JP6509081B2 - Highly flame retardant and highly processable synthetic resin composition - Google Patents

Description

The present invention, without impairing their inherent physical properties resin, relates to a flame retardant, and high workability and high flame-retardant synthetic resin composition having excellent processing properties.

Synthetic resins are excellent in molding processability, heat resistance, mechanical properties, etc. and have advantages of low specific gravity and light weight, and are widely used in various molded articles such as films, sheets and structural parts. . In addition, many attempts have been made to blend synthetic resins with other polymers to impart new physical properties such as impact resistance and elasticity.
However, since highly flammable synthetic resins such as polyolefin resins are widely used in a wide range of fields, it is essential to incorporate a flame retardant for imparting flame retardancy to these resins. As such a flame retardant, polyphosphoric acid or a salt of pyrophosphoric acid and a nitrogen-containing compound is used as a main component, and by forming a surface expansion layer (Intumescent) at the time of combustion, diffusion and heat transfer of decomposition products are suppressed to reduce flame resistance. Intomescent flame retardants that exhibit excellent flame retardancy.

  In applications that require extremely severe flame retardancy mainly for wire applications, a large amount of flame retardant is mixed, so that bubbles in the molded product and deterioration of the surface condition of the molded product due to poor dispersion of the flame retardant, etc. Processability defects occur. Therefore, techniques for adding processing aids such as silicone oil (for example, Patent Documents 1, 2 and 3) are known for the purpose of improving processability centering on the dispersibility of the flame retardant. Since there is a problem that a decrease in flame retardancy is seen due to the effect of the auxiliaries, there is a need for a resin composition having both high flame retardancy and good processability even when containing such processing aids. The

JP 02-084457 A JP, 2010-189601, A JP 2007-169444 A

  Therefore, the problem to be solved by the present invention is to provide a resin composition having excellent flame retardancy and excellent physical properties inherent to a resin and having excellent processing characteristics.

（Ｒは炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、炭素数４〜２２のシクロアルキル基及びシクロアルケニル基からなる群より選択される何れかの基を表し、Ａは炭素数２〜４のアルキレン基を表し、Ｘは水素原子、アルカリ金属、又はアンモニウム、アルキルアミン若しくはアルカノールアミンの４級アンモニウムカチオンであることを示す。ｎは０〜１００の整数であり、ｍは１又は２である。） Then, the present inventors came to the present invention as a result of earnestly examining in order to solve the above-mentioned subject.
That is, the present invention provides a flame retardant resin composition which contains the following components (A) and (B) as a flame retardant component and contains a component (C) as a processability improving agent.
Component (A): One or more melamine salts selected from the group of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate Component (B): One kind from the group of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate Piperazine salt (C) component selected as above: phosphate ester compound represented by the following general formula [1]

(R is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms and a cycloalkenyl group A represents an alkylene group having 2 to 4 carbon atoms, and X represents a hydrogen atom, an alkali metal, or a quaternary ammonium cation of ammonium, an alkylamine or an alkanolamine, n represents 0. And is an integer of 100 and m is 1 or 2.)

  The flame retardant resin composition of the present invention preferably further contains zinc oxide (component (D)) as a flame retardant component.

  The flame retardant resin composition of the present invention preferably further contains a silicone oil (component (E)) as a processing aid component.

  The present invention also provides a molded article obtained from any of the above-mentioned flame retardant resin compositions.

  ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding flame retardance and the outstanding physical property intrinsic | native to resin, and can also provide the resin composition which is excellent in a processing characteristic.

Hereinafter, the flame-retardant resin composition of the present invention will be described based on a preferred embodiment.
First, the synthetic resin component used for the flame retardant resin composition of the present invention will be described. It does not restrict | limit especially as resin used for the flame-retardant resin composition of this invention, For example, a thermoplastic resin, a thermosetting resin, crystalline resin, non-crystalline resin, biodegradable resin, non-biodegradable Resin, synthetic resin, resin produced by natural production, general-purpose resin, engineering resin, polymer alloy and the like.

