JP2001172636A - Compound flame-retardant and flame-retardant resin composition into which the flame retardant is compounded - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound flame-retardant comprising a non-bleeding organic halide-based flame-retardant and a hydrocarbon-based resin, and to provide a flame-retardant resin composition into which the compound flame retardant is compounded and which has excellent flame retardance, mechanical strengths and thermal deformation resistance. SOLUTION: This compound flame-retardant characterized by comprising (A) an organic halide-based flame-retardant and (B) a hydrocarbon-based resin containing a component originated from an aromatic monomer in an amount of >=50 wt.% and a softening temperature of 70 to 140 deg.C, in that the components (A) and (B) are solid solutions, respectively, and in that the weight ratio of the temperature (B) to the component (A) is 0.01 to 2.0. The compound flame- retardant is compounded into a resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite flame retardant which suppresses so-called bleeding of a flame retardant onto a surface of a molded article and a flame retardant resin composition thereof. The present invention provides a flame-retardant resin composition having excellent mechanical strength and heat deformation resistance.

[0002]

2. Description of the Related Art Heretofore, flame retardation of olefin resins has been achieved by adding a flame retardant to a resin, blending a flame retardant resin, and forming 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 organic halide flame retardants can impart high flame retardancy to olefin resins.

[0004]

However, the above-mentioned organic halide-based flame retardants can impart high flame retardancy to olefin resins, but have poor compatibility with olefin resins, so that they are uniform at the beginning of molding. In many cases, even when dispersed in a resin, the resin gradually exudes to 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.

[0005] For example, Japanese Patent Publication No. 50-23064 discloses that polypropylene has 2,2-bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl).
A polypropylene composition containing propane and chlorinated polyethylene has been disclosed as a flame retarded polypropylene composition having low bleed. However, even in the case of the polypropylene composition, the bleeding of the flame retardant onto the surface of the molded article was not completely eliminated, and the chlorinated polyethylene was thermally degraded, and the flame retarding effect was not sufficient.

Further, Japanese Patent Application No. 8-295381 discloses that an olefin resin such as polypropylene is added with 2,2-
An organic halogenated aromatic compound flame retardant such as bis (3,5-dibromo-4- (2,3-dibromopropyloxy) phenyl) propane and a component derived from an aromatic monomer in an amount of 50% by weight or more. With a softening temperature of 70-140 ° C
The hydrocarbon resin of the weight ratio of the hydrocarbon resin to the organic halogenated aromatic compound flame retardant is 0.2 to 0.2
The olefin composition blended to 1.5 is disclosed as a flame retarded olefin composition in which bleed is suppressed. However, the flame-retardant olefin-based resin composition contains a large amount of a hydrocarbon-based resin having a low softening temperature and poor compatibility with the olefin-based resin, although bleeding of the flame-retardant is suppressed. There was also a problem that the mechanical strength and the heat deformation temperature were greatly reduced, and the flame retardant performance could not be maintained stably.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a composite flame retardant having no bleed of a flame retardant without lowering its flame retardancy when blended with an olefin resin. And a flame-retardant resin composition which is excellent in mechanical strength and heat deformation resistance.

[0008]

Means for Solving the Problems The inventors of the present invention have solved the conventional drawbacks and have aimed to obtain a flame-retardant resin composition having no bleed and having excellent flame retardancy, mechanical strength and heat deformation resistance. As a result of intensive studies, it was found that the component derived from the aromatic monomer was 5%.
When a composite flame retardant which is a solid solution of a hydrocarbon-based resin and a flame retardant having a softening temperature of 70 to 140 ° C. at 0% by weight or more is used, bleeding is suppressed and the composite flame retardant is blended. The flame-retardant resin composition was found to be excellent in flame retardancy, stably maintain excellent flame retardancy, and was further excellent in mechanical strength and heat deformation resistance, and completed the present invention.

