JPH10182890A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin compsn. which is free from the bleeding of a flame retardant by compounding an olefin resin with an org. halogenated arom. compd. flame retardant, a styrene-methylstyrene copolymer resin in a specified ratio to the flame retardant, and an auxiliary flame retardant each in a specified amt. SOLUTION: This compsn. is prepd. by compounding and kneading 100 pts.wt. olefin resin (e.g. a polypropylene resin) with 0.5-40 pts.wt. org. halogenated arom. compd. flame retardant such as represented by formula I (wherein A is an alkylene, carbonyl, etc.; X is Br or Cl; and m+n is 1-10) (e.g. a halogenated diphenylmethane), 0.2-60 pts.wt. styrene-methylstyrene copolymer resin having a softening point of 70-140 deg.C in a wt. ratio to the flame retardant of 0.4-1.5, 0.1-30 pts.wt. auxiliary flame retardant (e.g. Sb2 O3 ), 0.05-5 pts.wt. phenol resin represented by formula II (wherein R1 is a 1-8C alkyl; R2 is H or a 1-8C alkyl; and n is 1-6), and 0.05-5 pts.wt. organotin compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which is excellent in flame retardancy and suppresses so-called bleeding of a flame retardant on a molded product surface.

[0002]

2. Description of the Related Art Conventionally, flame retardants of olefin resins and the like have been developed by adding a flame retardant to a resin, blending a flame retardant resin, and producing a flame retardant polymer by reacting with a flame retardant monomer. And so on.

[0003] Among them, a method generally used is a method of adding a flame retardant to a resin, and the flame retardation of many resins is performed by this method. In this method, as the flame retardant, an organic chlorinated compound, a halide such as a bromide, a phosphorus-containing compound such as a phosphoric ester or a phosphite, a simple phosphorus such as a red phosphorus, and a metal hydroxide are usually used. Antimony trioxide is commonly used as a flame retardant aid. In particular, it is known that an organic halogenated aromatic compound-based flame retardant can impart high flame retardancy to an olefin resin.

[0004]

However, the above-described organic halogenated aromatic compound-based flame retardant can impart high flame retardancy to an olefin resin, but has poor compatibility with the olefin resin and has a low crystallinity. Because of its high property, even if it is uniformly dissolved in the resin at the beginning of molding, it gradually crystallizes and often precipitates as white powder on the surface of the molded product. This phenomenon is generally referred to as bleeding, and particularly at high temperatures, this phenomenon is remarkably observed, and there is a problem in that the appearance of the product is impaired, and the electrical characteristics of the surface are deteriorated.

For example, Japanese Patent Publication No. 50-23064 discloses that 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) is added to polypropylene.
A polypropylene composition containing propane and chlorinated polyethylene is disclosed as a flame-retardant polypropylene composition having a low bleed.However, even in the polypropylene composition, the bleeding of the flame retardant to the surface of the molded article is not completely eliminated. In addition, thermal degradation of the chlorinated polyethylene occurred, and the flame retarding effect was not sufficient.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a flame-retardant resin composition having no bleed of a flame retardant without lowering the flame retardancy of an olefin resin. It is to be.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the drawbacks of the conventional flame retardants and to obtain a flame-retardant resin composition having low bleed and high flame retardancy. When a mixture of a methylstyrene-based copolymer resin and a flame retardant in a specific ratio is used, bleeding is reduced and an excellent flame-retardant effect is exhibited. Further, a phenolic compound and / or an organotin-based compound are used. By mixing at a specific ratio, it is possible to obtain a flame-retardant resin composition that is not only less bleeding and exhibits excellent flame-retardant effect, but also has excellent heat resistance and is economically advantageous. They have found that they can do this and have completed the present invention.

That is, the present invention relates to an olefin resin (A) 1
0.5 to 40 parts by weight of an organic halogenated aromatic compound-based flame retardant (B), 0.2 to 60 parts by weight of a styrene-methylstyrene-based copolymer resin (C), and a flame-retardant auxiliary with respect to 00 parts by weight. (D) 0.1 to 30 parts by weight, and the compounding ratio of the styrene-methylstyrene-based copolymer resin (C) to the compounding amount of the organic halogenated aromatic compound-based flame retardant (B) is 0.4 to 0.4; 1.5, and further, 0.05 to 5 parts by weight of a phenolic compound (E) and / or organotin with respect to 100 parts by weight of the olefin resin (A). A flame-retardant resin composition comprising 0.05 to 5 parts by weight of a compound (F).

Hereinafter, the present invention will be described in more detail.