  Examples of synthetic resins include polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, ethylene-propylene copolymer, etc. -Homopolymers or copolymers of olefins, polyunsaturated compounds such as α-olefins and conjugated dienes or non-conjugated dienes, copolymers of acrylic acid, methacrylic acid, vinyl acetate etc., polyethylene terephthalate, polyethylene terephthalate・ Linear polyesters such as isophthalate, polyethylene terephthalate, paraoxybenzoate, polybutylene terephthalate, acid-modified polyesters, biodegradable resins such as aliphatic polyesters, liquid crystalline polyesters, polycaprolactams, polyhexamethylene adipamides, etc. Liamides, liquid crystal polyamides, polyimides, polystyrenes, copolymers of styrene and / or α-methylstyrene with other monomers (eg, maleic anhydride, phenyl maleimide, methyl methacrylate, butadiene, acrylonitrile etc.) (eg, Acrylonitrile styrene copolymer (AS) resin, acrylonitrile butadiene styrene copolymer (ABS) resin, methyl methacrylate butadiene styrene copolymer (MBS resin), heat resistant ABS resin, etc.) polyvinyl chloride polyvinylidene chloride chlorine Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary Copolymerization Halogen-containing resins such as vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer, methyl (meth) acrylate, ethyl (meth) acrylate ( Polymers of (meth) acrylic acid esters such as octyl (meth) acrylate, polyether ketone, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, linear or branched polycarbonate, petroleum resin, coumarone resin, polyphenylene oxide, polyphenylene Thermoplastic resins such as sulfide, thermoplastic polyurethane, and fibrous resins; epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyester resins, thermosetting resins such as thermosetting polyurethanes; natural rubber, 3- Examples include aliphatic polyesters produced by microorganisms such as hydroxybutyrate, aliphatic polyamides produced by microorganisms, starch, cellulose, chitin / chitosan, resins produced by nature such as gluten / gelatin, general purpose resins, engineering resins, polymer alloys, etc. Even resin types can be used without limitation. Here, the polymer alloy is a polymer multicomponent system, and may be a block polymer by copolymerization or a polymer blend by mixing or the like.

  In the present invention, as the synthetic resin, isoprene rubber, butadiene rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, ethylene and an α-olefin such as propylene and butene-1, etc. Copolymer elastomers such as ethylene-.alpha.-olefin and ethylidene norbornene, ternary copolymer rubbers with non-conjugated dienes such as cyclopentadiene, .alpha.-olefin elastomers, silicone resins, etc., and these resins and / or Or, an elastomer or rubber alloyed or blended can also be used.

  In the present invention, the synthetic resin includes molecular weight, polymerization degree, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, kind and blending ratio of monomer as raw material, polymerization catalyst It can be used regardless of the type (eg, Ziegler catalyst, metallocene catalyst, etc.) and the like.

  Among these synthetic resins, in particular, thermoplastic elastomers or thermoplastic elastomer polymer alloys are preferable. Examples of thermoplastic elastomer resins used for these include styrene thermoplastic elastomers, polyolefin thermoplastic elastomers, polyvinyl chloride thermoplastic elastomers, polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, and polyamide thermoplastics. Elastomers, transpolyisoprene thermoplastic elastomers, fluororubber thermoplastic elastomers, chlorinated polyethylene thermoplastic elastomers, etc. may be mentioned. Among these, styrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers are preferable in the present invention. As a styrene-based thermoplastic elastomer, a copolymer of styrene and / or α-methylstyrene with another monomer (eg, maleic anhydride, phenyl maleimide, methyl methacrylate, butadiene, acrylonitrile, etc.), eg, acrylonitrile -Styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, methyl methacrylate-butadiene-styrene (MBS) resin, heat resistant ABS resin, styrene-butadiene-styrene (SBS) resin, acrylonitrile-acrylate-styrene (AAS) ) Resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin, acrylonitrile-ethylene-propylene rubber-styrene (AES) resin, Thermoplastic resins such as styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and styrene-ethylene-butylene obtained by hydrogenating the double bond of these butadiene or isoprene -Hydrogenated styrenic elastomer resin such as styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin, etc. These can be used alone or in mixtures of two or more.

  The polyolefin-based thermoplastic elastomer is an α-olefin polymer or copolymer having 2 to 20 carbon atoms, and specifically, ethylene-propylene resin, ethylene-butene resin, ethylene-hexene resin, ethylene-methylpentene resin And ethylene-octene resin, butene resin, butene-methylpentene resin, methylpentene resin, ethylene-vinyl acetate resin, ethylene-methacrylic acid resin, ethylene-methyl methacrylate resin, etc., which may be used alone or in combination of plural mixtures. It is usable.

