JPS59127724A - Manufacture of laminate - Google Patents

Abstract

PURPOSE:To obtain a phenolic resin laminate safely and efficiently, by coating a base material for a laminate to which a hardening agent is applied with a phenolic resin which does not contain any solvent to prepare a prepreg, layering a prescribed number of such prepregs, and molding them under heating and pressure. CONSTITUTION:A base material such as paper, glass fiber cloth, etc. for a laminate is previously impregnated well with a hardening agent (e.g. hexamethylenetetramine) for example by spraying. Then the base material is coated with a phenolic resin such as a novolak type phenolic formaldehyde resin, a drying oil-modified novolak type phenolic formaldehyde resin, etc. free from any solvent to produce a prepreg. A prescribed number of such prepregs are layered, a copper foil, if desired, is placed thereon, and they are pressed between a flat plate press and a flat plate at about 150 deg.C for about one hour under a pressure of approx. 10-150kg/cm<2> to obtain the desired laminate without using any solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION The invention relates to a method for manufacturing laminates or copper-clad laminates without bathing. The purpose of this is to eliminate the inconvenience of bath salts, eliminate the drying process when making Grigregs, and improve the efficiency of the VC manufacturing method. - A large amount of bath agent is used, and since the coating is applied in one warehouse just before production, the resin content or viscosity of the varnish is adjusted to f/(R1゜). Moreover, in the coating process of these bath additives, heat is added from the outside to dry and external VC is scattered.
,'r. From the viewpoint of dust safety, these bath salts are burned and then released into the outside air. By using it in bath salts in this way, the disadvantages of increased drying costs and pollution costs were borne. In addition, bath additives have the problem of increasing fire hazards. Apply the base material C on the phenol side to create a frigleg ligature.
2. After determining the number of sheets, remove the Lvc copper foil and heat and press mold it. A certain mold r
May be used.

By doing this, the solvent is removed and there is no drying process [
Laminated board manufacturing machine C and force S Xiaomiru.

A method for manufacturing phenolic resin laminates without using bath additives is to apply a hardening agent and resin strength to the base material together with a hardening agent and powdered Nobo2tsuk resin powder. The problem with this method is that the molding conditions have a narrow range. Is the present invention a hardening agent and a 2-ethanol side fat? Because it is separated and applied to the base material, it has the advantage of being easy to manufacture and control while controlling the molding conditions.

Uninvented? Let's take a closer look. The base materials for the laminates used in the invention include paper and cotton, natural fibers such as cicada (blank below), organic synthetic fibers such as cloth, holamide, polyester, polyvinyl alcohol, and acrylic, and non-imageable fibers such as glass and asbestos. These are non-woven mats and the like.

Considering the penetration of resin into the base material, the strength decreases by 0.3 to 0.6 depending on the degree of adhesion between the base material and paper, and the number of laminated layers V (
L, in case r (reduced cutting) causes a decrease in mechanical strength.

Other substrates can be used with few limitations. Regarding glass fiber cloth, non-woven fabric, and matte VC, are the base materials subjected to surface treatment? It is desirable to use it.

Furthermore, the phenolic resin used in the bath agent is a novolak-type phenol formaldehyde resin, tung oil, and linseed? Polyester resin or, if necessary, aromatic hydrocarbon resin such as xylene resin, is modified with novolak-type resin.Here, the bath agent 2 and 11 refers to the drying process of the resin solvent during the production of Gripreg. 1C and 2 meanings.

Novolac-type phenol trees are usually obtained by inversely comparing π-phenol, cresols, and formaldehyde in the presence of acid catalysts such as Yotsutaku hydrochloric acid and Shukinato, which are carried out in the process.
,/S. Phenols are difficult to produce.

The drying oil-modified novolanc resin is prepared by combining a drying oil such as tung oil or linseed oil with a noholac resin obtained by the above method in the presence of an acid catalyst such as kevaradruene sulfonic acid.
The reaction is carried out at 150°C, and the unreacted drying oil is neutralized with a basic substance such as triethylamine, diethylamine, or pyridine to prevent the reaction from proceeding even if heated. ^8 This is to prevent the reaction from proceeding during the coating process and gelation.Novolak-type phenol resin modified with an aromatic hydrocarbon resin such as xylene resin can be used with a xylene resin, e.g. Dicanol H (product name of Mitsubishi Gas Chemical Co., Ltd.) is reacted with phenol, cresols, etc. over a hostile catalyst such as kevaradruene sulfone, and then the formaldehyde is removed.
An 85-mol knife was used, and a 6r-thickness was removed from the novolata-type xylene denatured phenolic resin. Today, part 1
It may be used as a side wall for a laminated board, or it may be used after reacting with a drying oil such as tung oil as described above.

In addition, conventional flame retardant additives are mixed with the above novolac type phenolic resin and modified novolac type phenol resin to achieve even greater flame retardancy! R
It should be possible to manufacture laminated plates. In particular, examples of phosphorus-based flame retardants include triphenyl phosphate and tricresyl phos-7z-
), talesyl diphenyl phosphate, and xylyl di-2-enyl phos-2ate z are effective in lowering the viscosity of novolank-type phenolic resins, and are suitable for use with VCs when used with Glypref 2.

Since it is possible to supply the base material F (C) as a powder, the conventional kneading process can be omitted using a mineralized flame retardant such as antimony trioxide L and R. Lowered VCC future 0 base material π pre-applied as a curing agent f” I used as a curing agent for phenolic type phenol side fat fL hexamethylenetetramine, trioxane, resol type? enol formaldehyde &r 116
As a curing agent, hexamethylenetetraban, which is thermally stable and does not contain metal elements, is preferred.

