JPS6024817B2 - thermosetting resin flame retardant - Google Patents

Description

[Detailed description of the invention] The present invention relates to thermosetting resin flame retardants.

More specifically, the present invention relates to a flame retardant used in a thermosetting resin for laminates. Thermosetting resins have traditionally been used mainly in electrical and electronic equipment, and are extremely important.

In recent years, various regulations regarding flame retardancy have been established for these materials as a safety measure against fire, and most of these materials are now being used as flammable materials.

Furthermore, when a thermosetting resin is used as a laminate, it must not only have flame retardancy but also sufficiently satisfy heat resistance, dimensional stability, electrical properties, punching workability, bleedability, etc. As publicly known techniques for solving these problems, Tokusekki Sho 53-104 General No. 2 Publication, Tokkan Sho 53-108
180, JP-A-53-136083, etc. exist.

However, the reality is that even these known techniques cannot be said to have sufficiently solved the above problems. The present inventors have conducted intensive research to further improve the above-mentioned drawbacks, and as a result, have come to provide the present invention.

That is, a phenol-formalin condensate obtained by condensing 0.6 to 2.5 mol of formaldehyde or formalin per 1 mol of phenols and a compound of the general formula [in the formula R1
, R2 is an alkyl group having 1 to 5 carbon atoms or a haloalkyl group, and R3 is an alkyl group having 1 to 12 carbon atoms.

XI is CI, Br, X2 is day, CI, Br, and n and m are integers of 1 to 3. This is a thermosetting resin retardant for laminates made of a phosphorus-containing phenol-formalin condensate having a gel time of 40 to 600 seconds. The phenol-formalin condensate used in the present invention includes phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, noniphenol, phenol, phenylphenol, phenylphenol ether, and phenol. Enoxyphenol, styrenated phenol, monochlorostyrenated phenol, mo/promostyrenated phenol, hydroquinone, resorcinol,
Dihydroxyphenyl ether, dihydroxydiphenyl, pis(hydroxyphenyl)pentane, dihydroxydiphenylmethane, bis(hydroxyphenyl)butane, dihydroxydiphenyl sulfone, dihydroxydiphenyl ketone, dihydroxydiphenylmethane, bis(hydroxyphenyl) ) Propane, methylenebis(ethyl-tertiarybutylcresol), mixtures thereof, etc. are condensed with formaldehyde or formalin by a known method. In this case, the amount of formaldehyde or formalin is 0.6 to 1 mole of phenol.
2.5 mol is used.

Next, the organic phosphoric acid monohalodate represented by the general formula is, for example, dimethyl phosphate monochloridate, diethyl phosphate monochloridate, dipropyl phosphate monochloridate, dibutyl phosphate monochloridate, diamyl phosphate monochloridate, di(chloroethyl phosphate), etc. ) Monochloridate phosphate, di(promoethyl)
Mo/chloridate phosphate, monochloridate di(chloropropyl)phosphate, monochloride di(promopropyl)phosphate.

Lydate, monochloridate pis(dichloropropyl)phosphate, monochloridate bis(dipromopropyl)phosphate, monochloridate diphenylphosphate, monochloridate dicresylphosphate, mo/chloridate dixylenylphosphate, bis(propylphenyl) Monochloridate phosphate, monochloridate bis(butylphenyl) phosphate, monochloridate bis(amylphenyl) phosphate,
Bis(/nylphenyl) phosphate monochloridate, Pis(dodecylphenyl) phosphate monochloridate, Pis(
Chlorophenyl) monochloridate phosphate, bis(dichlorophenyl) monochloridate phosphate, bis(tricoo phenyl) monochloridate phosphate, pis(bromophenyl) monochloridate phosphate, bis(dibromophenyl) monochloridate phosphate Date, Pis(tribromophenyl)monochloridate phosphate, Pis(dichlorocresyl)monochloridate phosphate, Pis(bromocresyl)monochloridate phosphate, Bis(dibromocresyl)
These include monochloridate phosphate, monopromidate dicresyl phosphate, monobromidate di(phenyl)phosphate, and mixtures thereof. Next, the phosphorus-containing phenol-formalin condensate of the present invention is obtained by reacting the phenol-formalin condensate and the organic phosphoric acid halodate represented by the general formula by a known method,
And the gel time at 150°C is 40-60.

