JPS60233177A - Metal foil having adhesive layer and its manufacture - Google Patents

Abstract

PURPOSE:To manufacture the titled foil having excellent productivity and safety, continuously, by applying a photo-setting epoxy resin adhesive to a running continuous metallic foil, and irradiating the adhesive with ultraviolet radiation. CONSTITUTION:A running continuous metallic foil is coated with a photo-setting adhesive containing (A) an epoxy resin, (B) a photo-setting catalyst and (C) a thermally active hardener or catalyst, as essential components. Without interrupting the motion of the metallic foil, the photo-setting adhesive layer is irradiated with ultraviolet radiation. The objective metallic foil having an adhesive layer can be obtained by this process. The component C is preferably (i) a silicon compound forming silanol by ultraviolet radiation, (ii) an aluminum compound or (iii) an iodine- or sulfur-containing compound forming Lewis acid by ultraviolet radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an adhesive-coated metal foil that is excellent in productivity and safety in the manufacturing process, and a method for manufacturing the same.

[Technical background of the invention and its problems] Conventionally, adhesives used to bond metal foils and prepregs are thermoplastic resins such as butyral resin and nitrile rubber, melamine resins, 1-boxy resins, phenolic resins, etc. The adhesive solution is applied to the metal foil, and then the solvent is vaporized at high temperature. It is manufactured by semi-curing thermosetting resin with C.
There is.

However, in the method for producing metal foil with adhesive, a large amount of solvent is wasted, and a large amount of flammable solvent vaporizes, posing safety problems. In addition, in the above conventional method,
Because of the solvent vaporization, there is a limit to increasing the production speed, or there are problems such as the need for expensive equipment as the speed of III production increases.

[Objective of the Invention 1 The object of the present invention has been made to solve the above-mentioned problems, and is capable of manufacturing without using solvents or the like in the manufacturing process, and therefore can be manufactured at high speed and with simple equipment. The object of the present invention is to provide an adhesive-coated metal foil with excellent manufacturing productivity, safety, and workability, and a method for manufacturing the same.

[Summary of the Invention] As a result of extensive research to achieve the above object, the present invention has been developed by incorporating a photocuring catalyst and a thermally active curing agent or catalyst into a photocurable adhesive that is cured by irradiating ultraviolet rays, which will be described later. It has been discovered that the above object can be achieved by using the above in combination.

That is, the adhesive of the present invention (1) metal foil is a metal foil containing a photocurable resin composition containing (A) an epoxy resin, (B) a photocuring catalyst, and (C) a thermally active curing agent or catalyst. An adhesive characterized by being applied to the surface and irradiated with UV light (
=l metal foil.

Further, in the manufacturing method of the present invention, (A) an epoxy resin, (B)
A photocurable adhesive containing a photocuring catalyst and (C) a thermally active curing agent or catalyst as essential components is applied, and then photocured without interrupting the running of the metal foil! [This is a method for producing an adhesive-coated metal foil, which is characterized in that the adhesive-coated metal foil is continuously produced by irradiating the adhesive coated layer with ultraviolet rays at 04 L.

The present invention will be explained in more detail below.

The epoxy resin (A) used in the present invention is, for example, an epoxy resin or an epoxidized novolac resin obtained by condensing bisphenol A or bisphenol F or a halogen compound thereof with J-pychlorohydrin.

Typical examples include epoxidized cresol resin, epoxy-modified polybutadiene rubber, and alicyclic epoxy resin, and one or two of these resins may be used as a mixed system.

Furthermore, if necessary, a low-viscosity reactive diluent such as butyl glycidyl ether or noenyl glycidyl ether can be used in combination.

The (B) photocuring catalyst used in the present invention is as follows:
Examples include (a) silicon compounds that generate silanol when exposed to ultraviolet light, ([1) 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-ke-1-silyl group.

