JPS5947702B2 - Manufacturing method for thermosetting resin products - Google Patents

Description

Detailed Description of the Invention The present invention relates to a phenol-modified aromatic hydrocarbon formaldehyde resin, a compound-formaldehyde resin having a 5-triazine ring, a thermosetting resin composition comprising a phenol formaldehyde resin and an epoxy resin, or a phenol-modified aromatic resin. A thermosetting resin composition comprising a thermosetting resin obtained by reacting a group hydrocarbon resin, a compound having a 5-triazine ring, and formaldehyde, a phenol formaldehyde resin, and an epoxy resin, or phenol
I-modified aromatic hydrocarbon formaldehyde resin A thermosetting co-condensed resin composition obtained by reacting a phenol with a compound having a 5-triazine ring and formaldehyde and a resin composition consisting of an epoxy resin, an organic phosphorus-containing compound and an organic A method for manufacturing a flame-retardant thermosetting resin laminate, which is characterized by impregnating a laminate base material with a resin mixture containing a halogen-containing compound and laminating it. It is applied to bonded laminates and woven laminate pipes, and the aim is to create thermosetting resin laminates that have excellent flame resistance, high electrical properties, mechanical strength, dimensional stability, chemical resistance, and heat resistance. It is about providing.

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, these materials have undergone various improvements in terms of flame retardancy. Due to the regulations, it is now common practice to impart flame retardancy, and there are many known flame retardants that can be used.

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, When compared with fire-retardant laminates,
In practical terms, it is unavoidable that there are obvious limitations. The present invention has been made in view of these points, and as a result of various studies aimed at imparting flame retardancy without impairing the above characteristics, it has been found that organic It has been discovered that a composition containing a phosphorus-containing compound and an organic halogen-containing compound is extremely effective and gives 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 having an S-triazine ring, a formaldehyde tree, a phenol-formaldehyde resin, and an epoxy resin, or a phenol-modified aromatic hydrocarbon. A thermosetting resin composition obtained by reacting a resin, a compound having an S-triazine ring, and formaldehyde, a thermosetting resin composition consisting of a phenol formaldehyde resin, and an epoxy resin, or a phenol-modified aromatic hydrocarbon formaldehyde tree kite Phenol 5 to 50 parts of an organic phosphorus-containing compound and Manufacture of a flame-retardant thermosetting resin laminate, characterized by applying and impregnating a resin mixture containing 5 to 60 parts of an organic halogen-containing compound onto a laminate base material, stacking the required number of sheets, and heating and pressurizing them. Regarding.

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

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.

Moreover, 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 include 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 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 referred to in the present invention is a compound obtained by reacting a polyhydric phenol with a polynuclear phenol or an aliphatic polyhydric alcohol with epihalohydrin or dihalohydrin in an alkaline catalyst by a known method, and a ring containing a diene. It means a known compound obtained by epoxidizing a compound of the formula 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 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 compound-formaldehyde resin phenol formaldehyde resin having an S-triazine ring, and an epoxy resin as the thermosetting resin components. , as the preferred method (
1) A method obtained by mixing four components, (2) A method in which a phenol-modified aromatic hydrocarbon resin S-triazine ring-containing compound and formaldehyde are used as main reaction components, and a mixture thereof is heated and condensed in the presence of an alkali. A method of mixing the obtained thermosetting cocondensation resin composition with a phenol formaldehyde resin and an epoxy resin, (3) a method of mixing a phenol-modified aromatic hydrocarbon formaldehyde resin, a phenol, a compound having an S-triazine ring, and formaldehyde. Examples include a method of mixing a resin composition obtained by a heating reaction in the presence of an alkali and an epoxy resin.

The composition ratio of each of these resin components is particularly preferably 30% to 75% of phenol-modified aromatic hydrocarbon resin, 5% to 35% of S-triazine resin, and 5% to 3% of phenolic resin.
0% and epoxy resin in the range of 5% to 50%, but it is not necessarily limited to this depending on the degree of flame resistance required.

Flame retardants useful in the present invention are organic compounds having TEL of phosphorus or organic compounds containing halogen, 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 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 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, mixed nonwoven fabric of glass fabric and glass, asbestos paper, cotton fabric, synthetic fiber fabric, and nonwoven fabric, as well as paper containing antimony oxide, phenol tree melamine, etc. 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, 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 stated 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. However, the phenol-modified aromatic hydrocarbon formaldehyde resin component, the S-triazine ring compound-formaldehyde resin component, the phenol formaldehyde resin, and the epoxy resin component do not compensate for their respective drawbacks, and the improvement in curability cannot be achieved by each alone. As a result, it is presumed that the deterioration of various properties that would be impaired by the addition of flame retardants is prevented, and the quality is maintained as good as or better than that of flame-retardant laminates.

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 heated to 100° C. to 11° C. with vigorous stirring in a reactor equipped with a cooling tube.
The reaction was carried out at 0°C 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.
The mixture was dehydrated while heating under a reduced pressure of 60 mHg to obtain 440 parts of toluene formaldehyde resin.