In the present invention, the reaction molar ratio of phenols and formaldehyde or formalin is outside the range of 1:0.6 to 2.5, and the phosphorus-containing phenol-formalin condensate obtained therefrom has a gel time of 40 to 600 seconds. If it deviates from this range, the heat resistance and electrical properties of the obtained flame-retardant thermosetting resin laminate will decrease, and bleeding will occur.

Thermosetting resins for laminates targeted by the present invention include, for example, unsaturated polyester resins, epoxy resins, phenol resins, and melamine resins. The phosphorus-containing phenol-formalin condensate of the present invention is blended in an amount of 3 to 15 parts by weight per 100 parts by weight of the thermosetting resin. Although it is possible to mix more than this amount, it is economically restricted. Methods for using the phosphorus-containing formalin condensate include adding it at any stage during the production of the thermosetting resin, adding it to the thermosetting resin, and mixing it. In the present invention, in order to further improve flame retardancy, it is also possible to use an organic halogen-containing compound, antimony trioxide, etc. in combination.

Examples of the organic halogen-containing compound include halogenated phenol, halogenated aniline, halogenated pisphenol, halogenated diphenyl ether, halogenated phenylhydroxyethyl ether, and halogenated phenylglycidyl ether.

Furthermore, the phosphorous-containing formalin condensate of the present invention can be used in combination with commonly used modifiers such as vegetable oils, and plasticizers such as diphenylmonophenol phosphate and tricresyl phosphate. The thermosetting resin containing the phosphorus-containing phenol-formalin condensate of the present invention is generally used in the form of a solution dissolved in a solvent such as methanol, acetone, toluene, xylene, or the like.

The thermosetting resin laminate is manufactured according to a known method by adding phosphorphenol-containing formalin to the laminate base material, such as paper such as cotton linter paper or patterned paper, cotton cloth, synthetic fiber cloth, nonwoven fabric, glass cloth, etc. This is done by impregnating a thermosetting resin containing a condensate, overlapping the required number of resin-impregnated base materials, overlapping metal foil such as copper foil or silver foil as necessary, and applying heat and pressure. . According to the present invention, it is possible to obtain a thermosetting resin laminate having excellent flame retardancy, electrical properties, punching workability, and heat resistance.

Example 1 94 parts (1 mol) of phenol and 81 parts of 37% formalin were added as phenols to a reactor equipped with a reflux condenser and a reflux condenser.
．． 1 part (1 mol) and triethylamine 3 as catalyst
90 to 100 qo for 9 minutes.

5 while worshiping the obtained phenol-formalin condensate
Add 88 parts (1.1 mol) of 0% caustic soda aqueous solution,
Continue to stir the rope at 0 to 50 qo for 60 minutes to uniformly dissolve.
Next, 3 parts of toluene and 65 parts of methylene chloride were added and cooled, and 24 parts of monochloridate di(chloroethyl)phosphate was added.
1.5 parts (1 mol) was added dropwise between 20 and 30 o'clock. After the instillation is complete, continue the rope worship for 60 minutes. Next, p with 10% hydrochloric acid
Adjust H to 4-5 and wash with water 3 times. Separate the oily layer,
Adjust the boat to 7-8 with triethylamine and 60-80 under reduced pressure.
The solvent and water were distilled off at 0 qo to obtain 317.5 parts of a phosphorus phenol-formalin condensate (hereinafter referred to as compound A). Compounds B-1 were obtained in the same manner.

They are shown in Table 1. Ship Example 2 40 parts of the compounds listed in Table 1 of Example-1 were added to 100 parts of a commercially available phenolic resin varnish with a solid content of 60%, and a thickness of 0.
A 25mm cotton linter paper was impregnated to a resin content of 45% and dried to obtain a resin-impregnated base material.

