri Methoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-N-benzyl-γ-aminopropyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-amino Propyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-N-benzyl-γ-aminopropyltriethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-) N-benzyl) aminoethyl-N-benzyl-γ-aminopropylmethyldimethoxysilane Its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-N-benzyl-γ-aminopropylmethoxydimethylsilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) amino Hexyl-N-benzyl-γ-aminopropyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-2-phenylethyl) aminoethyl-N-2-phenylethyl-γ-aminopropyltrimethoxy Silane or its hydrochloride N-β- (2-styrylethyl-N-2-phenylethyl) aminoethyl-N-2-phenylethyl-γ-aminopropyltrimethoxysilane or its hydrochloride N-β- (N- Vinylbenzyl-N-benzyl) aminoethyl-γ-aminobutyltrimethoxysilane or its hydrochloride N-β- N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminopentyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminohexyltrimethoxysilane or its hydrochloric acid Salt N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminoheptyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminooctyl Trimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminononyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzyl-N-benzyl) amino Ethyl-γ-aminodecyltrimethoxysilane or its hydrochloride N-β- (N-vinyl ester) Dilaminoethyl) -N-benzyl-γ-aminobutyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzylaminoethyl) -N-benzyl-γ-aminopentyltrimethoxysilane or its hydrochloride N- β- (N-vinylbenzylaminoethyl) -N-benzyl-γ-aminohexyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzylaminoethyl) -N-benzyl-γ-aminoheptyltrimethoxysilane Or its hydrochloride N-β- (N-vinylbenzylaminoethyl) -N-benzyl-γ-aminooctyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzylaminoethyl) -N-benzyl-γ -Aminononyltrimethoxysilane or its hydrochloride N-β- (N-vinylbenzylaminoethyl ) -N-benzyl-γ-aminodecyltrimethoxysilane or its hydrochloride N-β-((N-vinylbenzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminobutyltrimethoxysilane or its Hydrochloride N-β-((N-vinylbenzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminopentyltrimethoxysilane or its hydrochloride N-β-((N-vinylbenzyl-N-benzyl ) Aminoethyl) -N-benzyl-γ-aminohexyltrimethoxysilane or its hydrochloride N-β-((N-vinylbenzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminoheptyltrimethoxysilane Or its hydrochloride N-β-((N-vinylbenzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminooctyl Lutrimethoxysilane or its hydrochloride N-β-((N-vinylbenzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminononyltrimethoxysilane or its hydrochloride N-β-((N-vinyl Benzyl-N-benzyl) aminoethyl) -N-benzyl-γ-aminodecyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-aminobutyltrimethoxysilane or its hydrochloride N-vinylbenzyl- N-benzyl-γ-aminopentyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-aminohexyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-aminoheptyltrimethoxysilane Silane or its hydrochloride N-vinylbenzyl-N-benzyl-γ Aminooctyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-aminononyltrimethoxysilane or its hydrochloride N-vinylbenzyl-N-benzyl-γ-aminodecyltrimethoxysilane or its hydrochloride Glass The amount of the silane coupling agent attached to the surface of the fiber (based on the solid content) is 0.001 to 0.5% by weight.
Is preferable, and more preferably 0.01 to 0.2.
It is in the range of% by weight.

The adhesion of the silane coupling agent to the surface of the glass fiber is carried out by using an aqueous solution containing the silane coupling agent represented by the general formula I or an organic solvent such as alcohols, ketones, glycols, ethers and dimethylformamide. It can be carried out by adhering the solution of 1 or a solution of a mixed solvent of water and these organic solvents to the glass fiber and then drying.

Further, at this time, in order to adjust the reactivity of the silane coupling agent of the general formula I to the matrix resin to be used, the silane coupling agent of the general formula I is 1
Or a mixture of two or more kinds, or one or more kinds of the silane coupling agent represented by the general formula I and one or more kinds of conventionally known silane coupling agents, the former silane coupling agent / the latter Weight ratio of silane coupling agent is 1
It can be used by mixing / 5 to 5/1. Further, the glass fiber is treated with one or more silane coupling agents of the general formula I and dried, and then treated with one or more conventionally known silane coupling agents and dried, or The processing may be performed in a different order.

Typical examples of conventionally known silane coupling agents include, for example, vinyltrichlorosilane, vinyltris (2-methoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.
Hydrochloride, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ
-Mercaptopropyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.

As a method of attaching the solution of the silane coupling agent to the glass fiber, various known methods such as a dipping method and a spray method can be used.

