JPS5929428B2 - Manufacturing method of thermosetting resin products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an organic phosphorus-containing compound based on 100 parts of a resin composition containing a phenol-gradient aromatic hydrocarbon formaldehyde resin, a phenol, a compound having a 5-triazine ring, and a formaldehyde. A method for producing a flame-retardant thermosetting resin laminate, which comprises impregnating a base material with a resin mixture containing 5 to 50 parts of a compound and 5 to 60 parts of an organic compound and 5 to 60 parts of an organic compound and laminate-molding the same. The purpose is to improve electrical properties, chemical resistance,
It is an object of the present invention to provide a flame-retardant laminate product having extremely excellent water resistance, heat resistance, and dimensional stability, and a method for producing the same, and in particular to provide a flame-retardant laminate product suitable for printed wiring boards.

Traditionally, thermosetting resin laminates have been widely used as substrates for printed wiring, mainly in electronic devices, and their importance is increasing significantly, but in recent years various regulations have been established regarding the flammability of these materials. It is now common practice to impart flame retardancy to these materials.

Many flame retardants and flame retardant aids are known that are used to make resins flame retardant, and although they can be used to impart the necessary flame retardancy to resins, the laminates obtained with these There is a problem that the properties such as electrical properties, chemical resistance, water resistance, heat resistance, and dimensional stability are significantly inferior to those without flame retardation, and they are subject to 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 thermosetting resins with a particular composition are extremely effective and satisfactory. Based on this discovery, we proceeded with various studies and completed this research.

That is, in the present invention, for 100 parts of a resin composition containing a phenol-gradient aromatic hydrocarbon formaldehyde resin, a phenol, a compound having a 5-triazine ring, and formaldehyde, 5 to 5 organic phosphorus-containing compounds are added.
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 containing 50 parts of organic compound and 5 to 60 parts of an organic compound containing . Phenols in the present invention refer to phenol, cresol, xylenol, resorcinol, bisphenol A, substituted phenol compounds, polynuclear phenols, etc., 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 formed by condensing formaldehyde with one or more of benzene, toluene, xylene, mesitylene, naphthalene, and other substituted aromatic hydrocarbons. Refers to the resulting reactive resin having ether bonds, acetal bonds, and methylol groups. 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. Refers to products condensed with formaldehyde to form resols, or products modified with one or more vegetable oils selected from tung oil, dehydrated castor oil, linseed oil, oak nut oils, urushiols, and rosin. The compounds having an S-triazine ring in the present invention are melamines and guanamines, and melamine-substituted melamine, acetoguanamine, and benzoguanamine are preferably used, and one or more of these can be used.

Formaldehydes as used in the present invention are compounds having a formaldehyde source such as formalin, paraformaldehyde, and α-polyoxymethylene, and one or more of these may be used.

Organic phosphorus-containing compounds and organic phosphorus-containing compounds used in the present invention
- Rogen compounds are used as flame retardants, but it is difficult to impart sufficient flame retardancy to a laminate when each is used alone, and the combination of both gives the most favorable results.

Organic phosphorus-containing compounds are generally known as flame retardants, and examples include triphenyl phosphate, tricresyl phosphate, trischloroethyl phosphate,
Triphenyl phosphite, substituted phosphonates, tris-2,3-dipromopropyl phosphate, trichloroethyl phosphate, phosphonitrile compounds, etc., and one or more of these may be used. Examples of organic halogen-containing compounds include chlorinated paraffins, halogenated epoxy compounds, halogenated phenols, halogenated bisphenols, A1 halogenated biphenyl, and head acids.1 These include all those generally known as flame retardants. One or more of these are used. Substrates that can be used in the present invention include paper whose main component is cellulose, glass nonwoven fabric, glass cloth, mixed nonwoven fabric of linter and glass, asbestos paper, mixed paper of paper and asbestos, cotton cloth, synthetic fiber cloth, and nonwoven fabric. It is also possible to use pre-treated substrates, such as paper treated with low condensation phenolic resins.

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 to be blended is 5 to 50 parts with respect to 100 parts of the resin composition containing the phenol-modified aromatic hydrocarbon formaldehyde resin, phenols, a compound having an S-triazine ring, and formaldehyde. is preferable, and the amount of the organic halogen-containing compound is preferably 5 to 60 parts.