The olefin resin (A) used in the present invention
As, various polymers mainly composed of olefins,
For example, low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-propylene Copolymers, ethylene-butene copolymers, propylene-butene copolymers, maleic acid-modified polypropylene, maleic acid-modified polyethylene, and the like are included, but are not particularly limited thereto.

As the organic halogenated aromatic compound flame retardant (B) of the present invention, at least one flame retardant selected from the group consisting of the flame retardants represented by the following general formulas (1) to (4): use.

[0012]

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(In the formula, A represents an alkylene group, a carbonyl group, or —O—. The alkylene group may be partially bonded to another position of the benzene ring to form a cyclic structure; X may further be substituted with a halogen, alkenyl group, aryl group or halogenated aryl group, X represents a bromine or chlorine atom, n and m are integers, and n + m = 1 to 1
0. )

[0014]

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(In the formula, B represents an alkylene group, a carbonyl group, a —O—, —S—, —SO— or —SO ₂ — group. One part of the alkylene group is located at another position of the benzene ring. X may be substituted with a halogen, alkenyl group, aryl group or halogenated aryl group, X represents a bromine or chlorine atom, and n and m are integers. , N + m = 1 to 8)

[0016]

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[0017] (wherein, E is an alkylene group, a carbonyl group, -0 -, - S -, - SO- or -SO ₂ -. A group and the alkylene group in addition to the position of a portion of the benzene ring X may be substituted with a halogen, alkenyl group, aryl group or halogenated aryl group, X represents a bromine or chlorine atom, and n and m are integers. , N + m = 1 to 8. Y is C
_i H _{2i + 1-z} X _{z An} alkyl halide represented by X _z ,
i = 1 to 8, z = 1 to 2i + 1. )

[0018]

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(Wherein D is a direct single bond, an alkylene group,
Oxyalkylene group, diphenylsulfone-ar, a
r'-diyl group, diphenyl oxide-ar, ar'-
A diyl group or a carbonyl group, and these divalent substituents excluding a direct single bond further include a halogen, an alkenyl group,
It may be substituted with an aryl group or a halogenated aryl group. X represents a bromine or chlorine atom. n and m are integers,
n + m = 1 to 8. Examples of the halogenated diphenyl compound represented by the general formula (1) include diphenylalkane, diphenylketone, diphenylether, diphenylsulfide,
And diphenyl sulfoxide and halides of diphenyl sulfone.

The halogenated diphenylalkane includes:
For example, diphenylmethane, diphenylethane, monobromo-substituted products such as diphenylpropane, dibromo-substituted products,
Substituted tribromo, tetrabromo, pentabromo, hexabromo, heptabromo, octabromo, nonabromo and decabromo derivatives are exemplified. Further, brominated and chlorinated hydrogenated products of styrene dimer, α-methylstyrene dimer, and β-methylstyrene dimer (hereinafter, referred to as “styrene dimer halide”) and 1- Methyl-3-phenylindane,
Brominated and chlorinated compounds such as 1,1-dimethyl-3-phenylindane (hereinafter, referred to as "indane halides") are exemplified. These methods include styrene,
There are known a method of halogenating hydrocarbons using α-methylstyrene and β-methylstyrene as raw materials, and a method using styrene, α-methylstyrene and β-methylstyrene previously halogenated as raw materials.

Examples of the halogenated diphenyl ether compound include, for example, pentabromodiphenyl ether, hexabromodiphenyl ether, heptabromodiphenyl ether, octabromodiphenyl ether, nonabromodiphenyl ether, decabromodiphenyl ether, pentachlorodiphenyl ether, hexachlorodiphenyl ether, hepta Chlorodiphenyl ether,
Octachlorodiphenyl ether, nonachlorodiphenyl ether, decachlorodiphenyl ether and the like can be mentioned.

Examples of the halogenated diphenyl ketone compound include dibromo diphenyl ketone, tribromo diphenyl ketone, tetrabromo diphenyl ketone, dichloro diphenyl ketone, trichloro diphenyl ketone, tetrachloro diphenyl ketone and the like.

Of these, decabromodiphenyl ether and decabromodiphenylethane are preferably used because of their excellent flame retardancy and industrial availability.

