JPS5929429B2 - Manufacturing method of thermosetting resin products - Google Patents

Description

Detailed Description of the Invention A thermosetting resin composition comprising a phenol-gradient aromatic hydrocarbon formaldehyde resin, a compound having a 5-triazine ring-formaldehyde resin, and an epoxy resin, or a phenol-gradient aromatic hydrocarbon resin and 5 - A resin mixture made by blending an organic phosphorus-containing compound and an organic halogen-containing compound with a thermosetting resin composition made of a thermosetting resin and an epoxy resin obtained by reacting a compound having a triazine ring with formaldehyde is used as a laminate product base material. This relates to a method for manufacturing flame-retardant thermosetting resin laminates, which is characterized by impregnating the product with a flame-retardant thermosetting resin and laminating it.It is applicable to ordinary laminates, laminates with copper foil, laminate bars, and laminate pipes. The objective is to provide a thermosetting resin laminate that has excellent flame resistance, high electrical properties, mechanical strength, dimensional stability, chemical resistance, and heat resistance.

Traditionally, thermosetting resin laminates have been widely used as insulating boards and printed wiring boards, mainly in electronic devices, and their importance is increasing significantly. However, in recent years, various regulations have been put in place regarding the flammability of these materials. As a result, it is now common practice to impart flame retardancy.
Many applicable flame retardants are also known.

Although these flame retardants achieve the purpose of imparting the necessary flame retardancy, they have a more or less negative effect on electrical properties, mechanical strength, heat resistance, dimensional stability, chemical resistance, etc., and as a result, they have been criticized. When compared with fuel laminated products, it is inevitable that they will be subject to obvious practical limitations. The present invention has been made in view of these points, and as a result of various studies aimed at imparting flame retardance without impairing the above properties, we have developed a thermosetting resin with a specific composition. It has been found that a composition containing an organic phosphorus-containing compound and an organic halogen-containing compound is extremely effective and produces satisfactory results.

That is, the method of the present invention uses a thermosetting resin composition consisting of a phenol-modified aromatic hydrocarbon formaldehyde resin, a compound-formaldehyde resin having an S-triazine ring, and an epoxy resin, or a phenol-modified aromatic hydrocarbon resin and an S-triazine ring-containing compound-formaldehyde resin. 5 to 50 parts of an organic phosphorus-containing compound and 5 to 50 parts of an organic halogen-containing compound to 100 parts of a thermosetting resin composition made of an epoxy resin and a thermosetting resin composition obtained by reacting a compound having a triazine ring with formaldehyde. The present invention relates to the production of a flame-retardant thermosetting resin laminate, characterized in that a resin mixture containing 60 parts of the resin mixture is laminated, coated and impregnated onto a layer base material, stacked in a required number of layers, and heated and pressurized.

Phenols as used in the present invention refer to phenols themselves, cresols, xylenol, substituted phenol compounds, polynuclear phenols, and the like.

The phenol-modified aromatic hydrocarbon formaldehyde resin in the present invention is an oxygen-containing aromatic carbonized resin obtained by condensing an aromatic hydrocarbon such as benzene, toluene, xylene, mesitylene, or naphthalene with formaldehyde under a strong acid catalyst such as sulfuric acid. Refers to a resol-type phenol-modified aromatic hydrocarbon formaldehyde resin in which formaldehyde is condensed under an alkaline catalyst to a phenol-modified aromatic hydrocarbon resin in which the above-mentioned phenols are post-condensed to a hydrogen formaldehyde resin under an acidic catalyst. It is a thermosetting material having a methylol group + CH2OH in the formula.

Further, the phenol-modified aromatic hydrocarbon resin refers to the resin before reacting with the final formaldehyde in the production process of the phenol-modified aromatic hydrocarbon formaldehyde resin. The compounds having an S-triazine ring in the present invention are melamines and guanamines, and melamine, substituted melamine, acetoguanamine, benzoguanamine, etc. can be preferably used.

The compound-formaldehyde resin having an S-triazine ring is obtained by reacting melamines and guanamines with formaldehyde under neutral or alkaline conditions.

The epoxy resin as 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 also contains a diene. It means a known compound obtained by epoxidizing a compound or an aliphatic compound by oxidation with a peracid.

For example, epoxy resins having the following molecular formula can be used.

These epoxy resins can be used without a curing agent or accelerator, but a curing agent or accelerator can also be used.

Preferred examples include aliphatic and aromatic polyamines, acid anhydrides, polyamides, BF3-amine complexes, dicyandiamide, and benzyldimethylamine. As described above, a thermosetting resin composition is obtained by composing a phenol-modified aromatic hydrocarbon formaldehyde resin, a compound-formaldehyde resin having an S-triazine ring, and an epoxy resin as the thermosetting resin components.
Preferred methods include (1) a method of mixing three components, (2) a method of obtaining a phenol-modified aromatic hydrocarbon resin, S-
Examples include a method in which a thermosetting co-condensed resin composition obtained by heating and condensing a mixture of a compound having a triazine ring and formaldehyde as main reaction components in the presence of an alkali and an epoxy resin is obtained.

The flame retardants useful in the present invention are phosphorus-containing organic compounds or halogen-containing organic compounds, but it is not preferable to use each alone to impart sufficient flame retardancy, and a combination thereof gives preferable results.

