JPS5929427B2 - Manufacturing method for thermosetting resin products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention uses 5 to 50 parts of an organic phosphorus-containing compound and 5 to 60 parts of an organic halogen-containing compound to 100 parts of a resin composition comprising a phenol-gradient aromatic hydrocarbon formaldehyde resin and an epoxy resin. The present invention relates to a method for manufacturing flame-retardant thermosetting resin laminates, which is characterized by impregnating a base material with a resin mixture made of The purpose of the present invention is to provide a flame-retardant laminate with extremely excellent chemical resistance, water resistance, heat resistance, and dimensional stability, and a method for producing the same, and to provide a flame-retardant laminate particularly suitable for printed wiring boards. It is in.

Traditionally, thermosetting resin laminates have been widely used as substrates for printed wiring, mainly in electronic devices, and their importance is increasing markedly.However, in recent years, various regulations regarding flammability of these materials have been introduced. It is now common practice to provide flame retardant properties to these materials.

Many flame retardants and flame retardant aids are known that are used to make resins flame retardant, and although the purpose of imparting the necessary flame retardants to resins can be achieved, the laminates obtained with these materials are There is a problem that any of the properties such as chemical resistance, water resistance, heat resistance, and dimensional stability are significantly inferior to those without flame retardation, and there are many practical restrictions. The present invention has been made in view of these points, and as a result of various studies aimed at solving the above problems, it has been found that a thermosetting resin with a particular composition has extremely effective and satisfactory results. Based on this discovery, we proceeded with various studies and completed this research.

That is, in the present invention, 5 to 50 parts of an organic phosphorus-containing compound and 5 to 60 parts of an organic halogen-containing compound are blended with 100 parts of a resin composition consisting of a phenol-gradient aromatic hydrocarbon formaldehyde resin and an epoxy resin. The present invention relates to a method for producing a flame-retardant thermosetting resin laminate, which comprises impregnating a base material with a resin mixture and performing laminate molding. Phenols as used in the present invention refer to phenol, cresol, xylenol, resorcinol, bisphenol A)-substituted phenol compounds, polynuclear phenols, and one or more of these may be used.

The aromatic hydrocarbon formaldehyde resin constituting the phenol-modified aromatic hydrocarbon formaldehyde resin of the present invention is the condensation of formaldehyde with one or more of benzene, toluene, xylene, mesitylene, naphthalene, and other substituted aromatic hydrocarbons. This refers to a reactive resin containing an ether bond, an acetal bond, and a methylol group.

In the present invention, the phenol-modified aromatic hydrocarbon formaldehyde resin is one obtained by condensing the above-mentioned aromatic hydrocarbon formaldehyde resin and the above-mentioned phenols under acidic conditions, and then condensing formalin, paraformaldehyde, etc. under alkaline conditions. Those that are condensed with formaldehyde to form resols, or these are used as tung oil, dehydrated castor oil,
Refers to oils denatured with one or more vegetable oils selected from linseed oil, oak nut oils, urushiols, and rosin.

Moreover, a compound obtained by appropriately co-condensing a compound having an S-triazine ring, such as melamine, guanamine, and substituted products thereof, can also be used. The epoxy resin used in the present invention is a compound obtained by reacting a polyvalent phenol, a polyvalent polynuclear phenol, or an aliphatic polyhydric alcohol with an epihalohydrin or a dihalohydrin in an alkaline catalyst by a known method, and an alicyclic resin containing a diene. It means a known compound obtained by eboxidizing a compound or an aliphatic compound by peracid oxidation.

For example, there are epoxy resins obtained from bisphenol A and epichlorohydrin. The organic phosphorus-containing compound and the organic halogen-containing compound used in the present invention are used as flame retardants, but it is difficult to impart sufficient flame retardance to a laminate when using each alone, so they are used in combination. gives the most favorable results.