That is, the present invention relates to a hydrocarbon resin (B) containing 50% by weight or more of a component derived from an organic halide flame retardant (A) and an aromatic monomer and having a softening temperature of 70 to 140 ° C. Wherein the weight ratio of the hydrocarbon-based resin (B) to the organic halide-based flame retardant (A) is 0.05 to 2.0, and (A) and (B) are solid solutions. The present invention relates to a flame retardant and a flame-retardant resin composition obtained by mixing 1 to 50 parts by weight with respect to 100 parts by weight of an olefin resin (C).

The organic halide flame retardant (A) used in the present invention is not particularly limited as long as it forms a solid solution with the hydrocarbon resin (B). And at least one flame retardant selected from bis (haloalkyl ether) -based compounds of halogenated bisphenols represented by the following general formula:

[0011]

Embedded image

Wherein A is an alkylene group, an alkylidene group, a carbonyl group, —O—, —S—, —SO—, —SO
Represents a _2- group, and the alkylene group and the alkylidene group may be partially bonded to other positions on the benzene ring to form a cyclic structure. Further, the alkylene group and the alkylidene group may be further substituted with a halogen, an alkenyl group, an aryl group, or a halogenated aryl group. X is a bromine or chlorine atom. n and m are integers, and n + m = 1 to 8. R is C _i
H _{2i + 1-z} Y is an alkyl halide represented by Y _z , wherein Y is a bromine or chlorine atom, i = 1 to 8, z = 1 to 2i +
One. Examples of the bis (haloalkyl ether) -based compound of halogenated bisphenol include bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) methane and 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. Among these, 2,2-bis (3,5-dibromo -4- (2,3
-Dibromopropoxy) phenyl) propane and bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone are preferably used in view of flame retardancy and industrial availability. The hydrocarbon resin (B) used in the above is particularly limited as long as the component derived from the aromatic monomer is 50% by weight or more and the softening temperature is in the range of 70 to 140 ° C. is not. A hydrocarbon resin containing less than 50% by weight of a component derived from an aromatic monomer is not preferable because the effect of suppressing bleeding is inferior. Those having a softening temperature of less than 70 ° C are not preferred because the hydrocarbon-based resin itself may bleed from the composition when blended with the olefin resin as a composite flame retardant, and those having a softening temperature of more than 140 ° C, When compounded with an olefin resin as a composite flame retardant, the mechanical strength of the composition is significantly reduced, which is not preferable.

As the hydrocarbon resin (B), for example,
Of the cracked oil fraction obtained by pyrolysis of petroleum, 14
Among hydrocarbon-based resins obtained by polymerizing using a raw oil obtained by distilling a fraction having a boiling point range of 0 to 220 ° C., hydrogenated resins thereof, and cracked fractions obtained by pyrolysis of petroleums, , A hydrocarbon-based resin obtained by polymerizing one or more polymerizable monomers obtained by distilling a fraction having a boiling point range of 140 to 220 ° C., and a resin obtained by mixing two or more of these resins. However, the present invention is not particularly limited to these. Here, of the cracked fraction obtained by the thermal cracking of petroleum, the boiling point range is 140 to 2
As the fraction at 20 ° C., styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene,
There are methylindene, dicyclopentadiene, ethylbenzene, trimethylbenzene, naphthalene and the like, among which styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene, methylindene and the like can be mentioned as polymerizable monomers.

In the present invention, the method for producing the hydrocarbon resin (B) includes, for example, radical polymerization, cationic polymerization, anionic polymerization, etc., provided that it falls within the scope of the claims of the present invention. The production method is not particularly limited.

In the present invention, in the composite flame retardant which is a solid solution of the organic halide flame retardant (A) and the hydrocarbon resin (B), the hydrocarbon resin (A) and the hydrocarbon resin (A) are used. The ratio of B) is from 0.05 to weight ratio.
2.0. If the weight ratio is less than 0.05, the effect of suppressing bleeding is inferior, and if the weight ratio exceeds 2.0, not only the flame retardancy of the composition decreases, but also the mechanical strength and heat deformation resistance of the composition decrease. It is also disadvantageous economically. The most preferable ratio of the hydrocarbon-based resin (B) to the organic halide-based flame retardant (A) is such that the bleeding of the flame retardant is suppressed and the mechanical strength and the heat deformation resistance of the composition are hardly reduced. The ratio is in the range of 0.05 to 0.2.