To obtain a resin composition from the constituent components of phenol-modified aromatic hydrocarbon formaldehyde resin, phenols, a compound having an S-triazine ring, and formaldehyde, phenol and formaldehyde are added to the phenol-modified aromatic hydrocarbon formaldehyde resin. A method of mixing a resol type resin obtained by the condensation of a compound having an S-triazine ring and a resin obtained by condensing formaldehydes, or a method of co-condensing a resin of a phenol, a compound having an S-triazine ring, and formaldehyde. A method of mixing a resol-type resin obtained by condensation of phenols and formaldehyde with a co-condensation resin of a phenol-modified aromatic hydrocarbon formaldehyde resin and a compound having an S-triazine ring,
Alternatively, it can be obtained by a method such as a method of mixing a co-condensed resin of phenols, a compound having an S-triazine ring, and formaldehyde, and 2 of the remaining components (b) excluding formaldehyde among the components constituting the resin composition. One or more resins may be reacted together with formaldehyde in advance and the reacted products may be mixed together, or all resins made of one type may be mixed. Further, these may be appropriately modified with the above-mentioned vegetable oil. The phenol-modified aromatic hydrocarbon formaldehyde resin used in the present invention preferably contains at least 35% by weight of aromatic hydrocarbon formaldehyde resin as a constituent component.

A resin obtained by blending an organic phosphorus-containing compound and an organic-containing... It is not clear why the mixture provides a laminate with excellent electrical properties, chemical resistance, water resistance, heat resistance and dimensional stability, especially a laminate with excellent heat resistance and dimensional stability, but none of these are essential. 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 pressurizing this with a press with a hot plate between two backing plates 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 can be appropriately blended with or co-condensed with one or more of epoxy resins, mixtures of epoxy resins and curing agents for epoxy resins, or partially reacted mixtures.

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 resin-impregnated base materials are 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 resin-impregnated base materials. In addition, at least one type of resin-impregnated paper is used as the resin-impregnated paper constituting the laminated product, and one or more types of resin-impregnated base material by other conventional methods are used to make the laminated product.
A laminated structure can be formed as appropriate within 0%. The laminate obtained by the method of the present invention has excellent flame retardancy, electrical properties, chemical resistance, water resistance, heat resistance, and dimensional stability, so it is suitable for electrical insulation materials, especially printed wiring boards. suitable for.

The present invention will be explained below with reference to Examples. 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. The mixture was poured into a large amount of water and washed repeatedly to thoroughly wash away the acid, and the mixture was dehydrated while heating under a reduced pressure of Bl6OmmHg 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 34% hydrogen and 12.91% oxygen, and the acid value was 0.14. 100 parts of this toluene formaldehyde resin and 60 parts of phenol are reacted at 95 to 100°C using para-toluenesulfonic acid as a catalyst,
After dehydration, neutralize with ammonia, then add 60 parts of toluene and 25 parts of paraformaldehyde and react under reflux using ammonia as a catalyst. After dehydration, dilute with toluene to obtain a resol type phenol-modified toluene formaldehyde resin solution with a resin content of 50%. (1) was obtained.

To 100 parts of this resin solution, 20 parts of a resol-type phenolic resin obtained by a conventional method from phenol and formalin, 20 parts of a melamine resin having methylol groups and methoxymethyl groups obtained by a conventional method from melamine and formalin, 20 parts of brominated biphenyl, 15 parts of tricresyl phosphate
The mixture was impregnated into a piece of linter paper previously treated with a low condensed phenol resin and dried to obtain a B-stage resin-impregnated paper with a resin content of 50%. Nine sheets of this impregnated paper were laminated, one sheet of 35μ thick copper foil was placed on the outer surface of one side, and the temperature was 170℃ and the pressure was 85k9/c between two hot plates!
The resin was heated and pressed for 50 minutes using il to obtain a plate-like copper-clad laminate with a thickness of 1.6 mm. The properties of this laminate are shown in Table 1. Example 2 100 parts of phenol, 100 parts of benzoguanamine, 37
% formalin 205 parts and hexamethylenetetramine 5 parts
The mixture was mixed and reacted under reflux, dehydrated and diluted with acetone to obtain a resol type phenol-benzoguanamine co-condensed resin solution with a resin content of 50%.