  Examples of polyurethane-based thermoplastic elastomers include ether-based polyurethane resins, ester-based polyurethane resins, ether ester-based polyurethane resins, carbonate-based polyurethane resins, and amide-based polyurethane resins. These may be used alone or in combination of two or more.

  In the present invention, the content of the synthetic resin in the flame retardant resin composition of the present invention is preferably 28% by mass to 79% by mass, more preferably 38% by mass to 69% by mass, and 43% by mass to 64% by mass Is even more preferred.

  The melamine salt of the component (A) used as the flame retardant component of the present invention is selected from the group of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate, and these may be used alone or in a mixture. Among these, melamine pyrophosphate is preferable in terms of flame retardancy. When these are used as a mixture, the higher the content of melamine pyrophosphate, the better. The ratio of pyrophosphoric acid to melamine in melamine pyrophosphate is preferably 1: 1.5 to 1: 2.5 in molar ratio, and most preferably 1: 2.

  The salts of these phosphoric acid and melamine can also be obtained by reacting melamine with the corresponding phosphoric acid or phosphate, respectively, but the melamine salt used in the component (A) of the present invention is melamine 1 ortho orthophosphate Are preferably heat-condensed melamine pyrophosphate or melamine polyphosphate, particularly preferably melamine pyrophosphate.

  The piperazine salt of the component (B) used as the flame retardant component of the present invention is selected from the group of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate, and these may be used alone or in a mixture. Among these, piperazine pyrophosphate is preferable from the viewpoint of flame retardancy, and in the case of using it in a mixture, the higher the content ratio of piperazine pyrophosphate, the more preferable. The ratio of pyrophosphate to piperazine in the piperazine pyrophosphate is preferably 1: 0.5 to 1: 1.5 in molar ratio, and most preferably 1: 1.

  These salts of phosphoric acid and piperazine can also be obtained by reacting the corresponding phosphoric acid or phosphate with piperazine, respectively, but the piperazine salt used in component (B) of the present invention is diorthophosphoric acid The piperazine pyrophosphate or piperazine polyphosphate obtained by heat-condensing one piperazine is preferable, and piperazine pyrophosphate is particularly preferable.

  The compounding amount of the component (A) is preferably 3 to 29% by mass, more preferably 5 to 24% by mass, and still more preferably 6 to 22% by mass in the flame retardant resin composition of the present invention. On the other hand, the blending amount of the component (B) is preferably 9 to 46% by mass, more preferably 14 to 38% by mass, and still more preferably 16 to 35% by mass in the flame retardant resin composition of the present invention.

  In addition, the total content of the component (A) and the component (B) exerts excellent flame retardancy, and does not impair the physical properties of the resin. 20-60 mass% is preferable, 30-50 mass% is more preferable, 35-45 mass% is further more preferable. If the amount is less than 20% by mass, sufficient flame retardancy may not be obtained, and if it exceeds 60% by mass, physical properties of the resin may be impaired.

  Moreover, it is preferable that the content ratio (mass reference | standard) of the said (A) component and said (B) component is (A) / (B) = 20/80-50/50, (A) / (B) More preferably, it is 30/70 to 50/50.

（Ｒは炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、炭素数４〜２２のシクロアルキル基及びシクロアルケニル基からなる群より選択される何れかの基を表し、Ａは炭素数２〜４のアルキレン基を表し、Ｘは水素原子、アルカリ金属、又はアンモニウム、アルキルアミン若しくはアルカノールアミンの４級アンモニウムカチオンであることを示す。ｎは０〜１００の整数であり、ｍは１又は２である。） Next, the processability improver used for the flame retardant resin composition of the present invention will be described.
The phosphoric acid ester compound of the component (C) used as the processability improver of the present invention is a compound represented by the following general formula [1] from the viewpoint of coexistence of high processability and high flame retardancy.

(R is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms and a cycloalkenyl group A represents an alkylene group having 2 to 4 carbon atoms, and X represents a hydrogen atom, an alkali metal, or a quaternary ammonium cation of ammonium, an alkylamine or an alkanolamine, n represents 0. And is an integer of 100 and m is 1 or 2.)

