JPS60231737A - Production of laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a laminated sheet at a high rate of production, by impregnating bases with a photocurable resin composition comprising an epoxy resin, a photocuring catalyst, and a thermally activatable curing agent or catalyst, irradiating the bases with light and laminating the obtained prepregs under application of heat and pressure. CONSTITUTION:A photocurable resin composition essentially consisting of 100pts. wt. epoxy resin, about 0.001-10pts.wt. photocuring catalyst (e.g., triphenylsilyl tert-butyl peroxide or trismethoxyaluminum) and about 0.5-90pts.wt. thermally activatable curing agent or catalyst (e.g., dicyandiamide or m-phenylenediamine) is applied to buses such as paper or cloth by impregnation. A plurality of the obtained prepregs are laminated under application of heat and pressure to obtain the purpose laminated sheet.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to a method for manufacturing a laminate, and more specifically, the present invention relates to a method for manufacturing a laminate, and more specifically, the method for manufacturing a laminate using prepreg, which is a material thereof, can be performed using high-speed, simple equipment, and has good productivity, safety, and workability. The present invention relates to a method for manufacturing a laminate that can be manufactured.

[Technical background of the invention and its problems] Conventionally, prepregs used for epoxy resin-based laminates are
Epoxy resin has been manufactured by dissolving epoxy resin in a large amount of solvent, passing the solution through a base material such as glass cloth to impregnate the resin solution, and then vaporizing the solvent at high temperature and simultaneously semi-curing the epoxy resin.

However, this conventional method wastes a large amount of solvent and poses safety problems due to vaporization of a large amount of flammable solvent. In addition, in this conventional method, it takes time to semi-cure the 1-poxy resin due to solvent evaporation, and therefore there is a limit to increasing the production speed further. [Objective of the Invention] The object of the present invention was to solve the above problems, and to remove ultraviolet rays without using unnecessary solvents. The present invention aims to provide a method for manufacturing a laminate, which semi-cures prepreg by irradiation, requires high-speed and simple equipment for manufacturing the prepreg, and has excellent productivity, safety, and workability.

[Summary of the Invention] As a result of intensive research to achieve the above object, the present inventors discovered that the above object could be achieved by using the resin composition described below, and in completing the present invention. This is what we have come to.

That is, the present invention is a paper fabric base material impregnated and coated with a photocurable resin composition containing (A>epoxy resin, (B) photocuring catalyst, and (CJ thermally active curing agent or catalyst) as essential components. There is a method for manufacturing a laminate, which is characterized in that a prepreg is obtained by irradiating the prepreg with ultraviolet rays, and the prepregs are laminated and heated and pressurized.

The present invention will be explained in more detail below.

The epoxy resin (A) used in the present invention includes, for example, an epoxy resin obtained by condensing bisphenol A or bisphenol F or its halogen compound with epichlorohydrin, an epoxidized novolac resin, an epoxidized cresol resin, an epoxy-modified resin. Typical examples include polybutadiene rubber and alicyclic epoxy resin, and these resins may be used alone or as a mixture of two or more. Furthermore, it is also possible to use a low-viscosity reactive diluent such as butyl glycidyl ether or phenyl glycidyl ether, if necessary.

The (B) photocuring catalyst used in the present invention includes:
Examples include (a) silicon compounds that generate silanol when exposed to ultraviolet light, (b) aluminum compounds, and (c) iodine- or sulfur-containing compounds that generate Lewis acids when exposed to ultraviolet light.

First, (a) the silicon compound that generates silanol when exposed to ultraviolet light needs to be a silicon compound having any one of a peroxysilane group, an 0-nitrobenzyloxy group, and an α-ketosilyl group.

(I> Compounds having a peroxysilane group include triphenylsilyl tertiary butyl peroxide, diphenylsilyl tert-butyl peroxide, trimethylsilyl tert-butyl peroxide, diphenylmethylsilyl tert-butyl peroxide, etc. ) As compounds having an o-nitrobenzyloxy group, trimethyl(0-nitrobenzyloxy)silane, dimethylphenyl(0-nitrobenzyloxy)
Silane, diphenylmethyl (Kanonitrobenzyloxy)
Silane, triphenyl(0-nitrobenzyloxy)silane, vinylmethylphenyl(0-nitrobenzyloxy)silane, t-butylmethylphenyl(〇-nitrobenzyloxy)silane, triethyl(0-21 to [7+
benzyloxy)silane, etc., (I[[')α
- Compounds having a ketosilyl group include triphenylebenzoylsilane, diphenylmethylbenzoylsilane, phenyldimethylbenzoylsilane, triphenylacetylsilane, etc. These compounds may be used alone or in combination of two or more. used as a system. The blending amount of these silicon compounds is 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the epoxy resin.
The weight range is %. If the blending amount is less than 0.1% by weight, sufficient curing properties cannot be obtained;
Although it is possible to use more than 20% of the catalyst, it is not preferable because it may lead to high cost and problems with decomposition products of the catalyst components.