Examples of organic phosphorus-containing compounds include triphenyl phosphate, tricresyl phosphate, trischloroethyl phosphate, triphenyl phosphite, substituted phosphonate, polyphosphate, polyphosphonate, tris dichloropropyl phosphate, phosphonitrile compounds, etc. It is.

Examples of organic halogen-containing compounds include chlorinated paraffins, halogenated epoxy compounds, halogenated phenols, and halogenated bisphenol A1 head acids.
However, both the organic phosphorus-containing compound and the organic halogen-containing compound are not limited to the exemplified compounds. The laminate base materials used in the present invention include paper, glass nonwoven fabric, glass cloth, mixed nonwoven fabric of linter and glass, asbestos paper, cotton fabric, synthetic fiber fabric, and nonwoven fabric, as well as paper containing antimony oxide, phenolic resin, Paper treated with melamine resin or the like is also suitably used.

The amount of flame retardant added to the thermosetting resin used in the present invention varies depending on the base material of the laminate, but in the case of paper base material, 10 parts of the organic phosphorus compound is added to 100 parts of the thermosetting resin composition.
Parts to 50 parts and organic halogen-containing compounds 10 to 60 parts are suitable. In the case of a glass base material, both the organic phosphorus-containing compound and the organic halogen-containing compound may be 1/2 or less of that of the paper base material. As mentioned above, it is not clear why excellent flame resistance, high electrical properties, mechanical strength, dimensional stability, chemical resistance, and heat resistance are obtained when thermosetting resin laminates are produced using the method of the present invention. , the phenol-modified aromatic hydrocarbon formaldehyde resin component, the S-triazine ring compound-formaldehyde resin component, and the epoxy resin component do not compensate for their respective drawbacks, and as a result, they each bring about improvements in curability that cannot be achieved alone. It is inferred that this prevents the deterioration of various properties that would be impaired by the addition of refractory agents, and maintains quality that is equal to or better than non-combustible laminates.

In the present invention, the phenol-modified aromatic hydrocarbon formaldehyde resin or the phenol formaldehyde resin can be optionally modified with a modifier such as drying oil or coconut oil in order to impart flexibility. In addition to phosphorus and halogen as flame retardant components, antimony compounds and other inorganic flame retardant aids can also be used in combination.

The details of a laminate to which copper foil is bonded will be described below in accordance with an example.

Example 1 400 parts of toluene, 120 parts of α-polyoxymethylene as a formaldehyde source, 200 parts of melamine, 22 parts of formalin (37% aqueous solution) and 660% hexamethylenetetramine were added to a 98% sulfate-modified toluene resin solution to give 80 parts of hexamethylenetetramine. The reaction was carried out at ~86°C for 3 hours, and then water and toluene generated by condensation were removed under reduced pressure, and diluted with an acetone-methanol mixed solvent to obtain a resin solution.

A mixture of 270 parts of bisphenol A type epoxy resin (epoxy equivalent: 500), 1.5 parts of benzyldimethylamine, 178 parts of triphenyl phosphate, and 178 parts of brominated biphenyl was added and mixed to this solution, and the mixture was treated with melamine resin in advance. A laminate was obtained in the same manner as in Example 1 by impregnating kraft paper with a thickness of 0.25 mm. Its properties are shown in Table 2. Examples 3, 4, 5 In the method of Example 1, compounds listed in Table 1 were prepared as flame retardant combinations other than the combination of tricresyl phosphate and brominated biphenyl.

All other conditions were the same as in Example 1 to obtain a laminate. Table 2 shows the properties of the obtained laminate. Example 6,
7 In the method of Example 1, xylene resin and mesitylene resin were prepared as the aromatic hydrocarbon resin other than toluene resin and used as Examples 6 and 7, respectively, and laminated products were produced under the same conditions as Example 1. I got it.

The characteristics are shown in Table 2. Example 8 A laminate was obtained in the same manner as in Example 1, except that the linter paper was not previously treated with phenolic resin.

The characteristics are shown in Table 2. Example 9 A laminate was produced in the same manner as in Example 1, except that a glass nonwoven fabric was used instead of the linter paper, and the resin was attached at a ratio of 1.6 to 1 of the base material. Obtained.

The characteristics are shown in Table 2. Comparative Example Ammonia-catalyzed resol type phenol formaldehyde resin (solid content 50%) obtained by a conventional method
A mixture of 1000 parts and 150 parts of triphenyl phosphate and 150 parts of brominated biphenyl was impregnated into a piece of linter paper with a thickness of 0.25 that had been previously treated with phenolic resin, and the same method as in Example 1 was carried out. A laminate was obtained.

Claims (1)

[Claims] 1. A phenol-modified aromatic hydrocarbon formaldehyde resin, a compound having an S-triazine ring - a thermosetting resin composition consisting of a formaldehyde resin and an epoxy resin, or a phenol-modified aromatic hydrocarbon resin and a compound having an S-triazine ring 5 to 50 parts of an organic phosphorus-containing compound and 5 to 6 parts of an organic halogen-containing compound per 100 parts of a thermosetting resin composition consisting of an epoxy resin and a thermosetting cocondensation resin composition obtained by reacting formaldehyde with formaldehyde.
1. A method for producing a flame-retardant thermosetting resin laminate, which comprises coating and impregnating a laminate base material with a resin mixture containing 0 parts of 0 parts, piling up a required number of sheets, and heating and pressurizing them.