Examples of the halogenated bisphenol compound represented by the general formula (2) include, for example, bis (3,5)
-Dibromo-4-hydroxyphenyl) methane, 1,1
-Bis (3,5-dibromo-4-hydroxyphenyl)
Ethane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) cyclohexane, bis (3,5-dibromo-4- Hydroxyphenyl) -phenylmethane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3,5-dichloro-
4-hydroxyphenyl) ethane, 2,2-bis (3,
5-dichloro-4-hydroxyphenyl) propane,
1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, bis (3,5-dichloro-4-
Hydroxyphenyl) -phenylmethane, bis (3,5
-Dibromo-4-hydroxyphenyl) ketone, bis (3,5-dibromo-4-hydroxyphenyl) ether, bis (3,5-dibromo-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-) Hydroxyphenyl) sulfone, bis (3,5-dibromo-4)
-Hydroxyphenyl) sulfoxide, bis (3,5-
Dichloro-4-hydroxyphenyl) ketone, bis (3,5-dichloro-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) sulfide, bis (3,5-dichloro-4-hydroxy) Phenyl) sulfone, bis (3,5-dichloro-4)
-Hydroxyphenyl) sulfoxide and the like, and among these, 2,2-bis (3,5-dibromo-4-
(Hydroxyphenyl) propane is preferably used in view of flame retardancy and industrial availability.

As the bis (haloalkyl ether) -based compound of halogenated bisphenol represented by the above general formula (3), for example, bis (3,5-dibromo-4-)
(2,3-dibromopropoxy) phenyl) methane,
1,1-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) ethane, 2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) Propane, 1,1-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl)
Cyclohexane, bis (3,5-dibromo-4- (2,
3-dibromopropoxy) phenyl) -phenylmethane, bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl) methane, 1,1-bis (3,5
-Dichloro-4- (2,3-dibromopropoxy) phenyl) ethane, 2,2-bis (3,5-dichloro-4-
(2,3-dibromopropoxy) phenyl) propane,
1,1-bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl) cyclohexane, bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl) -phenylmethane, Bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl)
Ketone, bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) ether, bis (3,5-
Dibromo-4- (2,3-dibromopropoxy) phenyl) sulfide, bis (3,5-dibromo-4- (2,
3-dibromopropoxy) phenyl) sulfone, bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) sulfoxide, bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl ) Ketone, bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl) ether, bis (3,5-dichloro-4- (2,3-dibromopropoxy) phenyl)
Sulfide, bis (3,5-dichloro-4- (2,3-
Dibromopropoxy) phenyl) sulfone, bis (3,
5-dichloro-4- (2,3-dibromopropoxy) phenyl) sulfoxide and the like.
2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane and bis (3,5-
Dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone is preferably used in view of flame retardancy and industrial availability.

Examples of the halogenated phthalimide compound represented by the general formula (4) include 1,2-bis (tetrabromophthalimide) ethane, bis (tetrabromophthalimide) propane, bis (tetrabromophthalimide) butane, Bis (tetrachlorophthalimide)
Ethane, bis (tetrachlorophthalimide) propanes, bis (tetrachlorophthalimide) butanes, bis (tetrabromophthalimidoethyl) ether, bis (tetrabromophthalimidopropyl) ether, bis (tetrabromophthalimidobutyl) ether, bis (tetra Chlorophthalimidoethyl) ether, bis (tetrachlorophthalimidopropyl) ether, bis (tetrachlorophthalimidobutyl) ether, bis (tetrabromophthalimidophenyl) sulfone, bis (tetrachlorophthalimidophenyl) sulfone, bis (tetrabromophthalimidophenyl) ketone , Bis (tetrachlorophthalimidophenyl) ketone, bis (tetrabromophthalimidophenyl) ketone, bis (tetrachlorophthalimidophenyl) ketone ) Ketone, and the like. Among these, 1,2-bis (tetrabromophthalimide) ethane is preferably used in view of flame retardancy and industrial availability.

The amount of the organic halogenated aromatic compound-based flame retardant (B) to be added to the olefin resin (A) is 0.5 to 40 based on 100 parts by weight of the olefin resin (A).
Parts by weight. If the amount is less than 0.5 part by weight, the flame-retarding effect is insufficient, and if it exceeds 40 parts by weight, not only the mechanical strength of the composition is remarkably reduced, but also economically disadvantageous. As the styrene-methylstyrene copolymer resin (C) used in the present invention, the copolymerization ratio of styrene and methylstyrene is styrene: methylstyrene = 90: 10-1.
Those having a range of 0:90 (weight ratio) are used. If the copolymerization ratio is out of the range, the effect of suppressing the bleeding of the organic halogenated aromatic compound-based flame retardant (B) may be poor.

The styrene-methylstyrene copolymer resin (C) used in the present invention usually has a softening point of 70.
Those having a temperature range of -140 ° C are used. Those having a softening point of less than 70 ° C are not preferred because the styrene-methylstyrene copolymer resin itself is blown out of the composition, and those having a softening point of more than 140 ° C are not only inferior in the effect of suppressing bleeding, but also have a poor mechanical effect. There is a case where the strength is remarkably reduced, which is not preferable.