(b) The aluminum compound is a compound having an organic group selected from the group consisting of an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, and an F carbonylphenorad group.

Specific compounds include trismethoxyaluminum, trisethoxyaluminum, trisisoproboxyaluminum, trisphenoxyaluminum, trisbaramethylphenoxyaluminum, isopropoxyjethoxyaluminum, trisbutoxyaluminum,
Examples include trisacetoxyaluminum, trisstearadoaluminum, trisbudylatoaluminum, trispropionatoaluminum, trisisobrobiona1-aluminum, trisacetylacetonadoaluminum, and the like. These aluminum compounds can be used singly or as a mixture of two or more, and the blending amount is 0.001 to 10% by weight based on the epoxy resin.
, more preferably in the range of 0.05 to 5% by weight.
If the amount is less than 0.001% by weight, sufficient curing properties cannot be obtained, while if it exceeds 10% by weight, it is undesirable because it causes increased costs and deterioration of electrical properties.

(c) Iodine or sulfur-containing compounds that generate Lewis acids when exposed to ultraviolet rays include aromatic iodonium cations,
At least one aromatic sulfonium cation;
BF4-, PF6-1SbF6-1SnC16-1S
Examples include at least one salt of anions such as bCI6'-1s+ CI5-. Specific examples of onium salts used include 4,4'-dimethyldiphenyliodonium hexafluoro07ospha[-14,
Examples include 4'-dimethyldiphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, and these may be used alone or in combination of two or more. I can do it. The blending ratio of the onium salt of Lewis acid should be in the range of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, based on the epoxy resin. If it is less than 0.1% by weight, sufficient curing properties cannot be obtained, and if it exceeds 10% by weight, problems such as high cost and corrosivity of decomposition products may occur, which is not preferable.

Examples of the thermally active curing agent or catalyst (C) used in the present invention include (a) curing agents such as dicyandiamide, hydrazides, organic acid anhydrides, aromatic amines, and organic polyamines; Examples of the catalyst include imidazoles, tertiary amines, and amine salts of Lewis acids. Specific examples include dicyandiamide, succinic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, phthalic anhydride, succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride. Examples include acids, pyromellitic anhydride, metaphenylene diamine, diaminodiphenylsulfone, boron trifluoride/monoethylamine, and these can be used alone or in combination of two or more.

The blending amount of these thermally active curing agents or catalysts is 0.5 to 90% by weight, more preferably 20 to 90% by weight for acid anhydrides, and 2 to 30% by weight for other substances, based on the epoxy resin.
% by weight. If the blending amount is 0.5% by weight without swirling, sufficient curing properties cannot be obtained, and if it exceeds 90% by weight, the storage stability is poor and the curing properties are also impaired, which is not preferable.

The photocurable resin composition used in the present invention includes epoxy resin,
It consists of a photocuring catalyst and a thermally active curing agent or catalyst, but if necessary, flame retardants, fillers, plasticizers, diluents, photosensitizers, antifoaming agents, mold release agents, and small amounts are added. Solvents, etc. can be added.

8 of the present invention! The method for producing an I-layer board is to impregnate and coat a glass cloth or paper base material with the photocurable resin composition described above by a known method, and then irradiate the prepreg with ultraviolet rays from both the front and back sides of the impregnated base material. Manufacture. Light sources for ultraviolet irradiation include low-pressure mercury lamps, high-pressure mercury lamps,
A xenon lamp, metal halide lamp, etc. can be used.

Further, an infrared lamp, a far-infrared lamp, etc. can be used in combination as necessary.

The light irradiation time varies depending on the type of resin composition, the type and thickness of the base material, and the type, arrangement, number, and output of the light sources, but is usually manufactured at a speed of 0.1 m/min to 30 m/min. I can do it. This prepreg can be manufactured in a batch manner, but continuous manufacturing provides cost benefits. The prepreg produced in this way has 3 to 10
A laminate can be produced by combining the sheets and heating and pressing them at a temperature of about 100 to 180° C. using a known method.