  Examples of the alkyl group constituting the general formula [1] showing the phosphoric acid ester compound of component (C) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group Group, isopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, Isotridecyl group, tetradecyl group, isotetradecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group, eicosyl group, isoeicosyl group, docosyl group, isodocosyl group, tetracosyl group, hexacosyl group, octacosyl group, triacontyl group, 3- 2-butylhexyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyl Examples thereof include dodecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexadecyl and monomethyl branched-isooctadecyl.

  As an alkenyl group, for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group And tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecel group, eicosenyl group, dococenyl group, tetracocenyl group, hexacocenyl group, octacocenyl group, triacontenyl group and the like.

  Examples of the aryl group include phenyl group, biphenylyl group, tolyl group, xylyl group, cumenyl group, mesityl group, ethylphenyl group, propylphenyl group, butylphenyl group, tertiary butylphenyl group, pentylphenyl group, hexylphenyl group , Heptylphenyl group, octylphenyl group, tertiary octylphenyl group, isooctylphenyl group, nonylphenyl group, dinonylphenyl group, decylphenyl group, undecylphenyl group, dodecylphenyl group, tetradecylphenyl group, hexadecylphenyl group Group, octadecylphenyl group, 2,4-di-tert-butylphenyl group, 2,4-di-tert-octylphenyl group, 2,4-di-tert-amylphenyl group, 2-tert-butyl-4- Methylphenyl group, 2,4-di-tert-butyl-5-methylphenyl group, , 6-di-tert-butyl-4-methylphenyl group, 2-cyclohexylphenyl group, p- (4-hydroxytamyl) phenyl group, benzyl group, phenethyl group, γ-phenylpropyl group, styryl group, cinnamyl group, Benzhydryl group, trityl group, cyclohexylphenyl group, styrenated phenyl group, p-cumylphenyl group, benzylphenyl group, α-naphthyl group, β-naphthyl group, di (1,1-dimethylethyl) -4-methylphenyl group, Examples include tri (1,1-dimethylethyl) phenyl group and di (1,1-dimethylethyl) phenyl group.

  The cycloalkyl group is, for example, cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, tetramethylcyclohexyl group, pentamethylcyclohexyl group, ethylcyclohexyl group, methylcyclo group A heptyl group is mentioned, As a cycloalkenyl group, a cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, a methyl cyclopentenyl group, a methylcyclohexenyl group, a methyl cycloheptenyl group etc. are mentioned, for example.

  The carbon number of the alkyl group is 1 to 30, preferably 1 to 18. Carbon number of an alkenyl group is 2-30, and 2-18 are preferable. The carbon number of the aryl group is 6 to 30, and 6 to 22 is preferable. The carbon number of the cycloalkyl group and cycloalkenyl group is 4 to 22, preferably 6 to 20. Any of these groups may be used alone or in combination of two or more.

  Moreover, as an example of a C2-C4 alkylene group of A which comprises General formula [1] which shows a phosphoric acid ester compound, ethylene group, a propylene group, 1-methyl ethylene group, 2-methyl ethylene group, a butylene group 1-methylpropylene group, 2-methylpropylene group, 3-methylpropylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-ethylethylene group, 2 -Ethyl ethylene group, and among them, an alkylene group having 2 or 3 carbon atoms is preferable. Any of these groups may be used alone or in combination of two or more.

  Moreover, X which comprises General formula [1] which shows a phosphoric acid ester compound is either a hydrogen atom, an alkali metal, or a quaternary ammonium cation. Examples of the alkali metal include lithium, sodium and potassium, and examples of the quaternary ammonium cation include quaternary ammonium cation of ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine and dipropylamine. Quaternary ammonium cations of alkylamines such as methylethylamine, methylpropylamine and ethylpropylamine; and quaternary ammonium cations such as alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, methylethanolamine and ethylethanolamine. It can be mentioned. Among these, a hydrogen atom, sodium, potassium and quaternary ammonium cations of ammonia, triethylamine and triethanolamine are preferable, and a hydrogen atom, a quaternary ammonium cation of ammonia and a quaternary ammonium cation of triethylamine are more preferable. These may be single or a mixture of two or more.