80 parts of this resin solution, 100 parts of the phenol-modified toluene formaldehyde resin solution (1) obtained in Example 1, parts of brominated bisphenol A2O, and 15 parts of polyphosphate were mixed and impregnated into a piece of linter paper that had been previously treated with phenolic resin. A copper-clad laminate was obtained in the same manner as in Example 1. The properties of this laminate are shown in Table 1. Example 3 100 parts of the toluene-formaldehyde resin obtained in Example 1 and 60 parts of phenol were reacted with para-toluene sulfonic acid as a catalyst, and after dehydration and hydration, 70 parts of toluene, 64 parts of acetoguanamine, and 120 parts of 37% formalin were added. The mixture was further reacted using ammonia as a catalyst, and after dehydration, it was diluted with acetone to obtain a resol type resin solution with a resin content of 50%.

In 140 parts of this resin solution, 20 parts of resol type cresol/formaldehyde resin obtained by a conventional method using ammonia as a catalyst from mixed cresol containing 40% meta-cresol and 37% formalin, 20 parts of brominated biphenyl, and 2 parts of tris.
, 3. Mix 15 parts of dipromopropyl phosphate,
This was impregnated into a piece of linter paper previously treated with phenolic resin to obtain a copper-clad laminate in the same manner as in the example. The properties of this laminate are shown in Table 1. Example 4 40 parts of toluene formaldehyde resin obtained in Example 1,
35 parts of phenol and 25 parts of tung oil were reacted with para-toluenesulfonic acid as a catalyst, dehydrated and neutralized, and diluted with toluene to obtain a resin solution with a resin content of 50%.

100 parts of this resin solution and 80 parts of the phenol-benzoguanamine co-condensed resin solution obtained in Example 2 were mixed to give 54%
The gelation time of the resin on a 150°C hot plate at ~56°C is 3
The reaction was continued until 20 minutes of brominated biphenyl was obtained.
A copper-clad laminate was obtained in the same manner as in Example 1 by blending 15 parts of tricresyl phosphate 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 In Example 1, the base material was replaced with glass paper that had been previously treated with a phenolic resin, and a resin-impregnated paper with a resin content of 65% was obtained under the same conditions as in Example 1 to obtain a copper-clad laminate.

The properties of this laminate are shown in Table 1. Example 6 In the resin mixed solution used in Example 1 to impregnate the base material,
Furthermore, using calcium hydroxide as a catalyst, phenol and 37
% of formalin by a conventional method and 10 parts of an epoxy resin (product name: DER33l, manufactured by TAU) were impregnated into untreated kraft paper. A copper-clad laminate was obtained in the same manner as in Example 1.

The properties of this laminate are shown in Table 1. Example 7 100 parts of xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical) and 70 parts of phenol were reacted using xylene sulfonic acid as a catalyst, and after neutralization with ammonia, 60 parts of toluene and 25 parts of paraformaldehyde were added and reacted with hexamethylenetetramine as a catalyst. The reaction was carried out to obtain a phenol-modified xylene formaldehyde resin solution having a resin content of 50%.

To 100 parts of this resin solution, 20 parts of the phenol resin obtained in Example 1, 20 parts of the melamine resin obtained in Example 1, and a weight ratio of epoxy resin (trade name: DER66l, manufactured by TAU)/diaminodiphenylmethane = 100/20. 15 parts of the partially reacted product, 20 parts of brominated biphenyl, and 15 parts of tricresyl phosphate were blended, and a piece of linter paper previously treated with phenolic resin was impregnated with the mixture in the same manner as in Example 1. A copper-clad laminate was obtained.

The properties of this laminate are shown in Table 1. Comparative Example 20 parts of a halogen-containing epoxy resin (trade name: DER542 manufactured by Tau) and 15 parts of triphenyl phosphate were mixed with 100 parts of a 50f solution of a resol type phenol formaldehyde resin obtained by a conventional method, and this was added to the phenol resin in advance. A copper-clad laminate was obtained in the same manner as in Example 1 by impregnating the treated linter paper.

The properties of the obtained laminate are shown in Table 1. It can be seen from Table 1 that the dielectric loss tangent, solder resistance, water absorption, trichlein resistance, and dimensional stability of the laminate produced by the method z of the present invention are superior to the comparative example produced by the conventional method.

Claims (1)

[Claims] 1 Resin composition 1 containing phenol-modified aromatic hydrocarbon formaldehyde resin, phenols, a compound having an S-triazine ring, and formaldehyde as constituent components
A flame-retardant thermosetting product characterized by impregnating a base material with a resin mixture obtained by blending 5 to 50 parts of an organic phosphorus-containing compound and 5 to 60 parts of an organic halogen-containing compound to 00 parts, and then laminating and molding the resin mixture. A method for manufacturing a plastic laminate product.