In the flame-retardant resin composition of the present invention, as the olefin resin (C) to be used, various polymers containing olefin as a main component, 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 copolymer, ethylene-butene copolymer, propylene-butene copolymer, Examples include maleic acid-modified polyethylene and maleic acid-modified polypropylene, but are not particularly limited thereto.

In the flame retardant resin composition of the present invention, the compounding amount of the composite flame retardant which is a solid solution of the organic halide flame retardant (A) and the hydrocarbon resin (B) with respect to the olefin resin (C) is as follows. And 1 to 50 parts by weight based on 100 parts by weight of the olefin resin (C). If the amount is less than 1 part by weight, the flame-retarding effect is insufficient, and if it exceeds 50 parts by weight, the mechanical strength and the heat deformation resistance of the composition are lowered, and it is economically disadvantageous.

In the flame-retardant resin composition of the present invention, it is preferable to add a flame-retardant aid (D) to further enhance the flame-retardant effect. The flame retardant aid (D) is not particularly limited as long as it has a flame retardant synergistic effect with the organic halide flame retardant (A) in the composite flame retardant. Antimony, antimony tetroxide, antimony compounds such as antimony pentoxide, tin oxide, tin hydroxide,
Examples include tin compounds such as zinc stannate and zinc hydroxystannate, molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, and boron compounds such as zinc borate and barium metaborate. . The compounding amount of these flame retardant assistants (D) in the flame retardant resin composition of the present invention is 0.2 to 30 with respect to 100 parts by weight of the olefin resin (C).
Parts by weight. If the amount is less than 0.2 parts by weight, no synergistic effect of flame retardancy is observed, and if it exceeds 30 parts by weight, the mechanical strength of the composition is reduced.

The composite flame retardant of the present invention is not particularly limited by the method for producing it. For example, an organic halide flame retardant (A), a hydrocarbon resin (B), and if necessary, Other additives can be blended in a predetermined amount, premixed with a mixer such as a Henschel mixer, a ribbon blender, or the like, and then melt-mixed with a heating pot, a granulator, or the like to form a solid solution. In addition, the composite flame retardant of the present invention includes, as necessary, generally used ultraviolet absorbers and light absorbers as long as the excellent flame retardancy and the bleed control effect of the flame retardant are not impaired. Various additives such as a stabilizer, a release agent, a lubricant, an antioxidant, a heat stabilizer, and a compatibilizer may be blended.

The flame-retardant resin composition of the present invention is not particularly limited by the method for producing the same. For example, an olefin resin (C), a composite flame retardant, a flame retardant auxiliary (D), and It can be easily produced by blending a predetermined amount of other additives as necessary, preliminarily mixing with a mixer such as a Henschel mixer, a ribbon blender, and then melt-kneading with an extruder, a hot roll, a Banbury mixer, or the like. . In addition, the flame-retardant resin composition of the present invention may have an excellent flame retardancy, an effect of suppressing bleeding of a flame retardant, a mechanical strength, and a heat-resistant deformation property, which are objects of the present invention, as long as necessary. UV absorbers, light stabilizers, mold release agents,
Various additives such as lubricants, colorants, fillers, foaming agents, antioxidants, heat stabilizers, antistatic agents, compatibilizers, impact modifiers, crosslinking agents, nucleating agents, glass fibers, carbon fibers, etc. There is no problem with mixing.

[0021]

As is clear from the above description, the composite flame retardant of the present invention is one in which the bleeding of the flame retardant is suppressed without lowering the flame retardancy, and the compounded flame retardant is difficult to obtain. The flame-retardant resin composition is excellent in flame retardancy, can also stably maintain excellent flame retardancy, and is excellent in bleed suppression, impact resistance, and heat deformation resistance.
It is useful as a material for electric wires, automobile parts, building materials, civil engineering materials, and the like.

[0022]

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 performed in 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 surfaces of the test pieces were observed with a reflection microscope and ranked as follows.

：: No bleed of flame retardant.

Δ: Flame retardant slightly bleeds.