  Furthermore, although polymerization degree n which comprises General formula [1] which shows a phosphoric acid ester compound is an integer of 0-100, 0-50 are preferable, 0-30 are more preferable, 0-20 are still more preferable. In addition, m is 1 or 2, but the monoester body of m = 1 and the diester body of m = 2 may be used alone or as a mixture. In the case of a mixture, the molar ratio of monoester body / diester body may be any ratio, but is preferably 100/0 to 30/70, and more preferably 90/10 to 40/60.

  Moreover, 0.01-10 mass% is preferable, and, as for content in the flame-retardant resin composition of this invention of the phosphoric acid ester compound of (C) component, 0.05-7 mass% is more preferable, and 0 .1-5% by weight is even more preferred.

  The phosphate ester compound of the component (C) is obtained by reacting a compound having a hydroxyl group corresponding to a target structure with diphosphorus pentaoxide or polyphosphoric acid, and then hydrolyzing it by the addition of water. It can also be obtained by dehydration condensation of a compound having a hydroxyl group corresponding to the target structure and phosphoric acid. In addition, when the target compound is a salt, it can be obtained by neutralizing these compounds with a base corresponding to the target structure.

Next, the component (D) of the present invention will be described.
The flame retardant resin composition of the present invention preferably further contains zinc oxide as a flame retardant component (D).
The zinc oxide may be surface treated. Commercially available zinc oxide can be used. For example, zinc oxide type 1 (Mitsui Metal Mining Co., Ltd.), partially coated zinc oxide (Mitsui Metal Mining Co., Ltd.), Nanofine 50 (average particle size) 0.02 μm ultrafine particle zinc oxide: made by Sakai Chemical Industry Co., Ltd., Nanofine K (ultrafine particle zinc oxide coated with zinc silicate having an average particle diameter of 0.02 μm: made by Sakai Chemical Industry Co., Ltd.), etc. .

  The content of the zinc oxide of the component (D) in the flame retardant resin composition of the present invention is 0. 0 from the viewpoint of flame retardancy with respect to a total of 100 parts by mass of the components (A) and (B). The content is preferably 10 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 1.0 to 7.5 parts by mass.

  In addition, the total content of (A) component, (B) component and (D) component when the (D) component is blended as a flame retardant component exhibits excellent flame retardancy and impairs the physical properties of the resin In order to be absent, in the resin composition of the present invention, 20 to 60% by mass is preferable, 30 to 50% by mass is more preferable, and 35 to 45% by mass is even more preferable. If the amount is less than 20% by mass, sufficient flame retardancy may not be obtained, and if it exceeds 60% by mass, physical properties of the resin may be impaired.

Next, the component (E) of the present invention will be described.
The flame retardant resin composition of the present invention preferably contains a silicone oil processing aid as component (E) to improve processability. Examples of silicone oils include side chains of polysiloxane, dimethyl silicone oil having all methyl groups at one end, methylphenyl silicone oil having part of side chains of polysiloxane at phenyl, and portions of side chains of polysiloxane. Amine-modified, epoxy-modified, cycloaliphatic epoxy-modified, and methyl hydrogen silicone oil etc. where hydrogen is hydrogen, and copolymers of these, and organic groups introduced to part of their side chains and / or ends Carboxyl modified, carbinol modified, mercapto modified, polyether modified, long chain alkyl modified, fluoroalkyl modified, higher fatty acid ester modified, higher fatty acid amide modified, silanol modified, diol modified, phenol modified and / or aralkyl modified modified silicone oil You may use

  Specific examples of the above silicone oil include, as dimethyl silicone oil, KF-96 (Shin-Etsu Chemical Co., Ltd.), KF-965 (Shin-Etsu Chemical Co., Ltd.), KF-968 (Shin-Etsu Chemical Co., Ltd.) KF-99 (Shin-Etsu Chemical Co., Ltd. product), KF-9901 (Shin-Etsu Chemical Co., Ltd.), HMS-151 (as a methyl hydrogen silicone oil or a silicone oil having a methyl hydrogen polysiloxane structure). Gelest, HMS-071 (Gelest), HMS-301 (Gelest), DMS-H21 (Gelest), and the like. Examples of methylphenyl silicone oils include KF-50 (Shin-Etsu). Chemical Co., Ltd., KF-53 (Shin-Etsu Chemical Co., Ltd.), KF-54 (Shin-Etsu Chemical Co., Ltd.), KF-56 Shin-Etsu Chemical Co., Ltd. product etc. are mentioned, As an epoxy modified product, X-22-343 (Shin-Etsu Chemical Co., Ltd. product), X-22-2000 (Shin-Etsu Chemical Co., Ltd. product), KF- 101 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-1001 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. 3701 E (manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of carbinol-modified products include X-22-4039 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of amine-modified products include KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  Further, the content of the processing aid of the component (E) in the flame-retardant resin composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.05 to 7% by mass, 0. 1 to 5% by weight is even more preferred.

