JPS5929430B2 - Manufacturing method of thermosetting resin products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a resin obtained by blending an organic phosphorus-containing compound and an organic halogen-containing compound with a thermosetting resin composition consisting of a phenol-gradient aromatic hydrocarbon formaldehyde resin, a phenol formaldehyde resin, and an epoxy resin. This invention relates to a method for producing a flame-retardant thermosetting resin laminate, which comprises impregnating a laminate base material with a mixture and performing laminate molding.
A thermosetting material that is applicable to ordinary laminates, copper foil-covered laminates, laminate bars, and laminate tubes, and has excellent flame resistance, high electrical properties, mechanical strength, dimensional stability, chemical resistance, and heat resistance. Our goal is to provide resin laminate products.

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, but in recent years these materials have come under various regulations regarding flammability. It is now common practice to provide flame retardance, and many flame retardants that can be used are also known. Although these flame retardants can achieve the purpose of imparting the necessary flame retardancy, they have poor electrical properties, mechanical strength, heat resistance, dimensional stability,
It has a more or less negative effect on chemical resistance, etc.
As a result, when compared with flame-retardant laminates, 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 discovered that a composition containing an organic phosphorus-containing compound and an organic halogen-containing compound is extremely effective and gives satisfactory results.

That is, in the method of the present invention, 5 to 50 parts of an organic phosphorus-containing compound and 5 parts of an organic halogen-containing compound are added to 100 parts of a thermosetting resin composition comprising a phenol-gradient aromatic hydrocarbon formaldehyde resin, a phenol formaldehyde resin, and an epoxy resin. The present invention relates to the production of a flame-retardant thermosetting laminate, characterized in that a resin mixture containing up to 60 parts of the resin mixture is coated and impregnated onto a laminate base material, and the required number of sheets are stacked 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 alkali catalyst to a phenol-modified aromatic hydrocarbon resin obtained by post-condensing the above phenols to a hydrogen formaldehyde resin under an acidic catalyst. It is a thermosetting compound 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 phenol formaldehyde resin as used in the present invention refers to a resol type resin obtained by reacting the phenols and formaldehyde in an alkaline environment, or a resol type resin modified with various modifiers. 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 a resin containing a diene. It means a known compound obtained by epoxidizing a cyclic compound or an aliphatic compound by peracid oxidation.

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 an accelerator can also be used.

Preferred examples include aliphatic and aromatic polyamines, acid anhydrides, polyamides, BF3-amine complexes, dicyandiamide, and benzyldimethylamine. A thermosetting resin composition is obtained by composing a phenol-modified aromatic hydrocarbon formaldehyde resin, a phenol formaldehyde resin, and an epoxy resin as the thermosetting resin components.
An example of this method is to mix two components.

The flame retardants useful in the present invention are phosphorus-containing organic compounds or halogen-containing organic compounds, but using each alone is not preferable for imparting sufficient flame retardancy, and using them in combination gives preferable results. .

Examples of organic phosphorus-containing compounds include triphenyl phosphate, tricresyl phosphate, trischloroethyl phosphate, triphenyl phosphite, substituted phosphonates, polyphosphates, polyphosphonates, tris dichloropropyl phosphate, and phosphonitrile compounds. be.

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, and melamine. Paper treated with 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, 1 part of the organic phosphorus compound is added to 100 parts of the thermosetting resin composition.
0 parts to 50 parts and 10 parts to 60 parts of the organic halogen-containing compound are suitable. In the case of a glass base material, both the organic phosphorus-containing compound and the organic halogen-containing compound may be contained in an amount of % or less of the paper base material. As described above, when producing a thermosetting resin laminate using the method of the present invention, it has excellent flame resistance, high electrical properties, mechanical strength,
The reason why dimensional stability, chemical resistance, and heat resistance are obtained is not clear, but the reason is that the phenol-modified aromatic hydrocarbon formaldehyde resin component, the phenol formaldehyde resin, and the epoxy resin component do not compensate for their respective drawbacks, and As a result of improving hardenability, which cannot be achieved alone, it is thought to prevent the deterioration of various properties that are damaged by the addition of flame retardants, and maintain good quality equivalent to or better than flame-retardant laminates. Ru.

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, for example.

Furthermore, melamine resin modification and guanamine resin modification can also be performed. 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 A mixture of 400 parts of toluene, 120 parts of α-polyoxymethylene as a formaldehyde source, and 80 parts of 98% sulfuric acid was vigorously stirred in a reactor equipped with a cooling tube, and the mixture was heated to \100-110.
℃ for 8 hours, and after the reaction was completed, the reaction mixture was poured into a large amount of water and washed repeatedly to thoroughly wash away the acid.
0m7! Dehydrated while heating under reduced pressure of LHg to 440
of toluene formaldehyde resin was obtained.

This resin is a brown viscous liquid resin with a carbon content of 79.750!
), the elemental analysis values were 7.34% hydrogen and 12.91% oxygen, and the acid value was 0.14. The toluene-formaldehyde resin thus obtained was reacted with 418 parts of phenol, 88 parts of toluene, and 190 parts of para-toluenesulfonic acid in a reactor equipped with a cooling tube while stirring at 90 to 100°C under reflux for 2 hours, and then under reduced pressure. When the temperature of the reaction mixture is 140
The reaction was completed by dehydration until the temperature reached ℃. Next, 308 parts of toluene was added to this and neutralized with ammonia. To this, 110 parts of paraformaldehyde and 22 parts of 28% ammonia were further added and reacted at 85 to 900C for 2.5 hours, and then by condensation under reduced pressure. Table 2 shows the properties of the phenol-modified toluene-formaldehyde resin solution obtained by removing generated water and toluene and diluting with toluene, and the resol-type phenol-formaldehyde resin solution (solid content 50%). . Examples 5 and 6 In the method of Example 1, xylene resin and mesitylene resin were prepared using the aromatic hydrocarbon resin other than toluene resin to prepare Examples 5 and 6, respectively, and the same method as Example 1 was carried out. A laminate was obtained under the conditions.

The characteristics are shown in Table 2. Example 7 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 8 A laminate product was produced in the same manner as in Example 1, except that a glass nonwoven fabric was used instead of the linter paper in Example 1, and the resin was attached at a ratio of 1.6 parts to 1 part 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 pre-treated with phenolic resin to a thickness of 0.25 m7! A laminated product was obtained in the same manner as in Example 1 by impregnating a piece of linter paper of t.

Claims (1)

[Claims] 1 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 thermosetting resin composition consisting of a resol-type phenol-modified aromatic hydrocarbon formaldehyde resin, a phenol formaldehyde resin, and an epoxy resin. 1. A method for producing a flame-retardant thermosetting resin laminate, which comprises coating and impregnating a laminate base material with a resin mixture prepared by blending the above, stacking the required number of sheets, and heating and pressurizing them.