JPS58212945A - Manufacture of laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing laminates using a novel radiation-cured resin. More specifically, it is a Noripreg obtained by applying and impregnating cloth or nonwoven fabric with a varnish consisting of a solyl phthalate (hereinafter referred to as DAP) resin skeleton and a terminal -〇H group, a polyene, and a photosensitizer, and drying the coating. 1. Copper foil and laminate. The present invention relates to a method for obtaining a laminate by obtaining an integrated product and curing the resin system by irradiating radiation such as ultraviolet rays or electron beams from the silipreg side.

Conventionally, the method for obtaining DAP resin-based laminates is to first
A resin varnish is made by dissolving AP-P, DAP monomers and a thermal polymerization initiator in a solvent, and this is impregnated into glass cloth, etc., and heated and dried to obtain Silipreg. A method is known in which laminated copper foil is inserted between hot plates and cured under heat and pressure. However, this method has poor productivity because it performs thermal polymerization between soles, and also has poor affinity and adhesion of DAP, P, and DAP monomers with glass fibers and copper foil.
Problems such as peeling between resins and poor adhesion of copper foil can be fatal.
The elongation was significantly lower than that of other resin laminates. On the other hand, DAP resin-based laminates have excellent performance not found in other resins, and it is also true that application to laminates has been a long-standing dream of the industry.

- Examples include a high degree of electrical insulation, a high degree of dimensional stability, and stability of high frequency performance over a wide range of frequencies.

On the other hand, many attempts have been made to rationally obtain laminates by impregnating base materials with acrylate or methacrylate radiation-curable resins. However, due to the following fundamental drawbacks, a method of manufacturing a laminate using only a radiation curing method without thermal polymerization has not been put into practical use.

That is, (1) Generally, acrylate-based resins have extremely high curing shrinkage, and when formed into a laminate, they tend to warp and twist significantly. In addition, in order to avoid this phenomenon, a large amount of inorganic filler is added.
If ~, the radiation transmittance decreases.

(2) Reactive monomers are generally used, but their toxicity is a problem, and since a large amount of low molecular weight monomers are used, the stickiness cannot be removed even after drying, resulting in extremely poor workability. . Furthermore, the types of heptamers are limited due to the copolymerizability of the added monomer with the prepolymer, and in addition, homopolymers are also formed, which significantly impairs the physical properties.

(3) The oxygen inhibition effect is significant and the surface becomes uncured.

In order to prevent this phenomenon, a large amount of initiator must be used, which increases the radical concentration and results in a brittle cured product.

The present inventors 1) Overcame the conventional drawbacks without impairing the excellent performance of AP resin, and in addition, conducted intensive studies to find a method for manufacturing a laminate using only radiation curing.
We have arrived at the present invention.

That is, the aryl; We have found a method using a resin varnish containing a polyene having the following properties and a photosensitizer. When this resin system is used, the following characteristics are exhibited.

(1) Since the polyene-polythiol reaction is used, the curing shrinkage of the resin is small, and warping and twisting when forming a substrate can be completely prevented.

(2) Since the polyene-polythiol reaction is used, restrictions on polyF selection due to copolymerizability are greatly relaxed. Incidentally, there are only a few monomers used for radical crosslinking of DAP-P, such as DAP monomer and styrene.

(3) 1) Since AP-P is end-treated and modified to -8H, the compatibility and adhesion with the sheet base material are greatly improved. .

(4) Because it is based on DAP/P, it has excellent film-forming properties, and the prepreg after coating and drying has no viscosity at room temperature, and is also flexible, making it easy to wrap IJ f-legs. It is possible to take it. This greatly improves productivity.

(5) The obtained silipreg becomes viscous by increasing the temperature, making it possible to laminate it with copper foil.
Furthermore, the cured layer also has excellent copper foil adhesion due to the -8H group.

(6) Because of the polyene-polythiol reaction, there is no oxygen inhibition effect, and the amount of initiator is small, which, combined with the effect of the base material, provides a tough cured product.

Therefore, a so-called flexible substrate having flexibility can also be obtained.

(7) Radiation hardening such as ultraviolet rays and electron beams is possible.

The present invention is groundbreaking, as no method of manufacturing a laminate having such characteristics has been seen in the past. DAP, P or 1θ01) AP-P used in the present invention described in detail below
may be an ordinary commercially available product, and its degree of polymerization can be selected as appropriate.

Considering the film-forming property after addition of POIJF, DAP-P with a degree of polymerization of 5 or more is preferable.

In addition, the general formula R-(
:5H)71 (where n is an integer of 2 to 4, R is an organic group not containing a reactive double bond) can all be used, but preferred compounds include mercaptocar+lp Examples of commonly used esters of acids and polyhydric alcohols include t, "C'U," methylolpropane, tristhioglycole-1-, and methylolpropane (β-merkanot 70 ropionate). ,
pentaerythrittetrakis (thioglycolate),
These include pentaerythrittetrakis (β-mercaptogropionate), tris(hydroxyethyl)isocyanurate doris (β-mercazotoprobionate) ethylenec IJ colbis (β-merkanotogropionate), and the like. It is also possible to use these in combination.

In addition, the mixing ratio of DAP-P and/or 1soDAP-P and polythiol during prepolymerization is
- P and/or iso, DAP-P 2 or more equivalents of polythiol are required with respect to 1 equivalent, and if it is less than this, glue will be produced during prepolymerization. However, if the polythiol component is added too much, free polythiol will increase, resulting in DAP and P in the final cured product.
And/or the iso DAP-P component decreases, resulting in a decrease in heat resistance.