Examples of the methylstyrene in the styrene-methylstyrene copolymer resin (C) used in the present invention include α-methylstyrene and β-methylstyrene. The blending amount of the styrene-methylstyrene-based copolymer resin (C) with respect to the olefin-based resin (A) is 0.2 to 60 parts by weight based on 100 parts by weight of the olefin-based resin (A). The styrene-methylstyrene copolymer resin (C) used in the present invention has a strong relationship with the compounding amount of the organic halogenated aromatic compound flame retardant (B), and the organic halogenated aromatic compound flame retardant (B) )), The blending ratio of the styrene-methylstyrene copolymer resin (C) is
It is in the range of 0.4 to 1.5. When the compounding weight ratio is less than 0.4, the effect of suppressing bleeding is inferior, and when the compounding weight ratio exceeds 1.5, not only the flame retardancy of the composition decreases, but also the mechanical strength of the composition decreases, It is economically disadvantageous.

The method for producing the styrene-methylstyrene copolymer resin used in the present invention includes radical polymerization, cationic polymerization, anionic polymerization and the like. The manufacturing method is not particularly limited.

The styrene-methylstyrene copolymer resin (C) significantly reduces bleed without reducing the flame retardant effect of the organic halogenated aromatic compound flame retardant (B) on the olefin resin (A). Suppress.

The flame-retardant resin composition of the present invention further comprises a flame-retardant aid (D) in order to further enhance the flame-retardant effect. Examples of the flame retardant aid (D) include antimony compounds such as antimony trioxide, antimony tetroxide and antimony pentoxide, tin compounds such as tin oxide, tin hydroxide, zinc stannate and zinc hydroxystannate, and molybdenum oxide And molybdenum compounds such as ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, and boron compounds such as zinc borate and barium metaborate.

The amount of the flame retardant aid (D) is strongly related to the organic halogenated aromatic compound flame retardant (B).
It is usually 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, based on 100 parts by weight of the olefin resin (A). When the amount is less than this, no flame-retardant synergistic effect is observed.

In the present invention, a phenolic compound (E) and / or an organotin compound (F) may be further added to the above-mentioned flame-retardant resin composition.

As the phenolic compound (E) of the present invention, at least one selected from the group consisting of phenolic compounds represented by the following general formulas (5) to (9) is used.

[0036]

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(In the formula, R ₁ represents an alkyl group having 1 to 8 carbon atoms, R ₂ represents hydrogen or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 6.)

[0038]

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Wherein R ₃ represents an alkyl group having 1 to 8 carbon atoms, and R ₄ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.
m represents an integer of 1 to 6, and p represents an integer of 10 to 20, respectively. )

[0040]

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(In the formula, R ₅ represents an alkyl group having 1 to 8 carbon atoms, and R ₆ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.
i shows the integer of 1-6. )

[0042]

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Wherein R ₇ represents an alkyl group having 1 to 8 carbon atoms, and R ₈ represents hydrogen or an alkyl group having 1 to 8 carbon atoms.
j represents an integer of 1 to 4. )

[0044]

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(Wherein, R ₉ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₁₀ and R ₁₁ each independently represent hydrogen, a methyl group or —C (CH 3) 2 —R ′ (where R ′ represents an alkyl group having 1 to 5 carbon atoms or a phenyl group.) And R ₁₂ represents hydrogen or a methyl group.) Examples of the compound represented by the general formula (5) include: ,
Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane, tetrakis [methylene-3- (3′-tert-butyl-5′-methyl) 4'-hydroxyphenyl) propionate] methane, tetrakis [methylene-3- (3'-
t-butyl-4'-hydroxyphenyl) propione-
G) methane and the like.

Examples of the compound represented by the general formula (6) include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and octadecyl-3- (3-t-butyl) -5-methyl-4-hydroxyphenyl) propionate, octadecyl-3
-(3-t-butyl-4-hydroxyphenyl) propionate and the like.

As the compound represented by the above general formula (7), for example, tris [(3,5-di-tert-butyl-4-)
(Hydroxybenzyl) isocyanurate, tris [(3
-T-butyl-5-methyl-4-hydroxybenzyl)
Examples include isocyanurate and tris [(3-t-butyl-4-hydroxybenzyl) isocyanurate.

The compound represented by the general formula (8) includes, for example, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t-butyl-4′-hydroxy Benzyl) benzene, 1,3,5-trimethyl-2,
4,6-tris (3′-tert-butyl-5′-methyl-
4'-hydroxybenzyl) benzene, 1,3,5-trimethyl-2,4,6-tris (3'-t-butyl-
4'-hydroxybenzyl) benzene and the like.