X: Flame retardant is significantly bleed.

<UL-94 flammability test> Five test pieces 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.

<Flame Retardancy Stability Test> A length 125 mm, a width 25 mm and a thickness 1.6 as in the UL-94 flammability test.
Using 50 test pieces of 50 mm in size, a vertical combustion test of Subject No. 94 of Underwriters Laboratory was performed.
Each test piece was ranked as follows.

V0 combustion: Flame burning time after the first flame contact and after the second flame contact is within 10 seconds each, the total time of flaming combustion and red heat combustion after the second flame contact is within 30 seconds, cotton ignition None, simultaneously satisfying no combustion reaching the clamp.

V1 combustion: The flaming combustion time after the first flame contact and the second flame contact is 30 seconds or less, respectively, the total time of flaming combustion and red heat combustion after the second flame contact is 60 seconds or less, cotton ignition None, simultaneously satisfying no combustion reaching the clamp.

V2 combustion: Flame burning time after the first flame contact and the second flame contact is 30 seconds or less, respectively, the total time of flaming combustion and red heat combustion after the second flame contact is 60 seconds or less, cotton ignition Yes, simultaneously satisfying no combustion reaching the clamp.

It was determined that the greater the number of test pieces ranked as V0 combustion among the 50 test pieces, the better the stability of flame retardancy.

<Izod impact strength> JIS K-71
It measured by the method of 10.

<Heat Deformation Temperature> Among the methods of JIS K-7207, the measurement was performed by a method in which a bending stress was 4.6 kgf / cm ² .

Tables 1 to 3 show details of the composite flame retardants used in Examples and Comparative Examples.

As the composite flame retardant, an organic halide flame retardant (A) and a hydrocarbon resin (B) are mixed in the proportions shown in Tables 1 to 3, respectively, and the mixture is heated in a 160 ° C. heating oven. It was obtained by melting and stirring for 20 minutes, then cooling and pulverizing.

The hydrocarbon resin was prepared according to the following preparation examples.

Preparation Example 1 Boron trifluoride phenolate as a catalyst was added in an amount of 0.6% by weight based on 100 parts by weight of a raw oil composed of 40% by weight of styrene and 60% by weight of α-methylstyrene and 70% by weight of xylene. And polymerized at 40 ° C. for 2 hours. After the polymerization, the catalyst was removed with an aqueous solution of caustic soda, and then washed with water to remove unreacted oil and low-polymerized substances by distillation, thereby obtaining a hydrocarbon resin B-1.

Preparation Example 2 Hydrocarbon resin B was synthesized in the same manner as in Preparation Example 1 except that a raw oil composed of 65 wt% of α-methylstyrene and 35 wt% of dicyclopentadiene was used and polymerized at 50 ° C. for 2 hours. -2 was obtained.

Preparation Example 3 Xylene 70% was added to 30% by weight of a feedstock oil composed of 65% by weight of α-methylstyrene and 35% by weight of dicyclopentadiene.
Synthesis was carried out in the same manner as in Preparation Example 1, except that 5 parts by weight of phenol was added to 100 parts by weight to which wt% was added, to obtain a hydrocarbon resin B-3.

Preparation Example 4 Synthesis was carried out in the same manner as in Preparation Example 1 except that polymerization was carried out at 50 ° C. for 2 hours to obtain a hydrocarbon resin B-6.

Preparation Example 5 A hydrocarbon resin B was synthesized in the same manner as in Preparation Example 1, except that a raw oil consisting of 65% by weight of α-methylstyrene and 35% by weight of dicyclopentadiene was polymerized at 30 ° C. for 2 hours. -7 was obtained.