The treatment of the glass fiber base material by the dipping method is carried out, for example, by immersing the sheet-like processed product in a solution of the silane coupling agent at a temperature close to room temperature for several seconds, and then performing 3 by mangle.
We squeeze the liquid so that the pickup is 0% by weight, and then 100
It can be performed by drying and curing at ˜180 ° C. for several seconds.

Next, the glass fiber reinforced resin laminate of the present invention will be described. The glass fiber reinforced resin laminate of the present invention is for reinforcing the glass fiber base material of the present invention described above.

The glass fiber reinforced resin laminate of the present invention can be obtained by the following method, for example.

First, a resin such as an epoxy resin, a polyester resin, or a polyimide resin is impregnated into the above-mentioned glass fiber base material of the present invention by a conventional method such as a dipping method or a spray method, and then semi-dried and solidified to obtain a prepreg. To get After that, a desired number of the prepregs are laminated and molded into a desired shape by a conventional method such as a pressing method or a compression molding method, whereby the glass fiber reinforced resin laminated plate of the present invention is obtained.

A glass fiber reinforced epoxy resin laminated board, which is often used in the production of printed wiring boards and the like, can be prepared, for example, by impregnating the glass fiber base material of the present invention with an epoxy resin varnish,
It can be obtained by the method described above.

Examples of the epoxy resin used in this case include diglycidyl ether of bisphenol A,
Examples thereof include diglycidyl ether of bisphenol F, brominated epoxy resin, and polyglycidyl ether of novolac resin.

A curing agent (accelerator) is usually used in combination with these epoxy resins, and examples of the curing agent (accelerator) include amine-based, acid anhydride-based, and epoxy-based curing agents (shown below). Accelerator). Examples of the amine-based curing agent include diethylenetriamine, triethylenetetramine, diethylaminopropylamine, tetraethylenepentamine, aliphatic polyethertriamine, dicyandiamide, 4,4′-methylenedianiline (MD
A), m-phenylenediamine (MPDA), 4,4-
Diaminodiphenylsulfone, 2,6-diaminopyridine (DAP), 33.3% MPD-33.3MDA-
33.3% isopropyl MPDA, 40% MDA-60
% Diethyl MDA, 40% MPDA-60% MDA, aminopolyamide, 2-ethyl-4-methylimidazole, 2,4,6-tris (dimethylaminoethyl) phenol and the like. Further, as an acid anhydride-based curing agent, phthalic anhydride, hexahydrophthalic anhydride, nadic methyl hydride, dodecyl succinic anhydride, chlorendican hydride, trimellitic anhydride, maleic anhydride, Examples thereof include succinic anhydride, methyltetrahydrophthalic anhydride, and 3,3 ′, 4,4′-benzophenone-tetracarboxylic dianhydride.
Further, as an epoxy curing agent, butyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, allyl glycidyl ether, pt-t-
Examples thereof include butyl phenyl glycidyl ether, phenyl glycidyl ether and cresyl glycidyl ether.

The glass fiber reinforced resin laminate of the present invention may have a conductive metal layer made of copper, gold, silver or the like on at least one of its main surfaces. Such a conductive metal layer can be formed by a conventional method such as a pressing method. Further, the glass fiber reinforced resin laminate of the present invention may have an inner layer circuit.

The glass fiber reinforced resin laminate having these conductive metal layers is suitable as a material for printed wiring boards and the like.

[0027]

EXAMPLES Examples of the present invention will be described below. Unless otherwise specified,% and parts mean% by weight and parts by weight, respectively.

Example 1 Production Example of Glass Fiber Base Material β- (N-Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.hydrochloride (Toray Dow Corning Ning Silicone Co., Ltd. SZ-6032) )
A compound included in the general formula I by adding 1 mol of benzyl chloride to 1 mol of the compound of the formula

[Chemical 7] N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminopropyltrimethoxysilane · hydrochloride represented by

[Chemical 8] A silane coupling agent containing N-β- (N-vinylbenzyl-N-benzyl) aminoethyl-γ-aminopropyltrimethoxysilane · hydrochloride as a main component was obtained. Using the obtained silane coupling agent, an aqueous solution containing 0.5% (solid content) and 2.0% acetic acid was prepared and used as a treatment liquid.

Next, as a material for the glass fiber base material, a heat-treated and deoiled glass fiber woven fabric (trade name: WEA 18W,
Nitto Boseki Co., Ltd.) was dipped in the above treatment solution, and squeezed with a mangle so that the pickup was 30%.
It was heated and dried at 10 ° C. to obtain a glass cloth made of glass fibers having the silane coupling agent of the general formula I adhered to the surface thereof.

Comparative Example 1 As a silane coupling agent, β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride (SZ-6032 manufactured by Toray Dow Corning Ning Silicone Co., Ltd.) Was treated in the same manner as in Example 1 except that the above was used to obtain a glass fiber base material having a silane coupling agent attached.

