JPS6346773B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to flame retardants for synthetic resins. Conventionally, flame retardant synthetic resins in which various halogen compounds, phosphorus compounds, and phosphorus-containing halogen compounds are added to synthetic resins as flame retardants, as well as various polymerizable synthetic resin monomers, oligomers, etc., have been produced using the above flame retardants. Flame-retardant synthetic resins obtained by adding and polymerizing are known. However, flame-retardant synthetic resins to which flame retardants have been added are not necessarily suitable for use in a wide variety of fields that require flame retardancy. Further, the flame retardant effect is lowered due to a decrease in physical properties and bleed out of the flame retardant from the flame retardant synthetic resin. Flame-retardant synthetic resins obtained by adding flame retardants to various polymerizable synthetic resin monomers, oligomers, etc. and polymerizing them are perfect in terms of flame retardancy, solvent resistance, physical properties, etc. do not have. In addition, when the above flame retardants are used in the production of synthetic resin adhesives, synthetic resin impregnated materials, etc., which are fields in which synthetic resins are used, there are problems such as insufficient flame retardancy, insufficient curing, and short pot life. exist. The present inventors have conducted intensive research to improve the above-mentioned drawbacks, and as a result, they have arrived at the present invention. That is,
This is a flame retardant for synthetic resins consisting of a compound represented by the following general formula () (hereinafter referred to as a compound represented by the general formula ()). (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are alkylene groups having 2 to 10 carbon atoms. P ₁ is an integer of 1 to 20. P ₂ , P ₃ and P ₄ are 0 or It is an integer of 1 to 20. Y is C ₁ or Br. n ₁ and m ₁ are integers of 1 to 4. A is -CH ₂ -, SO ₂ -,

【Formula】-or -O-.

[Formula] is H,

【formula】

[expression] or

[Formula]. ) Examples of the compound represented by the general formula () of the present invention include the following compounds. The compound represented by the above general formula () is a compound represented by the following general formula () (hereinafter referred to as general formula ()).
) and cinnamic acid, methacrylic acid, or acrylic acid, or a mixture thereof, in the absence of a solvent or in the presence of a solvent such as benzene, toluene, or xylene, by cation exchange with sulfuric acid, paratoluenesulfonic acid, or strong acid type cation. After carrying out a dehydration reaction in the air or nitrogen stream using a resin etc. as a catalyst, filtering or neutralizing, removing the catalyst by washing with water, distilling off the solvent, washing with alcohol or water-containing alcohol, and removing unreacted materials. obtained by removing . To prevent polymerization during the dehydration reaction, for example, 1000 ppm or less of methoxyhydroquinone as a polymerization inhibitor and 1000 ppm as an antioxidant are added to the reaction mixture.
It is desirable to add the following hindered phenols. (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are alkylene groups having 2 to 10 carbon atoms. P ₁ is an integer of 1 to 20. P ₂ , P ₃ and P ₄ are 0 or It is an integer from 1 to 20. Y is C ₁ or Br. n ₁ and m ₁ are integers from 1 to 4. A is -CH ₂ -, -SO ₂ -,