Examples of the compound represented by the general formula (9) include 2-t-butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-
3,5-di-t-pentylphenyl) ethyl] -4,6
-Di-t-pentylphenyl acrylate;

The mixing amount of the phenolic compound (E) with respect to the olefinic resin (A) is
It is 0.05 to 5 parts by weight based on 100 parts by weight.
If it is less than 0.05 part by weight, the effect of improving heat resistance is insufficient, and if it exceeds 5 parts by weight, it is economically disadvantageous.

The organotin compound (F) used in the present invention
Examples thereof include dimethyltin malate, dibutyltin malate, dioctyltin malate and the like.

The compounding amount of the organotin compound (F) with respect to the olefin resin (A) is 10
It is 0.05 to 5 parts by weight with respect to 0 parts by weight. 0.0
If it is less than 5 parts by weight, the effect of improving heat resistance is insufficient, and if it exceeds 5 parts by weight, it is economically disadvantageous.

The flame-retardant resin composition of the present invention comprises, for example, an olefin resin (A), the above components (B), (C),
Flame retardant aid (D), furthermore phenolic compound (E) and / or
Alternatively, a predetermined amount of the organotin-based compound (F), and other additives, if necessary, are blended and preliminarily mixed with a mixer such as a Henschel mixer, a ribbon mixer, etc., and then an extruder, a kneader, a hot roll, a Banbury mixer, etc. And can be easily manufactured by melt-kneading.

The flame-retardant resin composition of the present invention may be generally used, if necessary, as long as the excellent flame retardancy of the present invention and the effect of suppressing the bleeding of the flame retardant are not significantly impaired. UV absorbers, light stabilizers, release agents, lubricants, colorants, fillers, foaming agents, antioxidants, heat stabilizers, antistatic agents, compatibilizers, impact modifiers, crosslinkers, glass fibers And various additives such as carbon fiber.

The flame-retardant resin composition of the present invention comprises the olefin resin (A), the organic halogenated aromatic compound flame retardant (B) and the styrene-methylstyrene copolymer resin (C). When the styrene-methylstyrene-based copolymer resin (C) is mixed with the olefin-based resin (A) and the organic halogenated aromatic compound-based flame retardant (B) ) Have affinity with each other, and this is considered to be a factor that gives the above-mentioned bleed control effect.

By uniformly mixing the olefin resin (A) and the phenol compound and / or the organotin compound, the bleed control effect of the styrene-methylstyrene copolymer resin (C) is not impaired. This is considered to improve heat resistance, and is considered to be because hydrogen halide resulting from the dehalogenation reaction of the organic halogenated aromatic compound-based flame retardant (B) due to heat is effectively captured.

[0057]

As is apparent from the above description, the composition of the present invention is a flame-retardant resin composition in which the bleed is remarkably improved without lowering the flame retardancy. Since it can be applied and can provide a molded article having a good appearance, it is extremely useful as a material for electric / electronic parts, automobile parts, interior materials, building materials, and the like.

[0058]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples.

The methods of various tests carried out in the examples and comparative examples are as follows.

<Bleed test> After the test pieces were heated in a gear oven at 80 ° C for 120 hours, the appearance of the test piece surface was observed with a reflection microscope, and the following ranking was performed.

：: No bleeding of the flame retardant and no change in appearance. Δ: Flame retardant slightly bleeded. X: Flame retardant remarkably bleeds.

When bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone is used as the organic halogenated aromatic compound flame retardant, the method described above can be used. After heating the test piece in a gear oven at 80 ° C. for 120 hours, the flame retardant bleeding on the surface of the test piece was wiped with dioxane, and the weight change of the test piece before and after wiping was determined. Was attached.

<Heat cycle bleed test> A test piece was heated in a gear oven at 80 ° C for 12 hours, and then heated at room temperature for 1 hour.
It was left for 2 hours, and a cycle test was performed five times with this as one cycle, and the bleeding state of the test piece surface after the test was evaluated by the same method and criteria as in the above-mentioned bleeding test.

<UL-94 flammability test> Five test specimens each having a length of 125 mm, a width of 25 mm, a thickness of 3.2 mm or 1.6 mm were measured based on the vertical flammability test method of Subject No. 94 of Underwriters Laboratory. It measured using.

<Heat resistance test> After being kept in an injection molding machine set at 220 ° C. for 30 minutes, injection molding was resumed.
The difference between the color tone of the test piece at the third shot after the stay and the color tone of the test piece before the stay was compared with a color difference meter using the following equation.