(T) As a compound having a peroxysilane group, 1
~Rif I nylsilyl tertiary 11 butyl peroxide,
Diphenylsilyl tert-butyl peroxide, trimethylsilyl tert-butyl peroxide, diphenylmethylsilyl tert-butyl peroxide, etc. are mentioned, and (■) compounds having 0-nitrobenzyloxy group include 5-trimethyl (θ-21~[ cobenzyloxy)silane,
Dimethylphenyl(θ~nitrobenzyloxy)silane, Schiffnylmethyl(0-nitrobenzyloxy)silane, triphenyl(0-nitrobenzyloxy)silane, vinylmethylphenyl(0-nitrobenzyloxy)
Silane, dobutylmethylphenyl(0-2I-daypenzyloxy)silane, l-ethyl(0-nitrobenzyloxy)silane, etc., and compounds having an (nl)α-ketosilyl group include triphenyl Examples include compounds such as benzoylsilane, diphenylmethylbenzoylsilane, p[yldimethylbenzoylsilane, and trinoenyl acetylsilane, and these compounds may be used alone or as a mixture of two or more.

The blending amount of these silicon compounds is in the range of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the epoxy resin. If the amount is less than 0.1% by weight, sufficient curing properties will not be obtained, and although it is possible to use more than 20% by weight, problems such as high loss and decomposition products of catalyst components may occur. 6, which is not preferable. □ The ([co))aluminum compound is a compound having an organic group selected from the group consisting of an alkoxy group, an oxy group, an acyloxy group, a β-diketonate group, a 0-carbonylphenorad group, etc. be.

Specific compounds include trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphoxyaluminum, trisparamethylphenoxyaluminum, isopropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum , trisstearadoaluminum, trisbutyradoaluminum, trispropionatoaluminum, trisisopropionatoaluminum, trisacetylacetonadoaluminum, and the like. These aluminum compounds can be used alone or as a mixture of two parts-L.

The blending amount is 0.001 to 10 per boxy resin.
The amount is 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, this is not preferable 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;
BF, -, PF6-1SbF6-1SnCI6-1Sb
Examples include at least one salt of anion such as 'Cl6-13i C1, -. Specific examples of onium salts used include 4.4'-dimethyldiphenyliodonium hexaflu 1] phosphate, 4.4'
-dimethyldiphenyliodonium tetrafluoroborate, trinoenylsulfonium hexafluoroantimone, trinoenylsulfonium hexafluoroantimone, etc., which may be used singly or in combination of two or more. It can be used as

The blending ratio of the onium salt of Lewis acid is in the range of 0.1 to 10% by weight, more preferably in the range of 0.2 to 5% by weight, based on the epoxy resin.

If it is less than 0.1% by weight, sufficient hardening properties cannot be obtained, and if it exceeds 10% by weight, problems such as high cost and corrosivity of decomposition products arise, which is not preferable.

Examples of the (C) thermally active curing agent and optional thermal curing catalyst used in the present invention include (a) dicyandiamide, hydrazides, organic acid anhydrides, aromatic amines, organic polyamines, etc. Examples of the catalyst (b) include imidazoles, tertiary amines, and amine salts of Lewis acids. Specific examples include dicyandiamide, succinic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, phthalic anhydride, succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl anhydride. Examples include nadic acid, pyromellitic anhydride, metaphenylene diamine, diaminodiphenylsulfone, boron trifluoride/monoethylamine, and these can be used alone or in combination of 29 or more types.

The blending amount of these thermally active curing agents or catalysts is 0.5 to 90% by weight, preferably 20 to 90% by weight for acid anhydrides, and 2 to 30% by weight for other substances, based on the epoxy resin.
is within the range of If the amount is less than 0.5% by weight, 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, a thermally active curing agent, and if necessary a thermosetting catalyst, but it also contains flame retardants, fillers, plasticizers, diluents, photosensitizers, antifoaming agents, and release agents as necessary. molding agent,
A small amount of solvent, etc. can be added.

The adhesive-coated metal foil of the present invention can be produced by applying the photocurable adhesive described above to the metal foil by a known method and then irradiating the coated surface with ultraviolet rays. . Light sources for ultraviolet irradiation include low-pressure mercury lamps,
It is possible to do this without using high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. Also, if necessary, infrared lamp,
It is also possible to use a far infrared lamp or the like.