As described above, the manufacturing method of the present invention can manufacture a prepreg by photo-curing, and can also mold a laminate by heat-curing as in the conventional method. Of course, it is possible to use both photocuring and heat curing in the production of prepreg.
The present invention does not prevent this.

Prepreg can be used not only for laminates but also for other purposes such as adhesives and pinned depths.

[Embodiments of the invention] Examples of the present invention will be described in detail below.

Example 1 Bisphenol A epoxy resin Epicoat #1001
(Product name manufactured by Yuka Shell Epoxy Co., Ltd.) 300 (], Alicyclic epoxy resin ERL4221 Product name manufactured by UJCC Co., Ltd.>
3001j, butyl glycidyl ether 100g.

Epicor 1 to #828 (trade name manufactured by Yuka Shell Epoxy Co., Ltd.) 3000, triphenyl(0-nitrobenzyloxy)silane 20 (1), trisisopropionatoaluminum 5g, and finely ground dicyandiamide 40 (
+ and heated and stirred at 150°C for 10 minutes,
A uniform photocurable resin composition was obtained.

This resin composition was preheated to 50°C, the resin composition was impregnated and applied through glass cloth AS7628W (trade name manufactured by Asahi Siebel Co., Ltd.) into the resin, and then squeezed with a roll.
The prepreg was produced by passing it through two 80 W/cn+ high-pressure mercury lamps (lamp interval 20 cm) at a speed of 5 m7 min. After irradiation with ultraviolet rays, the prepreg has a hardened surface and can be cut, and the cut surface is not sticky and can be stored.

The resin content of the prepreg is 40% by weight, and the gel time is 160%.
℃ for 3 minutes. Five sheets of this prepreg and 35 μm thick copper foil were stacked and heated and pressed at 175°C and 50K (1/cm2) for 3 hours to produce a copper-clad laminate.

This laminate had sufficient strength and adhesive strength.

Example 2 Epicote #1001 (mentioned above) 200 (], E
RL4221 400g (mentioned above), Shrimp Coat #828
(Previously) 400 (1, 3 h of triphenino ρ silyl tert-butyl peroxide, 10 g of tris-arethylacetonado aluminum, 30 g of isophthalic acid dihydride
, and 2 g of 2-ethyl-4-methylimidazole were mixed and heated and stirred at 50° C. for 10 minutes to produce a uniform photocurable resin composition.

This resin composition was preheated to 50°C, the resin composition was impregnated and coated through a glass cloth AS7628W (mentioned above) into the resin, and then squeezed with a roll. interval 20cm) 5
The prepreg was produced by running at a speed of m7 min. After UV irradiation, the prepreg had a hardened surface and could be cut and stored.

The resin content of the prepreg is 38% by weight, and the gel time is 160%.
℃ for 2 minutes and 20 seconds. Five sheets of this prepreg were stacked and heated and pressed at 175° C. and 50 kg/cm 2 for 3 hours to produce a laminate. This laminate was sufficiently strong.

Example 3 Epicoat #1001 (mentioned above) 300 (J, 1 pico) to #828 (mentioned above) 200 (1, bisphenol F type epoxy resin Epicoat #, 807 (trade name manufactured by Yuka Shell Epoxy Co., Ltd.) 300 ( ] 1-butyl glycidyl ether 200 g, 4,4'-dimethyldiphenyliodonium hexafluorophosphate 5 g, isophthalic acid dihydrazide 60 (], ] 2-ethyl-4-methylimidazole 29 and methyl ethyl ketone 200 g
Each component was blended and heated and stirred at 50° C. for 10 minutes to produce a uniform photocurable resin composition.

This resin composition was preheated to 60°C, and the resin composition was impregnated and coated through a glass cloth AS7628W (mentioned above) into the resin, and after being wrung out with a roll, it was heated between two 80W/cm high-pressure mercury lamps ( Lamp interval 20cm) 7
A prepreg was produced by passing the sample at a speed of m7 minutes. After UV irradiation, the prepreg had a hardened surface and could be cut and stored.