Organic phosphorus-containing compounds are generally known as flame retardants, and examples include triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, substituted phosphonates, tris-2,3-dipromopropyl phosphate, and trischlor. Ethyl phosphate, phosphonitrile compounds, etc., and one or more of these compounds are used. Examples of organic halogen-containing compounds include chlorinated paraffins, halogenated epoxy compounds, halogenated phenols, halogenated bisphenols A1, halogenated biphenyl, and head acids. used. In the present invention, the base material includes paper whose main component is cellulose, glass nonwoven fabric,
One or more types of glass cloth, non-woven fabric made from a mixture of glass and linter, asbestos paper, paper made from a mixture of paper and asbestos, cotton cloth, etc., are used, and pre-treated base materials, such as paper treated with a low condensed phenolic resin, are used. material can be used.

Further, paper containing antimony trioxide or zinc borate can be used. Low-condensation phenolic resins, melamine resins, guanamine resins, and co-condensed resins thereof give preferable results in the treatment of paper containing cellulose as a main component, glass nonwoven fabric, and mixed paper of linter and glass. The amount of the organic phosphorus-containing compound added to 100 parts of the resin composition consisting of the phenol-modified aromatic hydrocarbon formaldehyde resin and the epoxy resin is preferably 5 to 50 parts, and the amount of the organic halogen-containing compound is 5 to 60 parts. is preferred.

The phenol-modified aromatic hydrocarbon formaldehyde resin is produced, for example, by the following method.

That is, an aromatic hydrocarbon formaldehyde resin and a phenol are reacted under acidic conditions in the presence or absence of vegetable oil, and then reacted with formaldehyde in the presence or absence of a compound having an S-triazine ring as an alkali. A method for producing a resol type resin, in which an aromatic hydrocarbon formaldehyde resin and a phenol are reacted under acidic conditions, and then in the presence or absence of at least one of a compound containing an S-triazine ring and a vegetable oil as an alkali. It is produced by reacting with formaldehyde to form a resol type resin. The resin composition consisting of a phenol-modified aromatic hydrocarbon formaldehyde resin and an epoxy resin contains aliphatic and aromatic polyamines, dicyandiamide, polyamide, acid anhydride, and BF3.
A method of mixing a phenol-modified aromatic hydrocarbon formaldehyde resin and an epoxy resin, in which one or more generally known curing agents for epoxy resins such as Complex, benzyldimethylamine, etc. can be appropriately blended;
A method in which a curing agent for epoxy resin is further mixed therein, a method in which a part of the epoxy resin and a curing agent for epoxy resin are mixed with a phenol-modified aromatic hydrocarbon formaldehyde resin, and a method in which a mixture of these is further mixed with a phenol-modified aromatic hydrocarbon formaldehyde resin Any method such as a method of partially reacting can be used. A resin mixture obtained by blending an organic phosphorus-containing compound and an organic halogen-containing compound with a resin composition consisting of a phenol-modified aromatic hydrocarbon formaldehyde resin and an epoxy resin has excellent electrical properties, chemical resistance, water resistance, heat resistance, and The reason for providing a laminate product with excellent dimensional stability, especially a laminate product with excellent heat resistance and dimensional stability, is not clear, but both are essential, and effective results can only be obtained with this combination.

The amount of the resin mixture impregnated into the base material is 30 to 400 parts, preferably 80 to 300 parts, per 100 parts of the base material.

Laminate molding is carried out in the usual way, by laminating one or more B-stage resin-impregnated base materials, heating and pressing this between two plates with a press with a hot plate to harden the resin,
A method similar to that used for plate-shaped laminated products is adopted. Also, laminated products such as laminated tubes can be obtained. The resin mixture to be impregnated into the base material includes phenolic resin,
One or more types of condensates of a compound having an S-triazine ring and formaldehyde, etc. can be appropriately blended or co-condensed.