Preparation Example 6 A hydrocarbon resin B was synthesized in the same manner as in Preparation Example 1 except that a raw material oil composed of 45 wt% of α-methylstyrene and 55 wt% of dicyclopentadiene was used, and phenol was used in an amount of 5 parts by weight. -8 was obtained.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

Examples 1 to 3 Polypropylene resin (manufactured by Chisso; trade name "Chisso Polypro K7014"), composite flame retardant 2, composite flame retardant 3, composite flame retardant 4, and antimony trioxide (trade name, manufactured by Tosoh Corporation; trade name) "Frame cut 610R") was mixed at the ratio shown in Table 4, and melt-kneaded with a twin-screw extruder set at 200 ° C to produce pellets of the composition. The pellets were subjected to an Izod impact strength, a heat distortion temperature, a UL-94 flammability test, and a bleed test using an injection molding machine set at 210 ° C. Izod impact strength, heat distortion temperature, UL-94 flammability test and bleed test were performed using the obtained test pieces. Table 4 shows the results.

The weight ratio of the hydrocarbon resin to the organic halide flame retardant was within the scope of the claims, and no bleeding of the flame retardant was observed. As a result of the UL-94 flammability test, all the flame retardancy grades were V-0.

[0050]

[Table 4]

Comparative Example 1 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane (composite flame retardant 2 of Example 1) And antimony trioxide (Example 1)
Example 1 except for mixing the same as shown in Table 4).
, A test piece was prepared, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

Compared with Examples 1 to 3, when no hydrocarbon resin was contained, 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-dibromopropoxy) phenyl) propane (of Example 1) A test piece was prepared in exactly the same manner as in Example 1, except that the same flame retardant as used in the composite flame retardant 2), antimony trioxide (same as in Example 1) and chlorinated polyethylene were mixed in the proportions shown in Table 4. Then, the same evaluation as in Example 1 was performed. The results are shown in Table 4.

When the amount of the chlorinated polyethylene resin is smaller than in Examples 1 to 3, the effect of suppressing the bleeding of the flame retardant by the chlorinated polyethylene resin is poor.
On the other hand, when the blending amount of the chlorinated polyethylene resin is large, the bleeding of the flame retardant can be suppressed, but the flame retardancy is reduced.

Comparative Examples 4 to 6 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane (of Example 1) The same as those used in the composite flame retardant 2), hydrocarbon resin B-1 (Example 1)
And the antimony trioxide (same as in Example 1), and the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant was the same as in Examples 1 to 3. In the same manner, a test piece was prepared in exactly the same manner as in Example 1 except for mixing at the ratio shown in Table 4, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

As compared with Examples 1 to 3, when the composite flame retardant of the organic halide flame retardant and the hydrocarbon resin was not used, the flame retardant bleed.

Example 4, Example 5, Comparative Example 7, Comparative Example 8 Polypropylene resin (same as in Example 1), composite flame retardant 5, composite flame retardant 6, composite flame retardant 1, composite flame retardant 7, and A test piece was prepared in exactly the same manner as in Example 1 except that antimony oxide (same as in Example 1) was mixed at the ratio shown in Table 5, and the same evaluation as in Example 1 was performed. Table 5 shows the results.

[0058]

[Table 5]

When the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant in the composite flame-retardant is within the scope of the present invention, no bleed of the flame-retardant is observed and the mechanical strength is reduced. Excellent and high heat distortion temperature. On the other hand, when the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant is smaller than the scope of the claims of the present invention, the flame-retardant bleeds and the weight ratio of the hydrocarbon-based resin to the organic halide-based flame-retardant is reduced. When it is larger than the claims of the invention, the bleed of the flame retardant can be suppressed, but the flame retardancy is reduced, the mechanical strength is remarkably inferior, and the heat deformation temperature is greatly reduced.

Examples 6 and 7 A polypropylene resin (as in Example 1), a composite flame retardant 5, a composite flame retardant 6, and antimony trioxide (as in Example 1) are mixed in the proportions shown in Table 6. Except for the above, a test piece was prepared in the same manner as in Example 1, and a flame resistance stability test was performed. The results are shown in Table 6.

[0061]

[Table 6]

In the case of the composite flame retardant, all 50 test pieces burned V0 and were excellent in flame retardancy stability.

Comparative Examples 9 and 10 Polypropylene resin (same as in Example 1), 2,2-bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane (of Example 6) The same as those used in the composite flame retardant 5, and the hydrocarbon resin B-1 (Example 6)
And the antimony trioxide (same as in Example 1) and the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant in Examples 6 and 7, respectively. In the same manner, a test piece was prepared in exactly the same manner as in Example 6 except that the mixture was mixed at the ratio shown in Table 6, and the same evaluation as in Example 6 was performed. The results are shown in Table 6.