Test Example 1 (impregnation test) First, test pieces for measuring impregnation having a length of 10 cm and a width of 6 cm were cut out from the glass fiber substrates obtained in Example 1 and Comparative Example 1, respectively. The test piece for measuring impregnability was floated on the following epoxy resin varnish (FR-4 formulation), and the epoxy resin varnish was completely impregnated between the filaments constituting the test piece while observing the impregnated state of the varnish by visual observation. The time until the completion (time required for impregnation) was measured for each test piece for measuring impregnation property.

[Composition of epoxy resin varnish] -Epicoat 5046-B-80 ... 100 parts (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.)-Epicoat 154 ... 20 parts (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) -Dicyandiamide ... 4 parts-Benzyldimethylamine ... 0.2 parts-Dimethylformamide ... 30 parts-Methylethylketone ... 15 parts These results are shown in Table-1.

[0033]

[Table 1] As is clear from Table-1, the impregnability of the epoxy resin varnish into the glass fiber base material obtained in Example 1 is superior to that of the epoxy resin varnish into the glass fiber base material obtained in Comparative Example 1. It was confirmed that

Example 2 Production Example of Glass Fiber Reinforced Resin Laminated Plate The glass fiber base material obtained in the above Example 1 was used as a reinforcing material,
The epoxy resin varnish (FR-4 formulation) having the above composition was dipped in these and predried to obtain a prepreg having a resin content of 43%. Then, 8 sheets of this prepreg were laminated, copper foil was laminated on the upper surface and the lower surface of the obtained laminate, and heat-molded by a conventional method to obtain a glass fiber reinforced epoxy resin laminated board having a thickness of 1.6 mm. Obtained.

Comparative Example 2 A glass fiber reinforced epoxy resin laminate was obtained in the same manner as in Example 2 except that the glass fiber base material obtained in Comparative Example 1 was used as a reinforcing material. Physical properties of the glass fiber reinforced epoxy resin laminates obtained in Example 2 and Comparative Example 2 were evaluated by the following methods.

Test Example 2 (Solder heat resistance test) The glass fiber reinforced epoxy resin laminate was subjected to an etching treatment to remove the copper layers on both sides of each glass fiber reinforced epoxy resin laminate, using a pressure cooker at 133 ° C. After the treatment, it was immersed in a solder bath at 260 ° C. for 20 seconds, and it was determined by visual observation whether or not the glass fiber-reinforced epoxy resin laminated plate after the immersion had blister. The results are shown in Table-2.

[0037]

[Table 2] As is clear from Table-2, the glass fiber reinforced epoxy resin laminate obtained in Example 2 is superior in heat resistance to the glass fiber reinforced epoxy resin laminate obtained in Comparative Example 2. Recognize.

[0038]

As described above, since the glass fiber base material of the present invention is treated with the silane coupling agent having excellent compatibility with the resin, it has excellent resin impregnation property and can be used in a short time. The resin is fully impregnated. Further, since the glass fiber base material of the present invention is treated with a silane coupling agent containing at least two benzene rings which are heat resistance imparting groups, the use of the glass fiber base material of the present invention excellent in solder heat resistance A glass fiber reinforced resin laminated board can be obtained.
Therefore, by using the glass fiber base material of the present invention, it becomes possible to manufacture a high quality glass fiber reinforced resin laminate with high productivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08J 5/08 CFC 7188-4F H05K 1/03 K 7011-4E

Claims (2)

[Claims] 1. The general formula I: [Q ¹ and Q ² in Formula I are represented by Formula II: Is a group represented by or hydrogen, and when n = 0, Q
¹ is a group represented by the formula II, and when n = 1 or 2, Q
^At least one of ¹ , Q ² is a group represented by the group of formula II. R ^{1 to} R ⁶ in formulas I and II are as follows. R ¹ : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ² : a divalent aliphatic hydrocarbon group having 6 or less carbon atoms R ³ : a divalent aliphatic hydrocarbon group having 10 or less carbon atoms group R ^4: 1 monovalent aliphatic having 6 or fewer carbon hydrocarbon group or an alicyclic hydrocarbon group or a phenyl group R ^5: an alkoxy group or an aryloxy group R ^6: 2-valent aliphatic having 6 or less carbon Group hydrocarbon group n is an integer of 0 or 1 or 2, and a is an integer of 0, 1 or 2. ] The glass fiber base material which consists of the glass fiber which the compound shown by these or its acid salt adhered to the surface. 2. A glass fiber reinforced resin laminate comprising the glass fiber base material according to claim 1 as a reinforcing material.