[Formula] - or -O-. ) Examples of the compound represented by the general formula () include the following compounds. When producing a flame-retardant synthetic resin, the compound represented by the general formula () of the present invention is added simultaneously with a copolymerizable compound and polymerized. Examples of copolymerizable compounds include all compounds having a group that can be polymerized with the compound represented by the general formula (). For example, unsaturated polyesters composed of fumaric acid or maleic acid esters, polybutadiene, styrene, polybutadiene glycol, alkyl vinyl ether-maleic anhydride copolymers, vinylphosphonic acid (bischloroethyl), glycidyl methacrylate, etc. Compounds having at least one double bond, epoxy acrylate resins or epoxy methacrylate resins, compounds having at least two ethylenically unsaturated double bonds such as diallyl phthalate, ethylenically unsaturated compounds such as triacrylisocyanurate, triacryl formal, etc. Examples include compounds having at least three or more double bonds. The amount of the compound represented by the general formula () of the present invention added is 1 to 300 parts per 100 parts of the copolymerizable compound. In addition, when the compound represented by the general formula () of the present invention is added as a flame retardant and polymerized to produce a flame-retardant synthetic resin, examples of polymerization methods include thermal polymerization using a radical-generating catalyst, photopolymerization, etc. , electron beam polymerization, radiation polymerization, and the like. The flame-retardant synthetic resin obtained by adding the compound represented by the general formula () of the present invention as a flame retardant and polymerizing it not only has excellent flame retardancy and solvent resistance, but also has a resin coating film that is free from scratches. It has advantages such as being hard to stick and having plasticity. Therefore, it is used as an electronic component coating material, a laminate, a resist ink casting resin, a wall covering material, an industrial material, etc. Examples of the present invention are listed below. In the examples, parts and percentages are by weight. Example 1 28.1 parts of cinnamic acid, 3 parts of para-toluenesulfonic acid,
2.6-Diterciabutyl-P-cresol 0.2
parts, 0.2 parts of methoxyhydroquinone, 200 parts of toluene
and reflux under a nitrogen stream to carry out a dehydration reaction. After the dehydration reaction is completed, the toluene is washed with the same amount of water, and then the toluene is distilled off. Next, add 300 parts of methanol, stir, and filter. The filtration residue was dried to obtain a compound having the following chemical structure and properties (hereinafter referred to as compound-A). Properties: acid value 0.05, saponification value 126.8 (127.8), bromine (%)
37.0 (36.4), melting point 121℃, decomposition start temperature 348℃, decomposition temperature 359℃, values in parentheses are theoretical values. same as below. Example 2 1 mol of ethylene glycol, 0.5 mol of phthalic anhydride, 0.5 mol of maleic anhydride, and 0.1% of the total amount of antimony trioxide were added to a reaction vessel, and after reacting for 5 hours at 190°C under a nitrogen stream, the mixture was further reduced to 20 torr at 230° C. The reaction was carried out at ℃ for 5 hours to obtain an unsaturated polyester resin. To a mixture of 100 parts of this unsaturated polyester resin, 10 parts of styrene monomer, and 40 parts of Compound A, 2 parts of tertiary butyl perbenzoate was added.
1 part and 2 parts of cobalt naphthenate were cast and cured, followed by curing at 80° C. for 2 hours. The obtained flame retardant unsaturated polyester resin was tested for flame retardancy and water resistance. Comparative examples were also carried out in the same manner. The results are shown in Table 1.

[Table] Example 3 100 parts of polyester resin (obtained by reacting 0.5 mol of ethylene glycol, 0.5 mol of propylene glycol, 0.5 mol of isophthalic acid, and 0.5 mol of maleic anhydride). (Properties: Bromine (%) 43.9 (44.6), melting point 88°C, decomposition temperature 337°C, obtained in the same manner as in Example 1.
It is hereinafter referred to as compound B. ) Trimethylolpropane triacrylate 8
1 part ditertiary butyl peroxide, 0.5 part benzoin methyl ether, 50 parts glass fiber,
Synthetic mica surface treated with 2 parts of triethylamine
50 parts of antimony trioxide and 5 parts of antimony trioxide were kneaded to obtain a flame retardant preservation sheet having a thickness of 1/2 inch. The storage stability of the obtained flame-retardant storage sheet was tested. A comparative example was conducted in the same manner. The results are shown in Table 2.

[Table] Example 4 The flame-retardant preservation sheet obtained in Example-3 was
After 60 seconds of irradiation with a 100W ultra-high pressure mercury lamp, 160 ~
A flame-retardant sheet was obtained by pressing at 165° C. and 50 kg/cm ² for 2 minutes. The flame retardancy of the obtained flame retardant sheet was tested. Comparative examples were also conducted in the same manner. However, the comparative example is an example.
Using 20 parts of hexabromodiphenyl ether instead of 30 parts of bisphenol A bishydroxyethyl ether bismethacrylate in Example 3,
A flame-retardant preservation sheet obtained in the same manner as in 3 was used. The flame retardancy of the obtained flame retardant sheet was tested. The results are shown in Table 3.