ΔE = [(L−L ₀ ) ² + (a−a ₀ ) ² +
^{_{(B-b 0) 2]}} 1/2 L, a, b: hue L ₀ of three shots after residence, a _0, b _0: color previous examples residence 1 to Example 3 Polypropylene resin (manufactured by Chisso; Product name "Nissopolypro K7014"), 2,2-bis (3,5-dibromo-
4- (2,3-dibromopropyloxy) phenyl) propane (manufactured by Tosoh Corporation; trade name: “Frame Cut 121”)
K "), styrene: α-methylstyrene = 30: 70
Styrene-α-methylstyrene copolymer resin (1) having a copolymerization ratio of (weight ratio) and a softening point of 85 ° C., and antimony trioxide (manufactured by Tosoh; trade name “Frame Cut 61”)
OR) was mixed at a ratio shown in Table 1 and melt-kneaded in a twin-screw extruder set at 200 ° C to produce a composition pellet. The pellets were set on an injection molding machine set at 210 ° C.
Test pieces for an impact resistance test, a bleed test, and a UL-94 flammability test were prepared. Using the obtained test pieces, an impact test, a bleed test, and a UL-94 flammability test were performed.
Table 1 shows the results.

[0067]

[Table 1]

As a result of the UL-94 flammability test, all of the flame retardancy grades were V-0, and no bleed was observed on the test pieces after the bleed test and the heat cycle bleed test.

Examples 4 and 5 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) propane (Example 1) ), Decabromodiphenyl-ter (manufactured by Tosoh Corporation, trade name: “Frame Cut 110R”), styrene-α-methylstyrene copolymer resin (1) (same as in Example 1), and antimony trioxide (Example) Ex. 1) were mixed in the proportions shown in Table 1 to produce test specimens in exactly the same manner as in Example 1.
The same evaluation as in Example 1 was performed. The results are shown in Table 1. Even when an organic halogenated aromatic compound flame retardant was used in combination, bleeding of the flame retardant could be suppressed by adding a styrene-α-methylstyrene copolymer resin.

Comparative Example 1 A test piece was prepared in exactly the same manner as in Example 1 except that the styrene-α-methylstyrene copolymer resin (1) was not added, and the same evaluation as in Example 1 was performed. . The results are shown in Table 1. As compared with Examples 1 to 3, when the styrene-α-methylstyrene copolymer resin was not added, the bleeding of the flame retardant was remarkable.

Comparative Examples 2 and 3 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) propane (Example 1) Chlorinated polyethylene (manufactured by Showa Denko; product name "Eraslen 40")
1A ") and antimony trioxide (same as in Example 1) were mixed in the proportions shown in Table 1 to produce test pieces in exactly the same manner as in Example 1, and evaluated in the same manner as in Example 1. went. The results are shown in Table 1. As compared with Examples 1 to 3, when the amount of the chlorinated polyethylene is small,
When the chlorinated polyethylene had a poor bleeding suppressing effect of the flame retardant, while when the amount of the chlorinated polyethylene was large, the bleeding of the flame retardant could be suppressed, but the flame retardancy was reduced.

Comparative Examples 4 and 5 Test pieces were prepared in exactly the same manner as in Example 1 except that the blending amount of the styrene-α-methylstyrene copolymer resin (1) was added at the ratio shown in Table 1. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 1. Example 1
Compared with Example 3, when the blending ratio of the styrene-α-methylstyrene copolymer resin to the blending amount of TBA-BP is less than 0.4, the bleeding of the flame retardant is remarkable,
When the compounding ratio exceeds 1.5, the impact resistance and the flame retardancy of the composition are lowered.

Examples 6 to 8 As styrene-α-methylstyrene copolymer resins, styrene-α having a softening point of 100 ° C. and a copolymerization ratio of styrene: α-methylstyrene = 30: 70 (weight ratio) were used. -Methylstyrene copolymer resin (2), styrene-α-methylstyrene copolymer resin (3) having a softening point of 120 ° C. and a copolymerization ratio of styrene: α-methylstyrene = 30: 70 (weight ratio), or styrene : Α-methylstyrene = 50: 5
A test piece was prepared in exactly the same manner as in Example 1 except that a styrene-α-methylstyrene copolymer resin (4) having a softening point of 85 ° C., which is a copolymerization ratio of 0 (weight ratio), was used. The same evaluation as in Example 1 was performed. Table 2 shows the results.

[0074]

[Table 2]

When a styrene-α-methylstyrene copolymer resin having a copolymerization ratio of α-methylstyrene to styrene and a softening point within the scope of the claims of the present invention is used, the flame retardant No bleed was observed, and the mechanical strength was excellent.