The most preferable result is that the blending amount should be in a range where the constituent units of the aromatic hydrocarbon formaldehyde resin constituting the resin mixture after blending it into the resin mixture are at least 15% by weight (based on solid content) of the total. give. Further, an inorganic powder flame retardant such as antimony trioxide, aluminum hydroxide, zinc borate, etc. can be appropriately blended into the resin mixture. When the resin-impregnated base material is laminated and molded, a copper clad laminate can be obtained by laminating and molding a copper foil over at least one of the outer sides of the laminated resin-impregnated base material.

In addition, at least one type of resin-impregnated paper is used as the resin-impregnated paper in the laminated structure, and one or more types of resin-impregnated base materials by other conventional methods are appropriately laminated to within 20% of the thickness of the laminate. Can be configured. The laminate obtained by the method of the present invention has excellent flame retardancy, electrical properties, chemical resistance,
Due to its water resistance, heat resistance and dimensional stability, it is suitable for application in electrical insulation materials, especially printed wiring boards.

The details of a laminate to which copper foil is bonded will be described below in accordance with an example. Example 1 A mixture consisting of 100 parts of toluene, 30 parts of α-polyoxymethylene, and 20 parts of 98% sulfuric acid was reacted at 100 to 110°C for 8 hours with vigorous stirring in a reactor equipped with a cooling tube, and after the reaction was completed, a large amount of The mixture was poured into water and washed repeatedly to thoroughly wash away the acid, and dehydrated while heating under reduced pressure of 60 mmHg to obtain 110 parts of toluene formaldehyde resin.

This resin is a brown viscous liquid resin with 79.75% carbon.
The elemental analysis values were 7.34% hydrogen and 12.91% oxygen, and the acid value was 0.14. 100 parts of this toluene formaldehyde resin and 80 parts of phenol were reacted with para-toluene sulfonic acid as a catalyst, and after dehydration, 7 parts of toluene
0 parts were added and neutralized with ammonia, and 23 parts of paraformaldehyde was added thereto to cause a reaction using hexamethylenetetramine as a catalyst. After dehydration, the mixture was diluted with acetone to obtain a resol type resin solution with a resin content of 50%.

To 100 parts of this resin solution, 15 parts of epoxy resin (trade name: DER66l, manufactured by TAU), 20 parts of brominated biphenyl, and 15 parts of tritalesyl phosphate were mixed, and a piece of linter paper previously treated with phenol resin was impregnated with this. After drying, a B-stage resin-impregnated paper with a resin content of 51% was obtained.
Nine sheets of this were laminated, a 35μ thick copper foil was layered on the outside of one side, and the temperature was 170℃ and the pressure was 90k9/C between two hot plates.
The product was heated and pressed for 60 minutes using TIt to obtain a copper-clad laminate having a thickness of 16 mm. The properties of this laminate are shown in Table 1. Example 2 80 parts of benzene, 30 parts of α-polyoxymethylene, and 20 parts of 60% perchloric acid were mixed, and 7 parts were prepared in the same manner as in Example 1.
A benzene formaldehyde resin that was reacted at 0 to 80°C for 10 hours, was brownish-yellow, viscous, and had elemental analysis values of 78.92% carbon, 7.18% hydrogen, and 13.9% oxygen, and an acid value of 0.12. I got it.

Using 100 parts of this, 50 parts of phenol, and 20 parts of paraformaldehyde, a resol type phenol-modified benzene formaldehyde resin solution with a resin content of 50% was obtained in the same manner as in Example 1. Add 100 parts of this resin solution to epoxy resin (
A mixture of 20 parts of Epicoat 828 (trade name manufactured by Ciel), 2.3 parts of brominated bisphenol A, and 15 parts of triphenyl phosphite was impregnated into a piece of linter paper that had been previously treated with phenolic resin, and the same procedure as in Example 1 was carried out. 16mm
A copper-clad laminate with a thickness of .