This resin is a brown viscous liquid resin with 79.75% carbon and
Elemental analysis values were 7.34% hydrogen and 12.91% oxygen, and the acid value was 0.14. To the toluene-formaldehyde resin obtained here, 418 parts of phenol and 8 parts of toluene were added.
8 parts of p-toluenesulfonic acid and 190 parts of paratoluenesulfonic acid were reacted for 2 hours under reflux at 90 to 100°C while stirring in a reactor equipped with a condenser, and then dehydrated and reacted under reduced pressure until the temperature of the reaction mixture reached 140°C. completed. Next, 308 parts of toluene was added and neutralized with ammonia, to which 110 parts of paraformaldehyde and 22 parts of 28 $I ammonia were added and reacted at 85° to 90°C for 25 hours, and then condensed under reduced pressure. The water and toluene generated by the process were removed, and the resulting phenol-modified toluene-formaldehyde resin solution and benzoguanamine 30 were diluted with toluene.
0 parts and 383 parts of formalin (37% aqueous solution) to pH 9.
5 and heated at 95°C for 2 hours, dehydrated under reduced pressure and diluted with acetone.Resin solution and resol type phenol formaldehyde resin solution (solid content 50%)
150 parts and 165 parts of bisphenol A type epoxy resin (epoxy equivalent weight 500) and 1 part of benzyldimethylamine
After uniformly mixing 5 parts with stirring, 155 parts of tricresyl phosphate and 155 parts of brominated biphenyl were added and mixed, and the mixture was impregnated into 0.25-thick linter paper previously treated with phenol resin. Seal and dry to achieve B stage. The amount of resin attached is 0.
The ratio was 9. Nine sheets of this impregnated paper were stacked, and a copper foil was further stacked on one side of the paper, which was heated and pressed for 60 minutes under normal conditions, and then cooled. Table 2 shows the properties of the obtained laminate. Example 2 Toluene formaldehyde resin 44 obtained in Example 1
0 parts, 480 parts of metacresol, 88 parts of toluene, and 190 parts of para-toluenesulfonic acid were reacted in a reactor equipped with a cooling tube with stirring at 90° to 100°C under reflux for 15 hours, and then the temperature of the reaction mixture was adjusted under reduced pressure. The reaction was completed by dehydration until the temperature reached 140°C, and then 30°C of toluene was added to it.
0 parts was added and neutralized with ammonia.

To the cresol-modified toluene resin solution obtained here, 7200 parts of melami, 660 parts of formalin (37% aqueous solution),
Add 22 parts of hexamethylenetetramine to 80-86℃
The mixture was allowed to react for 3 hours, and then water and toluene generated by condensation were removed under reduced pressure, and the mixture was diluted with a mixed solvent of acetone and methanol to obtain a resin solution. Add 150% of resol type phenol formaldehyde resin solution (solid content 50%) to this solution.
part and bisphenol A type epoxy resin (epoxy equivalent: 5
00) A mixture of 165 parts of diaminodiphenylmethane, 168 parts of triphenyl phosphate, and 168 parts of brominated biphenyl was impregnated into 0.25E thick kraft paper that had been previously treated with melamine resin. A laminate was obtained in the same manner as in Example 1. Its properties are shown in Table 2. Example 3 Phenol-modified toluene formaldehyde resin solution obtained in Example 1, 300 parts of melamine, 15 parts of phenol
A resin solution and bisphenol A obtained by reacting 0 parts of formalin (37% aqueous swelling 720 parts) and 24 parts of aqueous ammonia (28% aqueous solution) at 80°C for 3 hours, dehydrating it under reduced pressure and diluting it with acetone. After uniformly mixing 165 parts of type epoxy resin (epoxy equivalent: 500) and 1.5 parts of benzyldimethylamine, 155 parts of tricresyl phosphate and 155 parts of brominated biphenyl were added and mixed. A laminate was obtained in the same manner as in the example.

Its properties are shown in Table 2.

Examples 4, 5, 6 In the method of Example 1, compounds shown 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.

Examples 7 and 8 In the method of Example 1, xylene resin and mesitylene resin were prepared as the aromatic hydrocarbon resin other than toluene resin to prepare Examples 6 and 7, 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 9 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 10 A laminate was obtained 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 16 parts to 1 part of the base material. Ta.

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 150 parts of triphenyl phosphate and 150 parts of brominated biphenyl was added to 1,000 parts and impregnated into a piece of linter paper with a thickness of 0.25 m that had been previously treated with phenol resin. A laminate was obtained.

The characteristics are shown in Table 2.

Claims (1)

[Claims] 1 A thermosetting resin composition consisting of a phenol-modified aromatic hydrocarbon formaldehyde resin, a compound having an S-triazine ring-formaldehyde resin, a phenol-formaldehyde resin, and an epoxy resin, or a phenol-modified aromatic hydrocarbon resin and S-triazine A thermosetting cocondensation resin composition obtained by reacting a ring-containing compound with formaldehyde, a thermosetting resin composition consisting of a phenol formaldehyde resin and an epoxy resin, or a phenol-modified aromatic hydrocarbon formaldehyde resin, a phenol. 5 to 50 parts of an organic phosphorus-containing compound and 5 to 50 parts of an organic phosphorus-containing compound to 100 parts of a thermosetting cocondensation resin composition obtained by reacting a compound having an S-triazine ring with formaldehyde and an epoxy resin. A resin mixture containing 5 to 60 parts of a halogen-containing compound is applied and impregnated onto a laminate base material, and the required number of sheets are stacked,
A method for producing a flame-retardant thermosetting resin laminate, characterized by heating and pressurizing it.