JPS6026498B2 - Method of manufacturing laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a laminate, and more specifically, the present invention is useful for manufacturing a copper-clad laminate that does not cause colored spots at the interface between copper and resin, and The present invention relates to a method for manufacturing a laminate having excellent electrical properties and resistance to electrical contact.

In the production of copper-clad laminates using epoxy resin, dicyanamide or BF3 is used as a curing agent for the epoxy resin.
A knitted body is used because it facilitates the acceleration of curing of the epoxy resin, improves the storage stability of the obtained prepreg, and has excellent cold resistance after curing.

However, when the curing agent is a BF3 anchor, there are problems such as coloring after curing and a decrease in its corrosion resistance, and in the case of dicyanamide, it has poor compatibility with epoxy resin, causing discoloration of the resin and Another disadvantage is that colored spots (brown spots) occur at the interface between copper and resin in copper-clad laminates, and further heating causes discoloration and deterioration of the electrical properties.

The present inventors have conducted intensive research to eliminate the above-mentioned drawbacks of copper-clad laminates using epoxy resin, and as a result, we have discovered that an organic aluminum compound and a hydroxyl group directly bonded to a silicon atom or hydration We have discovered that copper-clad laminates obtained by using organosilicon compounds having decomposable groups do not produce colored spots at the interface between copper and resin and have excellent electrical properties, and have developed the present invention. It has been completed.

That is, in the present invention, a resin composition is prepared by mixing an epoxy resin, an organic aluminum compound, and an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom, and then the resin composition is mixed. This is a method for manufacturing a laminate board, which comprises impregnating sheet-like base materials, laminating the sheet-like base materials, and finally curing by heating and pressurizing.

The main components of the resin composition used in the method of the present invention are:
It is epoxy resin. As the epoxy resin, any commonly known epoxy resin may be used and is not particularly limited. For example, bisphenol A type epoxy resins: bisphenol F type epoxy resins; phenol noporac type epoxy resins: alicyclic epoxy resins; heterocyclic epoxy resins such as triglycidyl isocyanate and hydantoin epoxy; hydrogenated bisphenol A type epoxy resins : Aliphatic epoxy resins such as propylene glycol-diglycidyl ether and pentaerythritol-polyglycidyl ether; epoxy resins obtained by the reaction of aromatic, aliphatic or alicyclic carboxylic acids with epichlorohydrin ; Spi-ring-containing epoxy resin, glycidyl-enal type epoxy resin which is a reaction product of an ortho-allyl-phenol novolak compound and epichlorohydrin; an allyl group at the ortho-position of each hydroxyl group of pisphenol A; Examples include a glycidyl ether type epoxy resin which is a reaction product of a diallylbisphenol compound and epichlorohydrin. Both the organic aluminum compound and the organic silicon compound used in the method of the present invention function as a curing catalyst.

Among these, organic aluminum compounds with 1 to 1 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, etc.
IN-specific alkoxyl groups; acyloxy groups such as acetoxy, stearoyl, butyryloxy, propionyloxy, impropionyloxy * groups; aryloxy groups such as phenoxy and p-methylphenoxy groups, and acetylacetone , trifluoroacetylacetone, bentafluoroacetylacetone,
Examples include flange bodies having ethyl acetoacetate, salicylaldehyde, diethyl malonate, etc. as ligands.

These aluminum compounds may be used alone or in combination of two or more, and the amount added is 0.001 to 5% by weight based on the epoxy resin.

The organosilicon compound used as another curing catalyst component is characterized by having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom.

Among these, those having silanol hydroxide groups are:
Examples include organosilanes and organosiloxanes described below.

That is, the following general formula [1]: (wherein R, R', R'' may be the same or different and represent an alkyl group, a phenyl group, an aralkyl group, a vinyl group, an allyl group, Further, p, q, and r are positive integers from 0 to 3, and p+q+r is within 3.

) or the following general formula [□]
:(In the formula, R,, R2, R3, R4, R5, R6, R7
may be the same or different and represent an alkyl group, phenyl group, vinyl group, aralkyl group, allyl group or a hydrolyzable group, and s, t, x, y are positive integers of 0 to 2. s+t and x+y are each within 2, u and w are 0
A positive integer of ~2; a and b represent positive integers of 0 or 1 or more.

) is an organosiloxane represented by

Further, examples of those having a hydrolyzable group include organosilanes and organosiloxanes described below.

That is, the following general formula [m]: (In the formula, R, R', R'', R... may be the same or different, and are an alkyl group, a phenyl group, an aralkyl group, a vinyl group, an allyl group. , p, q, and r are positive integers from 0 to 3, and p+q10** r is within 3.

) or general formula [W]: (wherein R,, R2, R3, R4, R5, R6, R7,
R8, R9, R, and o may be the same or different and are an alkyl group, a phenyl group, a vinyl group, an aralkyl group, an allyl group, or a hydrolyzable group, at least one of which is a hydrolyzable group. It is the basis.

S't'×'y is a positive integer from 0 to 2, and is a positive integer from 0 to 2.
are each within 2, u and w are positive integers from 0 to 2, a, b
is a positive integer of 0 or 1 or more. ) is an organosilane shown by

These organosilicon compounds may be used alone or in combination of two or more, and the amount added is 0.0001 to 10% by weight, preferably 0.0% by weight based on the epoxy resin.
It is 1 to 5%.