The light irradiation time varies depending on the type of photocurable adhesive, type of base material, thickness, type of light source, coordination, number, output, etc.
Production is usually possible at a speed of 0.1 m/min to 30 m/min.

In this way, the adhesive-backed metal foil of the present invention can be semi-cured by UV irradiation alone, but since it contains a thermally active curing agent or catalyst, heating can also be used. . The manufacturing method of the present invention, in which an adhesive is applied to a running long metal foil and ultraviolet rays are irradiated without interrupting the running of the metal foil, is the most efficient.

The adhesive metal foil produced in this way is combined with 3 to 10 semi-cured prepregs impregnated with various resins, and is exposed to light by applying pressure at a temperature of 10°C to 180°C using a known method. A metal-clad laminate can be obtained by converting the adhesive to hot sand. That is, since the adhesive-coated metal foil of the present invention contains a thermally active curing agent or catalyst, it can be heated and formed into a 1f shape by a conventional method.

“Embodiments of the invention” Next, embodiments of the present invention will be described.

Example 1 Bisphenol A epoxy resin 1 Bicoat #1001
(Product name manufactured by Yuka Shell Epoxy Co., Ltd.) 30 (Ig, alicyclic epoxy resin ERI-4221 (=-Product name manufactured by Nion Carbide Co., Ltd.) 300 g, butyl glycidyl ether 100 g, 1 Bicoat #828 (Yuka Shell Epoxy Co., Ltd.) 300(], triphenyl(0-2l-lobenzyl Axy)silane 20!], 5g of l-lisisopropionatoaluminum, and 40g of finely ground dicyandiamide were heated at 5()°C. The mixture was heated and stirred for 10 minutes to obtain a uniform photocurable adhesive.

After preheating this adhesive to 50°C and applying it to the electrolytic copper foil,
Under two 80W/cn+ high pressure mercury lamps (10c
An adhesive-coated copper foil was produced by passing the copper foil through a tube (under 5 m) at a speed of 5 m and 7 minutes. The surface of the adhesive after irradiation with ultraviolet rays is hardened and can be stored, and the amount of adhesive applied is 42 (8 sheets of C
It was 2. This copper foil with adhesive is 175℃
A copper-clad laminate was obtained by heating and pressing at 120 kg/cm2 for 3 hours. This characteristic is shown in Table 1, and this is the copper clad f
It had sufficient characteristics as an M-layer board.

Example 2 Shrimp]-1 to #1001 (mentioned above) 200 (1, ER
L4221 (previously mentioned> 4001J, shrimp coat #8
28 (supra) 400 (], ]l Lauryenylsilyl tert-butyl peroxide 30], ]i Millis acetylacetonado aluminira 110 isophthalic acid dihydrazide' 30 g, and 2-, ethyl-4-methylimidazole 2 g, Each component was heated and stirred at 50°C for 10 minutes to obtain a uniform photocurable adhesive. After preheating this adhesive to 50°C and applying it to electrolytic copper foil,
/ cm under two high-pressure mercury lamps (10 cm below).
The adhesive (=l copper foil) was produced by passing it through at a speed of m7 min.

The surface of the adhesive after irradiation with ultraviolet rays was hardened and could be stored, and the amount of adhesive applied was 40 g/In2.

This adhesive-coated copper foil and 8 sheets of prepreg impregnated with phenolic resin were stacked at 175℃ and 120 kg.
/Cl112 for 3 hours to obtain a copper-clad laminate.

Its properties are shown in Table 1, and it had sufficient properties as a copper-clad laminate.