In comparison with Examples 6 and 7, when the composite flame retardant of an organic halide-based flame retardant and a hydrocarbon-based resin was not used, the number of V0 combustion test specimens out of 50 specimens Decreased, the number of test pieces for V2 combustion increased, and the stability of flame retardancy was poor.

Examples 8 to 11, Comparative Examples 11 to 13 Polypropylene resin (same as in Example 1), composite flame retardant 8, composite flame retardant 9, composite flame retardant 10, composite flame retardant 11,
Except that the composite flame retardant 12, the composite flame retardant 13, the composite flame retardant 14, and the antimony trioxide (the same as in Example 1) were mixed at the ratio shown in Table 7, the test was performed in exactly the same manner as in Example 1 to prepare a test piece. Then, the same evaluation as in Example 1 was performed. Table 7 shows the results.

[0066]

[Table 7]

The weight ratio and the softening temperature of the component derived from the aromatic monomer of the hydrocarbon resin used in the composite flame retardant are within the scope of the claims of the present invention.
No heat was observed, the mechanical strength was excellent, and the heat deformation temperature was high. On the other hand, if the softening temperature of the hydrocarbon resin used for the composite flame retardant is lower than the scope of the claims of the present invention, the flame retardancy and the heat deformation temperature are reduced, and also in the bleed test, not only the flame retardant, The hydrocarbon resin itself was seeping out. Conversely, when the softening temperature of the hydrocarbon-based resin used in the composite flame retardant was higher than the claimed range of the present invention, the flame retardant bleed, and the flame retardancy and mechanical strength decreased. When the weight ratio of the component derived from the aromatic monomer of the hydrocarbon resin used in the composite flame retardant was less than 50% by weight, the flame retardant bleed.

Examples 12 to 14 Polypropylene resin (same as in Example 1), composite flame retardant 1
5, a composite flame retardant 16, a composite flame retardant 17, and antimony trioxide (the same as in Example 1) were mixed in the proportions shown in Table 8 in exactly the same manner as in Example 1 to prepare a test piece.
The same evaluation as in Example 1 was performed. Table 8 shows the results.

[0069]

[Table 8]

The weight ratio of the hydrocarbon resin to the organic halide flame retardant was within the scope of the claims, and no bleeding of the flame retardant was observed. As a result of the UL-94 flammability test, all the flame retardancy grades were V-0.

Comparative Example 14 A polypropylene resin (same as in Example 1), a screw (3,5)
-Dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone (same as that used in the composite flame retardant 15 of Example 12) and antimony trioxide (same as Example 1) in the proportions shown in Table 8 Except for mixing, a test piece was prepared in exactly the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 8.

Compared to Examples 12 to 14, when no hydrocarbon resin was contained, the bleeding of the flame retardant was remarkable.

Comparative Examples 15 to 17 Polypropylene resin (same as in Example 1), bis (3,5)
-Dibromo-4- (2,3-dibromopropoxy) phenyl) sulfone (same as that used in the composite flame retardant 15 of Example 12), and a hydrocarbon-based resin B-1 (in the case of the composite flame retardant 15 of Example 12). The same as those used in Example 12) and antimony trioxide (the same as in Example 1), so that the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant would be the same as in Examples 12 to 14, respectively. A test piece was prepared in exactly the same manner as in Example 1 except for mixing at the ratio shown in Table 8, and the same evaluation as in Example 1 was performed. The results are shown in Table 8.

As compared with Examples 12 to 14, when the composite flame retardant of an organic halide flame retardant and a hydrocarbon resin was not used, the flame retardant bleed.