In the method of the present invention, first, a resin composition is prepared by mixing predetermined amounts of the epoxy resin, organic aluminum compound, and organic silicon compound detailed above.

At this time, no problem will arise even if various acid anhydrides, phenols, vinyl compounds, imide compounds, acrylic compounds, etc. are further blended. The obtained resin composition is impregnated into a sheet-like base material by a conventional method. The sheet-like base material to be used may be any material that is normally used for forming laminates, such as glass cloth or its non-woven fabric, carbon fiber cloth or non-woven fabric, ceramic fiber cloth or non-woven fabric, etc. can be given. Next, a plurality of impregnated sheet-like substrates are laminated and subjected to heating and pressure treatment according to a conventional method to form a laminate. The present invention will be explained below based on examples.

Example 1 Ebicoat 1001 (product name, Shell Chemical ■
6 parts by weight of Bisphenol A-based epoxy resin (manufactured by Shell Chemical), 4 parts by weight of Epikot 1 (trade name, phenol novolak epoxy resin manufactured by Shell Chemical), 3 parts by weight of trisacetylacetonatoaluminum, and diphenyljetoxysilane. A varnish with a non-volatile content of 5% by weight was prepared by dissolving 3 parts by weight in 10 parts by weight of methyl ethyl ketone.
The obtained varnish was impregnated into a glass cloth treated with epoxy silane to a thickness of 0.175 mm, and then heated at 140°C for 20 minutes.
A prepreg was prepared by drying for a minute.

Laminated 9 sheets of prepreg like this, then layered copper foil on top and bottom, and applied a pressure of 40k9/ground to 19
A hardening treatment was performed at 0oo for 100 minutes to create a double-sided steel-clad laminate. Example 2 Epiquat 1001: 90 parts by weight, Epiquat 828 (
Product name: 5 parts by weight of bisphenol A-based epoxy resin (manufactured by Shelley B Gaku■), 3 parts by weight of trisethyl acetoacetatoaluminum, and 3 parts by weight of triphenylmethoxysilane.
Part by weight was dissolved in 140 parts by weight of acetone to prepare a varnish with a non-volatile content of 5% by weight.

The obtained varnish was impregnated into a glass cloth treated with evoxysilane on the 0.175 thickness side, and then heated at 140°C for 10 minutes.
A prepreg was prepared by drying for a minute. Next, we layered nine sheets of this prepreg, and then layered copper foil on top and bottom.
Heat under the conditions of 180qo, 40k9/ground, 100 minutes.
A double-sided steel-clad laminate was created by pressure treatment. Example 3 Parts by weight of Eupikoat 1001:5, Eupikoat 1004
(trade name, bisphenol A epoxy resin manufactured by Shell Chemical ■) 20 parts by weight, YJCN220HH (trade name, cresol novolak resin manufactured by Toto Kasei ■) 3 parts by weight, trisacetelacetonalminium 3 parts by weight A homogeneous varnish was prepared in the same manner as in Example 2 using 3 parts by weight of diphenylsilane diol.

The same glass cloth used in Examples 1 and 2 was impregnated with the obtained varnish, and then dried at 13 mm for 10 minutes to prepare a prepreg.

Next, nine sheets of this prepreg were laminated, copper foil was layered on top and bottom of the prepreg, and a double-sided steel-clad laminate was produced by heating and pressurizing the prepreg at 18 pi, 40 k9/ground, and 100 minutes.

Comparative Example In the component composition of Example 1, 3 parts by weight of trisacetylacetonatoaluminum and 3 parts by weight of diphenylethoxysilane.
Instead of parts by weight, 3 parts by weight of dicyanamide and 0.5 parts by weight of 1-penzyl-2-methylimidazole were used, and methyl ethyl ketone-methyl cellosolve** (volume ratio: 1:1) was used instead of methyl ethyl ketone. A varnish with 50% non-volatile content was prepared.

A prepreg was prepared using this varnish in the same manner as in Example 1, nine sheets of this prepreg were laminated, and steel foil was further layered on top and bottom of the prepreg, and heated under the conditions of 175 qo, 40 k9/w, and 100 minutes. A double-sided copper-clad laminate was produced by pressure treatment.

For the above four double-sided steel laminates, we measured the presence or absence of brown spots, the presence or absence of discoloration after heating at 200°C for 2 hours, and the specific volume resistivity, yield rate, and positive dielectric saddle at each temperature. The results are summarized in the table.

As is clear from the table, the double-sided steel-clad laminate obtained by the method of the present invention has no colored spots or discoloration after heating and has superior electrical properties compared to the conventional one (comparative example). There was found.

Claims (1)

[Claims] 1. A resin composition is prepared by mixing an epoxy resin, an organic aluminum compound, and an organosilicon compound having a hydroxyl group or a hydrolyzable group directly bonded to a silicon atom, and then the resin composition is applied to a sheet-like base material. A method for manufacturing a laminate, which comprises: after impregnating, the sheet-like substrates are laminated, and finally cured by heating and pressurizing.