Comparative Examples 6 to 9 As styrene-α-methylstyrene copolymer resins, styrene-α having a softening point of 65 ° C. and a copolymerization ratio of styrene: α-methylstyrene = 30: 70 (weight ratio). -Methylstyrene copolymer resin (5), styrene-α-methylstyrene copolymer resin (6) having a softening point of 150 ° C., which is a copolymerization ratio of styrene: α-methylstyrene = 30: 70 (weight ratio), styrene: α-methylstyrene = styrene having a softening point of 85 ° C. and a copolymerization ratio of 5:95 (weight ratio)
-Methylstyrene copolymer resin (7) or styrene: α
-Methylstyrene = 95: 5 (weight ratio) A test was conducted in exactly the same manner as in Example 1 except that a styrene-α-methylstyrene copolymer resin (8) having a softening point of 85 ° C, which is a copolymerization ratio, was used. A piece was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0077]

[Table 3]

When a styrene-α-methylstyrene copolymer resin having a copolymerization ratio of styrene and α-methylstyrene and / or a softening point outside the scope of the present invention is used, heat cycle In the bleed test, bleeding of the flame retardant was observed.
When the styrene-α-methylstyrene copolymer resin (5) at a temperature of ° C was used, the flame retardant itself had oozed out.

Comparative Examples 10 and 11 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) propane (Example 1) Same as above), hydrocarbon resin (1), polystyrene having an average molecular weight of 2,000, poly-α-methylstyrene having an average molecular weight of 1,000,
A test piece was prepared in exactly the same manner as in Example 1 except that antimony trioxide and antimony trioxide (same as in Example 1) were mixed in the proportions shown in Table 3, and the same evaluation as in Example 1 was performed. The results are shown in Table 3. Polystyrene in heat cycle bleed test, poly-α-methylstyrene in bleed test and heat cycle bleed test,
Each of the flame retardants bleed, and the styrene-methylstyrene copolymer resin of the present invention was inferior in the bleed control effect.

Examples 9 to 12 As the olefin resin (A), a high-density polyethylene resin (manufactured by Tosoh; trade name "Nipolon Hard # 4010") or a low-density polyethylene resin (manufactured by Tosoh; trade name "Petrocene # 202") Decabromodiphenyl ether (manufactured by Tosoh Corporation; trade name "Frame Cut 110R") or N, N 'as an organic halogenated aromatic compound flame retardant (B)
-Ethylene bis (tetrabromophthalimide) (manufactured by Albemarle; trade name "Saytex BT-93"), and a styrene-methylstyrene-based copolymer resin (C) having a weight ratio of copolymerization of α-methylstyrene to styrene of 2.3. A styrene-α-methylstyrene copolymer resin having a softening point of 85 ° C. and antimony trioxide (same as in Example 1) as a flame retardant auxiliary (D) were mixed in the proportions shown in Table 4 to obtain a high-density polyethylene resin. Was melt-kneaded with a twin-screw extruder set at 200 ° C. for low-density polyethylene resin and 170 ° C. for low-density polyethylene resin to prepare composition pellets. From these pellets, 220 for high density polyethylene resin
Bleed test and UL-94 with an injection molding machine set to 180 ° C and 180 ° C for low density polyethylene resin.
Test pieces for the flammability test were prepared. A bleed test and a UL-94 flammability test were performed using the obtained test pieces. Table 4 shows the results.

[0081]

[Table 4]

As the organic halogenated aromatic compound flame retardant, styrene-α-styrene can be used regardless of whether a halogenated diphenyl compound or a halogenated phthalimide compound is used.
Bleeding of these flame retardants was not observed by adding the methylstyrene copolymer resin.

Comparative Examples 12 to 15 Except that no styrene-α-methylstyrene copolymer resin was added, a test piece was prepared in exactly the same manner as in Examples 8 to 11 to prepare test pieces. The same evaluation as in Example 11 was performed. The results are shown in Table 4. As compared with Examples 8 to 11, when no styrene-α-methylstyrene copolymer resin was added, bleeding of the flame retardant was observed.

Examples 13 to 24 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) propane (Example 1) ), Bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone, styrene-α-methylstyrene copolymer resin (1) (same as in Example 1), antimony trioxide (Same as in Example 1), tetrakis [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, tris [(3,5-di-t-butyl-
4-hydroxybenzyl) isocyanurate, 1,3,
5-trimethyl-2,4,6-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) benzene,
2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate and dibutyltin malate oligomer (trade name: “Stann BM ( N))) were mixed in the proportions shown in Table 5 to produce test pieces in exactly the same manner as in Example 1. Thereafter, the same evaluation and heat resistance test as in Example 1 were performed. Table 5 shows the results. No bleeding of the flame retardant was observed and the heat resistance was excellent.