Example 3 Epicoat #10:01 (see above) 3oog, Ebikoat #828 (see above) 200o, bisphenol F type epoxy resin Epicoat #807 (product name manufactured by Yuka Shell Epoxy Co., Ltd.) 300<1. Butyl glycidyl ether 200g, 4. 1-5 g of 1-dimethyldiphenyliodonium hexafluorophosphate, 601 J of isophthalic acid dihydrazide, 2 g of 2-ethyl-4-methylimidazole, and 200 q of methyl ethyl ketone were heated and stirred at 50°C for 10 minutes to form a uniform mixture. After preheating this adhesive to 60°C and applying it to the electrolytic steel part, it was heated under two 80 W/cm high-pressure mercury lamps (10 cn+) at a speed of 7 m and 7 min. After irradiation with UV rays, the adhesive has a hardened surface and can be stored, and the amount of adhesive applied is 3.
It was 5g/ra2.

14- Layer this adhesive-coated copper foil and 8 sheets of prepreg impregnated with phenol resin and call it C, and heat at 175°C for 120k (]/
A copper-clad laminate was obtained by heating and pressing at cm2 for 3 hours.

Its properties are shown in Table 1, and it had sufficient properties as a copper-clad laminate.

Example 4 ■Picot 1 to #828 (mentioned above) 500g, butyl glycidyl ether 200Q, ERL 4221 (
The following ingredients were heated and stirred at 50°C for 10 minutes to form a homogeneous mixture: A photocurable adhesive was obtained.

After preheating this adhesive to 50°C and applying it to the electrolytic copper foil,
Under two 80W/cm metal halide lamps (1
0 cm F) at a speed of 10 m/min to produce an adhesive-coated copper foil. The surface of the adhesive after UV irradiation is hardened and can be stored, and the application m is 38 (1/
It was m2. This adhesive coated copper foil was stacked with 8 sheets of prepreg impregnated with phenol resin, and heated at 175℃ for 1 hour.
A copper-clad laminate was obtained by heating and pressing at 20 k(]/cm2 for 3 hours. Its properties are shown in Table 1, and it had sufficient characteristics as a copper-clad laminate.

Example 5 The photocurable adhesive obtained in Example 4 was preheated to 50°C and applied to aluminum foil, and then heated at a speed of 10 m/min under two 80 W/cm metal halide lamps (10 cm below). Through the adhesive, aluminum foil was produced.
The surface of the adhesive after irradiation with ultraviolet rays was hardened and could be stored, and the coating amount was 350/l12. Layer this adhesive 1 aluminum foil on 8 sheets of prepreg impregnated with phenolic resin at 115℃ and 120kO.
/cm2 for 3 hours to obtain an aluminum-clad laminate. Its properties are shown in Table 1, and it had sufficient properties as an aluminum-clad laminate.

Table 1* Tests were conducted on copper-clad laminates coated with a commercially available thermosetting adhesive.

[Effects of the Invention] As explained above, according to the present invention, adhesive-coated copper foil can be manufactured at high speed and with simple equipment without using a solvent, improving manufacturing productivity and safety. It has a remarkable effect on properties and workability, and it is possible to obtain a metal-clad laminate having f'X properties equivalent to conventional ones, so its industrial value is extremely high at 6%.

Claims (1)

[Claims] 1 (A) an epoxy resin, (B) a photocuring catalyst, and (C
) A metal foil with an adhesive, which is made by applying a photocurable adhesive containing a heat-activated curing agent or catalyst as an essential component to the metal foil and irradiating it with ultraviolet rays. 2. The photocurable catalyst is (a) a silicon compound that produces silanol when exposed to ultraviolet light, (b) an aluminum compound, or (c) an iodine or sulfur-containing compound that produces silanic acid when exposed to ultraviolet light. The metal foil with adhesive according to item 1. 3. On the running long metal foil, (A>epoxy resin, (
B) A photocurable adhesive whose essential components are a photocuring catalyst and (C) a thermally activated curing agent or catalyst.The adhesive is applied, and then the photocurable adhesive coating layer is applied without interrupting the running of the metal foil. 1! Adhesive-coated metal foil characterized in that the adhesive-coated metal foil is continuously produced by irradiating ultraviolet rays on the adhesive-coated metal foil. ! Construction method.