Example 15 A high-density polyethylene resin (manufactured by Tosoh Corporation; trade name "Nipolon Hard # 4010"), a composite flame retardant 3, and antimony trioxide (same as in Example 1) were mixed at the ratio shown in Table 9. The mixture was melt-kneaded with a twin-screw extruder set at 200 ° C. to produce pellets of the composition. Test pieces for the Izod impact strength, heat distortion temperature, UL-94 flammability test, and bleed test were prepared from the pellets using an injection molding machine set at 220 ° C. Izod impact strength, heat distortion temperature, UL-94 flammability test and bleed test were performed using the obtained test pieces. Table 9 shows the results.

[0076]

[Table 9]

Comparative Example 18 High-density polyethylene resin (same as in Example 15), 2, 2
-Bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane (same as that used in the composite flame retardant 3 of Example 15), and antimony trioxide (same as Example 1) Were prepared in exactly the same manner as in Example 15 except that the components were mixed in the proportions shown in Table 9 to prepare test pieces, and the same evaluation as in Example 15 was performed. The results are shown in Table 9.

Comparative Example 19 High-density polyethylene resin (same as in Example 15), 2, 2
-Bis (3,5-dibromo-4- (2,3-dibromopropoxy) phenyl) propane (same as that used in the composite flame retardant 3 of Example 15), hydrocarbon resin B-1
(Same as used in composite flame retardant 3 of Example 15),
And antimony trioxide (same as in Example 1) except that they were mixed at the ratios shown in Table 9 so that the weight ratio of the hydrocarbon-based resin to the organic halide-based flame retardant was the same as in Example 15. A test piece was prepared in exactly the same manner as in Example 15, and the same evaluation as in Example 15 was performed. Table 8 shows the results.
Shown along with.

In the case of a composite flame retardant of an organic halide flame retardant and a hydrocarbon resin, no bleeding of the flame retardant was observed. In addition, as compared with Example 15, in the case where no hydrocarbon resin was contained, and in the case where the compound was not a composite flame retardant of an organic halide flame retardant and a hydrocarbon resin, the flame retardant bleed.

Claims (8)

[Claims] An organic halide-based flame retardant (A) and a hydrocarbon-based resin (B) containing at least 50% by weight of a component derived from an aromatic monomer and having a softening temperature of 70 to 140 ° C. The ratio of the hydrocarbon resin (B) to the organic halide flame retardant (A) is 0.05 to 2.0 by weight.
And (A) and (B) are solid solutions. 2. The weight ratio of the hydrocarbon resin (B) to the organic halide flame retardant (A) is 0.05 to 1.
The composite flame retardant according to claim 1, wherein the composite flame retardant is 5. 3. The weight ratio of the hydrocarbon resin (B) to the organic halide flame retardant (A) is 0.05 to 0.5.
The composite flame retardant according to any one of claims 1 to 2, wherein 4. The method according to claim 1, wherein the organic halide flame retardant (A) is at least one flame retardant selected from bis (haloalkyl ether) compounds of halogenated bisphenols represented by the following general formula. The composite flame retardant according to any one of claims 1 to 3, wherein Embedded image (In the formula, A is an alkylene group, an alkylidene group, a carbonyl group, -O -, - S -, - SO -, - SO 2 - represents a group, an alkylene group and an alkylidene group partially other benzene ring And the alkylene group and the alkylidene group may be further substituted with a halogen, an alkenyl group, an aryl group, or a halogenated aryl group, and X is a bromine or chlorine atom. .
n and m are integers, and n + m = 1 to 8. R is C _i H _{2i + 1-z} Y _z
Wherein Y is a bromine or chlorine atom, i = 1 to 8, z = 1 to 2i + 1. ) 5. The composite flame retardant according to claim 1, which is present in an amount of 1 to 5 per 100 parts by weight of the olefin resin (C).
A flame-retardant resin composition comprising 0 parts by weight and 0.2 to 30 parts by weight of a flame-retardant aid (D). 6. The flame-retardant resin composition according to claim 5, wherein the olefin resin (C) is a propylene resin. 7. The flame-retardant resin composition according to claim 5, wherein the olefin resin (C) is an ethylene resin. 8. The flame-retardant aid (D) is at least one selected from the group consisting of antimony compounds, tin compounds, molybdenum compounds, zirconium compounds and boron compounds. 7. The flame-retardant resin composition according to any one of items 7 to 7.