[0085]

[Table 5]

Examples 25 to 30, Comparative Examples 16 to 17 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) )) Phenyl) propane (same as in Example 1), bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone (same as in Example 23), styrene-α-methylstyrene copolymer Resin (1) (Example 1
, Antimony trioxide (same as in Example 1), tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (same as in Example 13) , Octadecyl-3- (3,5-
Di-tert-butyl-4-hydroxyphenyl) propionate (same as in Example 14), 2-tert-butyl-6- (3
-T-butyl-2-hydroxy-5-methylbenzyl)
-4-methylphenyl acrylate (same as in Example 17) and dibutyltin malate oligomer (Example 18)
Example 1 except for mixing the same as shown in Table 6).
, A test piece was prepared, and the same evaluation as in Example 13 was performed. Table 6 shows the results.

[0087]

[Table 6]

When the amount of the phenolic compound and / or the organotin compound was outside the scope of the present invention, no bleeding of the flame retardant was observed, but the heat resistance was slightly inferior. When the blending amount of the styrene-α-methylstyrene copolymer resin was out of the scope of the claims of the present invention, the flame retardant bleed.

Claims (7)

[Claims] An organic halogenated aromatic compound-based flame retardant (B) is added to 100 parts by weight of an olefin-based resin (A).
5 to 40 parts by weight, 0.2 to 60 parts by weight of a styrene-methylstyrene-based copolymer resin (C), and 0.1% of a flame retardant auxiliary (D).
1 to 30 parts by weight, and the compounding ratio of the styrene-methylstyrene-based copolymer resin (C) to the compounding amount of the organic halogenated aromatic compound-based flame retardant (B) is 0.1% by weight.
A flame-retardant resin composition, which is 4 to 1.5. 2. The flame-retardant resin composition according to claim 1, wherein the styrene-methylstyrene copolymer resin (C) has a softening point of 70 to 140 ° C. 3. The organic halogenated aromatic compound-based flame retardant (B) is at least one selected from the group consisting of flame retardants represented by the following general formulas (1) to (4). The flame-retardant resin composition according to claim 1 or 2, wherein Embedded image (In the formula, A represents an alkylene group, a carbonyl group, or —O—, and the alkylene group may be partially bonded to another position of the benzene ring to form a cyclic structure. Further halogen, alkenyl group, aryl group,
It may be substituted with a halogenated aryl group. X represents a bromine or chlorine atom. n and m are integers and n + m = 1 to
It is 10. ) (Wherein B is an alkylene group, a carbonyl group, -O-,-
S -, - SO- or -SO ₂ - represents a group, the alkylene group may form a cyclic structure bonded to the other position of the part of the benzene ring, also, the alkylene group further halogen, It may be substituted with an alkenyl group, an aryl group, or a halogenated aryl group. X represents a bromine or chlorine atom. n and m are integers, and n + m = 1 to 8. ) (Wherein E is an alkylene group, a carbonyl group, -0-,-
S -, - SO- or -SO ₂ - represents a group, the alkylene group may form a cyclic structure bonded to the other position of the part of the benzene ring, also, the alkylene group further halogen, It may be substituted with an alkenyl group, an aryl group, or a halogenated aryl group. X represents a bromine or chlorine atom. n and m are integers, and n + m = 1 to 8. Y is C _i
An alkyl halide represented by H _{2i + 1-z} X _z ,
i = 1 to 8, z = 1 to 2i + 1. ) (Wherein D represents a direct single bond, an alkylene group, an oxyalkylene group, a diphenylsulfone-ar, ar′-diyl group, a diphenyloxide-ar, ar′-diyl group or a carbonyl group, excluding the direct single bond. These divalent substituents further include a halogen, an alkenyl group, an aryl group,
It may be substituted with a halogenated aryl group. X represents a bromine or chlorine atom. n and m are integers and n + m = 1 to
8 ) 4. The flame-retardant resin composition according to claim 1, wherein the olefin resin (A) is a propylene resin. 5. The flame-retardant resin composition according to claim 1, wherein the olefin resin (A) is an ethylene resin. 6. The flame-retardant auxiliary (D) comprises an antimony compound,
The flame-retardant resin composition according to any one of claims 1 to 5, wherein the composition is at least one selected from the group consisting of a tin compound, a molybdenum compound, a zirconium compound, and a boron compound. 7. Further, 0.05 to 5 parts by weight of the phenolic compound (E) and / or 0.05 to 5 parts by weight of the organotin compound (F) are added to 100 parts by weight of the olefin resin (A). The flame-retardant resin composition according to any one of claims 1 to 6, which is blended.