Therefore, it is important to use a polythiol with as little acid as possible that does not generate pores during prepolymerization.

Although the reaction proceeds even in the absence of a catalyst, it is also effective to add a radical initiator if necessary.

Furthermore, prepolymerization is usually carried out in a solvent, and the final composition is generally obtained in the form of a so-called varnish.
Any solvent that can dissolve -P and/or isoDAP-P can be used, and DAP-P and/or 18oDAP-P are further dispersed and dissolved in liquid polythiol, and the solvent is finally added to the heated reaction layer. It is also possible. The preferred solvent varies depending on the use of the composition, but since the varnish is applied to a sheet-like substrate and the solvent is removed by drying, a low boiling point solvent such as acetate, methyl ethyl ketone, or methyl isobutyl ketone is preferred.

Next, 1
A polyene compound having two or more reactive carbon-carbon unsaturated bonds in the molecule is added.

DAP, P and /° or 1θo 1) Thiol modification of AP-P improves compatibility with various polyenes and significantly improves copolymerizability, so polyenes such as acrylate compounds, methacrylate compounds, allyl Any compound can be used, but from the viewpoint of ease of control of reactivity, it is preferable to use a monomer compound.

Nine examples of shellfish include triaryl cyanurate, triaryl cyanurate-1, noaryl isophthalate, noaryl malate, noaryl itaco*-1,
Examples include noaryl chlorate, triaryl trimellitate, and the like, and these can be used alone or in combination.

Furthermore, free funds are generated by irradiating the above-mentioned polythiol sol polymer solution tobolyene mixture with radiation such as ultraviolet rays and electron beams. A photosensitizer is added, and examples of this compound include benzophenone, benzoin methyl ether, benzoin ethyl ether, etc. alone or in combination. The amount of these additions is 0.01 to 0.01 to the total resin.
Three layers are sufficient. It is also possible to add stabilizers, colorants such as pigments and dyes, extenders, etc. to the above composition as necessary.

The resin varnish thus obtained is applied to various sheet-like substrates. In this case, any sheet-like base material can be used as long as it has radiation transparency, but glass cloth, glass nonwoven fabric, polyester cloth, polyester nonwoven paper, etc. are particularly preferable from the viewpoint of radiation transparency. preferable.

In addition, it is appropriate for the resin coating area to be 30 to 70% thick after removing the solvent; if it is less than 30%, it will cause poor adhesion to the copper foil during lamination, and if it is more than 70%, the resin will have 20% −
The amount is large, causing trouble during lamination.

The coated impregnated layer is dried at a temperature of 120° C. or lower to remove the solvent, and then cooled. After cooling, it has no viscosity at room temperature and is an excellent prepreg. Next, one or more of the obtained silicone pregs and copper foil are laminated using a thermal laminator or the like. In a hot state, moderate viscosity is developed, so strong adhesiveness can be obtained. The laminate is then irradiated with radiation from the Silipreg side to completely cure the resin. Since irradiation for 10 seconds or less is sufficient, this is an extremely productive manufacturing method.

Therefore, an excellent single-sided metal-clad board can be obtained, which can be applied to f+, 1-int wiring boards, etc.
Its industrial significance is extremely high.

Examples are shown below.

Example I 600 parts by weight of powdered DAPf repolymer (manufactured by Osaka Soda ■, trade name: Daiso Dot: 7'A) and 400 parts by weight of methyl ethyl ketone (MFliK) were mixed in a 5-t flask to form a uniform solution.

Then, this solution was added with intererythrittetrakis (β-
Mercaptopropionate) 700 parts by weight were added,
Reacted at a temperature of 60°C for 2 hours, -8H content 2.4
A polythiol polymer of m-m01/f was obtained. This resin solution was then cooled, and 350 parts by weight of triaryl isocyanurate, 1 part by weight of benzophenone and MF;
A homogeneous varnish composition was obtained by adding and mixing K 1000 heavy weight.

Next, apply the above varnish to a glass cloth and lo.

After drying at a temperature of .degree. C., a highly flexible silicone preg without any stickiness was obtained. The two layers of Zorizoreg were stacked, and then a copper foil of Aμ was superimposed on top of the two layers, and laminated by passing between rolls set at 150'C. An integrated laminate product with adhesive properties was obtained. Next, the silicon preg side of the integrated product was irradiated with ultraviolet rays for 10 seconds using a high-pressure mercury lamp. The silipreg was completely hardened by irradiation, and a single-sided steel plate was obtained. The obtained copper laminate was excellent in flexibility, completely free from warping and twisting, and could be fully used as a circuit board.

Claims (1)

[Claims] Diaryl phthalate polymer (hereinafter referred to as DAP-P) and/or innoaryl phthalate sol polymer (hereinafter referred to as ODAP, P) and the general formula R-GSH
)n (wherein R is an organic group containing no reactive carbon-carbon unsaturated bond, n is an integer of 2 to 4) is a polythiol represented by the aryl group in DAP, P and/or iso DAP-P. A thiol sol polymer varnish (A ) and a photosensitizer ((
Step 8 (Step 81) for obtaining a resin varnish containing 3) as a main component, and applying and impregnating the varnish on a sheet-like base material such as a cloth or nonwoven fabric made of a fibrous material having radiation transmittance. A step of drying (Step 1), a step of overlapping the impregnated dried material by 1 mm or more and laminating it with copper foil to obtain an integrated laminate (Step 1II), and a step of applying radiation to the side of the impregnated dried material opposite to the copper foil. A method for producing a laminate, comprising the step of obtaining a copper-clad laminate by three-dimensionally cross-linking and curing the resin by irradiating the resin with water (step (2)).