When using a curing agent, it is necessary to apply 2 to 25 parts [72 parts] per 100 parts VC of the non-foil agent phenolic resin to the base material afterwards.This invention Is there a good way to make prepreg? I will explain in more detail about 1lvc. 01 curing agent can be impregnated into the VC base material using the dipping tank method, the one-way method, the kiss coating method, etc.
:/1)01￥7. Power DPP water in a drying oven? It is allowed to evaporate and harden for several months to form a residual formula. The flexible base material V (high temperature (softening point of Senso, crystallization temperature of 120°C to 50°C) F
From the set resin tank, pass through the resin and apply resin, and then slide it onto the surface with a heated roll. C
In this case, the temperature of the hot roll and the softening point of the phenol resin must be adjusted in consideration of the formability of the laminate.

The softening point of phenolic resin is -10°C considering the castle shape.
~50°C is preferred. There are novolac-type drying oil-modified phenolic resins with low softening points (V) for improving the low-temperature punching properties of laminates. Moσノ is
Since it is solid at room temperature, this finely pulverized powder contains two hardening agents and is sprinkled on the substrate. Next, heat it with a hot roll (at a temperature above the softening point) to make 7 legs.

Lay down several sheets of the GrisLev primary foot and press 1'tU [
100-15 Clkg/pressure of moromi 1'15 between springboards
Lamination can be achieved by heating at 0°C for 1 hour, and when powdered phenolic resin is used, the flowability of the resin can be improved. 0jcQ, rL) IQ, which is difficult to adjust, is convenient because the resin flow n can be suppressed by using C and Vt, which are used on a hot plate with protrusions around the periphery instead of a flat plate press.

Examples 1-6 vElliLo, 6 g/cm'm weight 125 g
A hexamethylenetetramine-treated base material 7 was prepared by impregnating 5wt% of hexamethylenetetramine bath solution on a cotton linter paper with a weight of /m2 and drying it. ) After spraying Boding Novolac 4111 powder on the table below, melt or melt it and apply it to the base material to create Brigretz. Molding pressure 80kg/crr in the mold
P. A phenol resin laminate was obtained by lamination molding at 150°C for 60 minutes.

Synthesis Example 1 Into a three-necked 61 flask were added 1000 g of bispropylene, 560 g of formalin, and 5 g of oxalic acid and refluxed. After 60 minutes, the reaction solution was dehydrated and concentrated under reduced pressure to reach a softening point of 7.
Stop the reaction when the temperature reaches 0°C, take it out of the pot on a metal pad, cool it, and then crush it with a mixer.7.0 This powder? Above (1)
A prepreg gun was prepared by scattering it on cotton linter paper and heating it at 80° C. for 1 kettle to melt it (Example 1).The layer weight with side fat was 77% (relative to the base material r).

@bottom side 2 m-p-talesol (m/p
Ratio = 6/4) 1000 g, formalin 525 g, 8% hydrochloric acid aqueous solution 110 g n Gradually heated 0 When the reaction solution stopped generating heat, it was 80℃ 1 and the temperature r was higher than the reaction h1fjt,
After 60 minutes of emulsification, the mixture was dehydrated and concentrated under reduced pressure. When the softening point reached 60°C, the 002'L was taken out into a metal knot to stop the reaction, cooled, and pulverized with a mixer.
Melt it and apply it on the above tip-ton linter paper.
Example 2) The amount of resin deposited was 102% (based on the base layer). Example 6 200 g of tung oil @ D19' was placed in a 61 Mitsuro flask.
Novolac type phenolic street fat made with J2 500g'
After adding 2 g of n-paratoluenesulfone (mO) and 2 g of khD, the reaction was completed at 80° C. for 1 hour. After the reaction was completed, 0.2 g of triethylamine was added to neutralize. No. 11 was melted and applied to the above-mentioned cotton linter paper (based on Example 6), and the adhesion amount of the resin was 82% (based on the substrate).

Comparison V1 1000 g of phenol and 5 paraform in a 61 flask
10g, formalin 276g'K)) 62gk of D-trimethylamine water bath solution was added and the reaction was carried out at 70°C. When gelling was performed on a hot plate at 160°C...J2 was added and the point at which it reached 180 seconds was taken as the end point. To do this, I adjusted the methanol 2 sword Rie a January credit to 48% and created a festoon, ft, 0 I used it for this varnish and it was dishonest J! A prepreg was made by impregnating the cotton linter paper used in 1i12, and a laminate was made by heating and pressing under the same conditions as in the example.

The side fat layer was 85% (relative to the base material) T″0. The properties of the laminate are shown in Table 1 below.

Table 1 Characteristics of laminate *I 11JM based on Jr's-c 6481
L*,.

Comparing Examples and Comparative Examples, characteristic V (has almost no change, 0, i.e., solvent-free type σ as in Example), Novolank type 2
□ Even when used in norformaldehyde resin, it can have the same characteristics as the conventionally used resol type phenol resin. Therefore, there is no need for an inventive method or bath additives, and the drying process is only required, which has a cost-effective effect.

Claims (1)

[Scope of Claims] 1. A layer of curing agent is applied to the base material for the laminate in advance, and then a phenolic resin containing a solvent is applied to the base material to remove the pre-pre-fluid. aNne or son
Nikaishi Hakuga■ Lay down the sword 1 and mold it by heat and pressure. Also known as 't'V
The manufacturing method for the 2nd and 7th generation of the 1st month purchase. 2. Claim 1, which states that the base material is paper
Method for manufacturing the laminate described in Section 1. 3. The method for producing a laminate according to claim 1, wherein the curing agent is hexamethylenetetramine, and 64%. 4. The thermosetting resin containing the bath agent is a drying oil-modified novolak type phenol formaldehyde resin''C.
1. A method for producing a laminate according to claim 1, in which the percentage is expressed as silk.