The resin content of the prepreg is 40% by weight, and the gel time is 160%.
℃ for 2 minutes and 10 seconds. Four sheets of this prepreg were stacked and heated and pressed at 175° C. and 50 kg/cn+2 for 3 hours to produce a laminate. This laminate is strong enough. It was something.

Example 4 1 Biquat 9828 (supra) 500 (1, Butylglycidyl T-Til 200 (1, EH11221 (supra)
300Q, triphnylsulfonium hexafluorophosno-I-t 1h1h lisacedelacetonadoaluminum 5g1 and triphenylmethoxysilane 20
Each component of g was blended and heated and stirred at 50° C. for 10 minutes to produce a uniform photocurable resin composition.

This resin composition was preheated to 50°C, and the resin composition was impregnated and coated through a glass cloth AS7628W (mentioned above) into the resin, and then squeezed with a roll. 200 m ) at a speed of 10 m/min to produce prepreg. After UV irradiation, the prepreg has a hardened surface, making it difficult to cut or
Storage was possible.

The resin content of the prepreg is 38% by weight, and the gel time is 160%.
℃ for 2 minutes and 50 seconds. Stack these 4 sheets of prepreg, roughly layer 35μm thick copper foil on the front and back,
A double-sided copper-clad laminate was manufactured by heating and pressing at a temperature of 50 kg/Cll12 for 3 hours. This double-sided copper-clad laminate had sufficient strength and adhesive strength.

Comparative Example 1 Epicoat #1001 (mentioned above) 300 (1, Epicoat #1004 (trade name manufactured by Yuka Shell Epoxy Co., Ltd.) 20
0 g, dicyandiamide 30 g, 2-ethyl-4-methylimidazole 1.01; l, and acetone 50
0g of each component was blended, dissolved and stirred at 30°C for 1 hour,
A homogeneous resin solution was obtained.

Glass cloth AS7628W was used in this resin solution at 30°C.
(mentioned above), and after squeezing with a roll, the prepreg was passed through an oven at 150° C. (height: 3 m) for 3 minutes at a speed of 2 ta/min to obtain a prepreg. After drying, the prepreg had evaporated solvent and was not sticky and could be cut and stored.

Compared to Example 1, twice the amount of resin was required to produce the same amount of prepreg. When a laminate was manufactured using this prepreg in the same manner as in Example 1, Example 1
It was practical to the same extent.

Comparative Example 2 Epikote #1001 (mentioned above) 200Q, Epikoat #1004 (mentioned above) 3oog, dicyandiamide 2
5g, 2-ethyl-4-methylimidazole 1.5g,
400g of acetone and 100g of methyl ethyl ketone
Each component was blended, dissolved and stirred at 30° C. for 1 hour to obtain a uniform resin solution.

Glass cloth As7628W was used in this resin solution at 30°C.
(mentioned above), and after squeezing with a roll, the prepreg was passed through an oven at 150° C. (height: 8 m) at a speed of 5 m and 7 min for 3 minutes to obtain a prepreg. After drying, the prepreg had evaporated solvent and was not sticky and could be cut and stored.

Compared to Example 2, twice the amount of resin was required to produce the same amount of prepreg. When a laminate was manufactured using this prepreg in the same manner as in Example 2, Example 2
It was equally practical.

[Effects of the Invention] According to the present invention, there is no need to use solvents or the like in the production of prepreg, and therefore prepreg can be produced with high productivity, workability, and safety using high-speed and simple equipment. The properties of the laminate manufactured using this method are also the same as those of conventional products. As described above, the industrial value of the production method of the present invention is extremely large.

Claims (1)

[Claims] 1 (A) an epoxy resin, (B) a photocuring catalyst, and (C
) After impregnating and applying a photocurable resin composition containing a thermally active curing agent or catalyst as an essential component to a paper fabric base material, irradiating it with ultraviolet rays to obtain a prepreg, laminating the prepregs and heating and pressurizing them. A method for manufacturing a laminate, characterized by: 2 (B) A patent claim in which the photocuring catalyst is (a) a silicon compound that produces silanol when exposed to ultraviolet rays, (b) an aluminum compound, or (c) a compound containing iodine or sulfur that generates lyluis acid when exposed to ultraviolet rays. A method for producing a laminate according to item 1. 3. A claim that continuously manufactures a prepreg by impregnating and applying a photocurable resin composition to a running long paper fabric base material and then irradiating it with ultraviolet rays without interrupting the running of the paper fabric base material. A method for manufacturing a laminate according to item 1 or 2.