The properties of this laminate are shown in Table 1. Example 3 Resol-type metacresol-modified toluene formaldehyde resin solution 1 with a resin content of 50% obtained in the same manner as in Example 1 from 100 parts of toluene formaldehyde resin obtained in Example 1, 50 parts of metacresol, and 50 parts of 37% formanone.
00 parts, epoxy resin (trade name DER66l manufactured by TAU)
), 0.05 parts of benzyldimethylamine, 20 parts of brominated bisphenol, and 15 parts of triphenyl phosphate were mixed, and the mixture was impregnated into a piece of linter paper that had been previously treated with phenolic resin, in the same manner as in Example 1. A copper-clad laminate was obtained.

The properties of this laminate are shown in Table 1. Example 4 45 parts of toluene formaldehyde resin obtained in Example 1,
A resol type resin solution having a resin content of 50% was obtained in the same manner as in Example 1 by reacting 30 parts of phenol and 25 parts of tung oil under acidic conditions and then with 13 parts of paraformaldehyde under alkaline conditions.

To 100 parts of this resin solution, 15 parts of epoxy resin (trade name: DER66l, manufactured by TAU), 3 parts of diaminodiphenylmethane
A copper-clad laminate was obtained in the same manner as in Example 1 by blending 20 parts of partially brominated biphenyl and 15 parts of tricresyl phosphate and impregnating it into kraft paper previously treated with phenolic resin. The properties of this laminate are shown in Table 1. Example 5 The resin content was 6 in the same manner as in Example 1 except that the base material was changed to glass paper pretreated with phenol-benzoguanamine-formaldehyde resin.
A 5% resin-impregnated paper was obtained to obtain a copper-clad laminate.

The properties of this laminate are shown in Table 1. Example 6 25 parts of acetoguanamine-phenol-formaldehyde co-condensation resin having a methylol group containing 55% acetoguanamine obtained by a conventional method in 100 parts of the resin solution with a resin content of 50% obtained in Example 1, 15 parts of epoxy resin (Tau product name DER66l), 20 parts of brominated biphenyl
A copper-clad laminate was obtained in the same manner as in Example 1 by impregnating untreated kraft paper with 15 parts of tricresyl phosphate.

The properties of this laminate are shown in Table 1. Example 7 A copper-clad laminate was obtained under the same conditions as in Example 1, except that 20 parts of brominated biphenyl was replaced with 20 parts of a halogen-containing epoxy resin (trade name: DER542, manufactured by TAU).

The properties of this laminate are shown in Table 1. Example 8 A resol-type oil-modified phenolic resin obtained by a conventional method from the resin mixed solution impregnated into the base material of Example 1, and further added 70 parts of phenol, 25 parts of tung oil, 5 parts of rosin, and 60 parts of 37% formalin. A copper-clad laminate was obtained by mixing 15 parts with the other conditions being the same as in Example 1.

The properties of this laminate are shown in Table 1. Example 9 A copper-clad laminate was obtained under the same conditions as in Example 1, except that the toluene formaldehyde resin in Example 1 was replaced with meta-xylene resin (manufactured by Mitsubishi Gas Chemical).

The properties of this laminate are shown in Table 1. Comparative Example 20 parts of brominated biphenyl and 15 parts of triphenyl phosphate were blended into 100 parts of a 50% solution of a resol type phenolic resin obtained by a conventional method from phenol and 37% formalin, and this was treated in advance with a low condensation phenolic resin. A copper-clad laminate was obtained in the same manner as in Example 1 by impregnating the prepared linter paper.

The properties of this laminate are shown in Table 1. Table 1 shows that the dielectric loss tangent, solder resistance, water absorption, trichlein resistance, and dimensional stability of the laminate produced by the method of the present invention are superior to the comparative example produced by the conventional method.

Claims (1)

[Claims] 1. A resin mixture prepared by blending 5 to 50 parts of an organic phosphorus-containing compound and 5 to 60 parts of an organic halogen-containing compound to 100 parts of a resin composition consisting of a phenol-modified aromatic hydrocarbon formaldehyde resin and an epoxy resin. A method for producing a flame-retardant thermosetting resin laminate, which comprises impregnating a base material and laminating the product.