JPS5929426B2 - Manufacturing method of thermosetting resin products - Google Patents

Description

Detailed Description of the Invention The present invention relates to a thermosetting resin composition comprising a phenol-gradient aromatic hydrocarbon formaldehyde resin, a compound-formaldehyde resin having a 5-triazine ring, or a phenol-gradient aromatic hydrocarbon resin and a 5-triazine ring-containing compound-formaldehyde resin. - A resin mixture obtained by blending an organic phosphorus-containing compound and an organic halogen-containing compound with a thermosetting resin obtained by reacting a compound having a triazine ring with formaldehyde is impregnated into a laminate base material, and laminated molding is performed. This relates to the manufacturing method of flame-retardant thermosetting resin laminates, which are characterized by their superior flame resistance. The objective of the present invention is to provide thermosetting resin laminates that have 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, 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 may have a more or less adverse effect on electrical properties, mechanical strength, heat resistance, dimensional stability, chemical resistance, etc. When compared with non-combustible 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 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 provides satisfactory results.

That is, the method of the present invention uses a thermosetting resin composition consisting of a phenol-graded aromatic hydrocarbon formaldehyde resin, a compound-formaldehyde resin having an S-triazine ring, or a phenol-modified aromatic hydrocarbon resin and an S-triazine ring. 5 to 50 parts of an organic phosphorus-containing compound and 5 parts of an organic halogen-containing compound to 100 parts of a thermosetting resin composition obtained by reacting a compound having
The present invention relates to the production of a flame-retardant thermosetting resin laminate, which is characterized by coating and impregnating a laminate base material with a resin mixture containing 60 parts to 60 parts, stacking the required number of sheets, and heating and pressurizing them.

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

In the present invention, the phenol-modified aromatic hydrocarbon-formaldehyde resin includes benzene, toluene, xylene,
Phenol-modified aromatic carbonization in which the above-mentioned phenols are post-condensed to oxygen-containing aromatic hydrocarbon formaldehyde resin, which is obtained by condensing aromatic hydrocarbons such as mesitylene and naphthalene with formaldehyde under a strong acid catalyst such as sulfuric acid, and the above-mentioned phenols under an acidic catalyst. It refers to a resol-type phenol-modified aromatic hydrocarbon formaldehyde resin in which formaldehyde is condensed to a hydrogen resin under an alkali catalyst, and is a thermosetting resin having a methylol group (-CH2OH) in its structural 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. Compounds having an S-triazine ring as used in the present invention include melamines and guanamines, including melamine,
Substituted melamine, acetoguanamine, benzoguanamine, etc. can be suitably used.

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

As described above, a thermosetting resin composition is obtained by composing a phenol-modified aromatic hydrocarbon formaldehyde resin and a compound-formaldehyde resin having an S-triazine ring as the thermosetting resin component, and a preferred method is (1). (2) phenol-modified aromatic hydrocarbon resin, a compound having an S-triazine ring, and formaldehyde are the main reaction components, and the mixture is heated and co-condensed in the presence of an alkali. One example is the power method that can be obtained by

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 in combination to impart sufficient flame retardancy, but a combination gives preferable results.

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

Further, examples of organic halogen-containing compounds include chlorinated paraffin, halogenated epoxy compound, halogenated phenol, halogenated bisphenol A1 pat acid, and the like. 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 1/2 or less of that of the paper base material. As mentioned above, it is not clear why excellent heat 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, and the S-triazine ring compound-formaldehyde resin component do not compensate for the drawbacks of each, and as a result, they each bring about an improvement in curability that cannot be achieved alone. It is presumed that this prevents the deterioration of various properties that would otherwise be impaired, and maintains good quality equivalent to or better than that of non-combustible laminate products.

In the present invention, the phenol-modified aromatic hydrocarbon formaldehyde resin may be modified with a modifier such as drying oil, oak nut oil, etc., or a phenol resin, an epoxy resin, etc., as needed, for example, in order to impart flexibility. can.

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.
10 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. Dehydrated while heating under reduced pressure of LHg 4
40 parts of toluene formaldehyde resin was obtained.

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. The obtained toluene formaldehyde resin was reacted with 418 parts of phenol, 88 parts of toluene, and 190 parts of para-toluene sulfonic acid under reflux at 90 to 100°C for 2 hours while stirring in a reactor equipped with a cooling tube, 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, and 110 parts of paraformaldehyde and 22 parts of 28% ammonia were added thereto and reacted at 851 to 90°C for 2.5 hours, followed by condensation under reduced pressure. The water and toluene generated by were removed, and the resulting phenol-modified toluene-formaldehyde resin solution, 300 parts of benzoguanamine, and 383 parts of formalin (37% aqueous solution) were diluted with toluene.
9.5, heated at 95°C for 2 hours, dehydrated under reduced pressure, diluted with acetone, mixed homogeneously with stirring, and further added tricresyl phosphate 1
A mixture of 50 parts of brominated biphenyl and 150 parts of brominated biphenyl was pre-treated with phenolic resin to a thickness of 0.25 cm.
Impregnate a piece of m-wing linter paper and dry it to form the B stage. The amount of resin deposited was at a ratio of 0.9 to 1 of the base material. 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 1.90 parts of para-toluenesulfonic acid were reacted under reflux at 900 to 100°C for 1.5 hours with stirring in a reactor equipped with a condenser, and then reacted under reduced pressure. The reaction was completed by dehydration until the temperature of the mixture reached 140°C, and then 300 parts of toluene was added thereto and neutralized with ammonia.

To the cresol-modified toluene resin solution obtained here, 200 parts of melamine, 660 parts of formalin (37% aqueous solution),
22 parts of hexamethylenetetramine was added and reacted at 80 to 86 °C for 3 hours, 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 150 parts of triphenyl phosphate and 150 parts of brominated biphenyl was added to this solution and impregnated into kraft paper having a thickness of 0.25 ml and 1 L that had been previously treated with melamine resin.
A laminate was obtained in the same manner as above. Its properties are shown in Table 2. Examples 3, 4, 5 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 6 and 7 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, 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 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 obtained 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 to 1 of the base material. Ta.

The characteristics are shown in Table 2. Example 10 In Example 1, in addition to the phenol-modified toluene formaldehyde resin and benzoguanamine formaldehyde resin as the thermosetting resin, 150 parts of a resol type phenol formaldehyde resin solution (solid content 50%) was added, and tricresyl phosphate 175 was added. A laminate was obtained in the same manner as in Example 1, except that 175 parts of brominated biphenyl and 175 parts of brominated biphenyl were added and mixed.

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 m and 71 L that had been previously treated with phenol resin, and then mixed using the same force method as in Example 1. A laminate product was obtained.

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, or a phenol-modified aromatic hydrocarbon resin, a compound having an S-triazine ring, and formaldehyde 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 the thermosetting cocondensation resin composition obtained by the reaction is applied and impregnated onto the base material of the laminate. Seshime,
A method for producing a flame-retardant thermosetting resin laminate, which comprises stacking the required number of sheets and heating and pressurizing them.