Next, seven layers of the resin-impregnated base material were bonded and heated at 160°C and 80k.
Pressing was carried out for 50 minutes under the conditions of 9/10 to obtain a laminate with a thickness of 1.6 mm.

Using a similar process, tetraph is used as an additive-type brood retardant.

A test was also conducted in which 1 part of modiphenyl ether and 2033 parts of Sb were added. As a comparative example, a laminate was similarly obtained using the compounds listed in Table 1 of Example-1 and triphenyl phosphate. The properties of those laminates are shown in Table 2. Table 2 * Visual determination of oily ooze after storage at 120°C for 48 hours (Shoichi 1) The following examples are also of the same machine and will not be described.

Example 3 94 parts of phenol, 108 parts of cresol, 60 parts of the compound in Table 1 of Example 1, 37% formalin 2
40 parts, add triethylamine side, 90-100 pm
I reacted while worshiping koji for two hours.

After that, it was dehydrated under reduced pressure, methanol was added, and the resin content was 6
Adjust to 0% to obtain resol varnish. 10 parts of the obtained varnish was added with 1 part of tetrabromodiphenyl ether and 3 parts of SQ0 as an additive retardant, and impregnated on cotton linter paper with a thickness of 0.25 to a resin content of 45%. , and dried to obtain a resin-impregnated base material. Next, 7 sheets of the resin immersion base material were laminated, and 160008
Pressing was carried out for 50 minutes under the condition of 0k9/ground to obtain a laminate with a thickness of 1.6 skin.

Similarly, tetrabromodiphenyl ether and SQ03
We also conducted experiments without adding .

As a comparative example, a laminate was obtained in the same manner using Compound 1 in Table 1 of Example 11. The properties of those laminates are shown in Table 3. Table 3 Example 4 Epoxy resin (trade name, Epicort 828) 50% M old K solution 10 sparse parts, dicyandiamide 3 parts and Example 1
Mix and dissolve two parts of the compounds in Table 1.

Cotton linter paper with a thickness of 0.25 was immersed in the resulting solution, impregnated to a resin content of 45%, and dried to obtain a resin-impregnated base material. Next, seven sheets of the resin-impregnated base material and copper foil were stacked on one side and pressed for 60 minutes at 160°C and 80k9/base to obtain a laminate with a thickness of 1.6 ribs.

Similarly, 15 parts of the compound shown in Table 1 of Example-1 and 5 parts of tetrabromodiphenyl ether as an additive retardant,
A sample containing 32 parts of SQ0 was also tested.

As a comparative example, a laminate was similarly obtained using the compounds listed in Table 1 of Example 11.

The properties of those laminates are shown in Table 4.

Table 4 Example 5 Resin liquid 1 containing 8% by weight of trimethylolmelamine
Add 5 parts of the compound in Table 1 of Example 1 and 3 parts of acetamide, and then add methanol to bring the total amount to 10 parts.
It is set as 0 part.

Then, in the obtained melamine resin solution, 150 sails (vertical) and 1 (horizontal)
A patterned paper of 0 sq.m. was impregnated, squeezed to a weight increase of 80%, pre-dried at 60 to 80 qo, and further cured at 170 qo for 30 minutes to obtain a patterned paper.

As a comparative example, tetrabromobisphenol A (hereinafter T
Patterned paper was obtained in the same manner using BA.

Table 5 shows the properties of those patterned papers.

Claims (1)

[Claims] 1. A phenol-formalin condensate obtained by condensing 0.6 to 2.5 moles of formaldehyde or formalin per mole of phenols, and a general formula ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ [In the formula, R^1 and R^2 are carbon numbers 1 to 5
Alkyl groups and haloalkyl groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ where R_3 is H and an alkyl group having 1 to 12 carbon atoms. X^1 is Cl, Br, X^2 is H, Cl, Br,
n and m are integers of 1-3. ] obtained by reacting the organic phosphoric acid monohalodate shown in
A thermosetting resin flame retardant for laminates comprising a phosphor-containing phenol-formalin condensate having a gel time of 40 to 600 seconds.