[Table] Example 5 50 parts of 1.2-polybutadiene (molecular weight 3000), 1:1 mixture of compound-A and compound-B
50 parts, glass fiber 100 parts, mica treated with triethylamine 2 parts
100 parts and 2 parts of shicumyl peroxide were kneaded and pressed at 170°C and 200 kg/cm ² for 10 minutes to obtain a flame-retardant sheet. The obtained flame retardant sheet was tested for flame retardancy and solvent resistance. Comparative examples were also conducted in the same manner. The results are shown in Table 4.

[Table] Example 6 50 parts of unsaturated polyester (obtained by reacting 0.5 mol of ethylene glycol, 0.5 mol of propylene glycol, 0.5 mol of phthalic acid, and 0.5 mol of maleic anhydride). (Obtained in the same manner as in Example-1.Hereinafter referred to as Compound-C) Trimethylolpropane triacrylate 10
A mixture of 2 parts of penzoin ethyl ether, 10 parts of methyl ethyl ketone, and 1 part of dicumyl peroxide was applied onto a copper plate and kept at room temperature for 1 hour.
Dry at 80°C for 20 minutes. The thickness of the resin coating layer is
It was 30μ. Next, it was exposed to direct sunlight in August for 2 hours. The flame retardancy and peelability of the obtained flame-retardant resin-coated copper plate were tested. Comparative examples were also conducted in the same manner. The results are shown in Table 5.

[Table] Example 7 100 parts of polyester resin (obtained by reacting 0.5 mol of trimellitic anhydride, 0.5 mol of maleic anhydride, and 1.0 mol of ethylene glycol). (Obtained in the same manner as in Example-1. Hereinafter referred to as Compound-D) 1 part of ditertiary butyl peroxide, 1 part of benzoin methyl ether, 3 parts of antimony trioxide
Mica treated with 1 part and 2 parts of triethylamine
100 parts were kneaded to obtain a sheet. This sheet was applied using a Ford-type scanning electron beam irradiation device at a voltage of 270 KV, a current of 65 mA, and an irradiation time of 5 seconds.
A flame-retardant cured product was obtained by curing in a butane gas stream. The flame retardancy of the obtained flame retardant cured product was tested. The results are shown in Table 6.

[Table] Example 8 100 parts of methacrylic acid compound (obtained by reacting 1 mole of bisphenol A diglycidyl ether and 2 moles of methacrylic acid) (Obtained in the same manner as in Example-1.Hereinafter referred to as Compound-E.) A glass cloth was impregnated with a mixture of 10 parts of tribromophenyl methacrylate, 10 parts of xylylene diisocyanate, 10 parts of methyl ethyl ketone, and 3 parts of benzoin ethyl ether. I let it happen. The impregnated glass cloth was left at room temperature for 12 hours and then dried at 80°C for 30 minutes. Next, it was irradiated with a 100W high-pressure mercury lamp for 60 seconds to obtain a flame-retardant photocured product. The resin content of flame-retardant photocured material is 80
It was %. The flame retardancy of the obtained flame-retardant photocured material was tested. The results are shown in Table 7.

【table】

Claims (1)

[Claims] 1. A flame retardant for synthetic resins comprising a compound represented by the following general formula () (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ are alkylene groups having 2 to 10 carbon atoms. P ₁ is an integer of 1 to 20. P ₂ , P ₃ and P ₄ are 0 or It is an integer from 1 to 20. Y is C ₁ or Br. n ₁ and m ₁ are integers from 1 to 4. A is -CH ₂ -, -SO ₂ -, [Formula] - or -O --. [Formula] is H, [Formula] [Formula] or [Formula].)