Furthermore, it is also preferable to mix | blend a lubricant with the flame retardant resin composition of this invention as needed. As such lubricants, pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, low molecular weight polyethylene, polyethylene wax and the like; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids Fatty acid amide-based lubricants such as fatty acid amides and bis fatty acid amides; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, ester-based lubricants such as fatty alcohol esters of fatty acids (ester waxes) Metal soaps, fatty alcohols, polyhydric alcohols, polyglycols, polyglycerols, partial esters of fatty acids and polyhydric alcohols, fatty acids and polyglycols, lubricants of partial esters of polyglycerols, silicone oils, mineral oils, etc. It is.
0.01-5 mass parts is preferable with respect to 100 mass parts of synthetic resin components in the flame-retardant resin composition of this invention, and, as for the compounding quantity of these lubricating agents, 0.3-3 mass parts is more preferable.

  In the flame retardant resin composition of the present invention, one or more of organic or inorganic flame retardants and flame retardant assistants, which do not contain a halogen, are used if necessary, as long as the effects of the present invention are not impaired. can do. As these flame retardants and flame retardant aids, triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, dialkyl phosphinic acids Examples thereof include salts, silicone flame retardants, metal oxides, boric acid compounds, expandable graphite, other inorganic flame retardant aids, and other organic flame retardants.

  Examples of the triazine ring-containing compounds include: ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene di-amine Melamine, hexamethylene dimelamine, 1,3-hexylene dimelamine and the like can be mentioned.

  Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (trademark of magnesium hydroxide manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

  Examples of the phosphate ester flame retardant include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, tris dichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl. Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropyl phenyl) Le) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

Examples of the condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.
Red phosphorus is mentioned as said inorganic phosphorus type | system | group flame retardant.
Examples of the dialkyl phosphinates include aluminum diethylphosphinate, zinc diethylphosphinate and the like.

  As said other inorganic type flame retardant adjuvant, inorganic compounds, such as a titanium oxide, aluminum oxide, magnesium oxide, titanium dioxide, a hydrotalcite, and its surface treatment goods are mentioned, for example. Specific examples thereof include, for example, TIPAQUE R-680 (trademark of titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), Kyowamag 150 (trademark of magnesium oxide manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite: Kyowa Various commercial products such as Chemical Industry Co., Ltd., Alkamizer 4 (trademark of zinc-modified hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.), and the like can be used.

  The flame retardant resin composition of the present invention may optionally contain a phenolic antioxidant, a phosphorous antioxidant, a thioether antioxidant, an ultraviolet light absorber, a hindered amine light stabilizer, an antiaging agent, etc. You may

Examples of the above-mentioned phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4) -Hydroxybenzyl) phosphonate, 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) ) Isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-tert-butyl) Tributyl-4-hydroxyphenyl) propionate, methyl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [ 3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl Terephthalate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3 -Tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane And triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these phenol type antioxidants, 0.05-5 mass parts is more preferable.

Examples of the above-mentioned phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] Phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di) Tert-Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol di- Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1 1,1,3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6- Tributylphenyl) -octadecyl phosphite, 2,2'-ethylidene bis (4,6- Tert-Butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl) And oxy] ethyl) amine, a phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, tris (2,4-di-tert-butylphenyl) phosphite and the like.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these phosphorus antioxidants, 0.05-5 mass parts is more preferable.

Examples of the above-mentioned thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid esters Can be mentioned.
0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these thioether type antioxidants, 0.05-5 mass parts is more preferable.

Examples of the UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone). And the like; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chloro; Benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-third) Octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis ( 2-tert-octyl-6- (benzotriazolyl) phenol), 2- (2'-hydroxyphenyl) such as 2- (2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl) benzotriazole Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di Benzoates such as tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyl oxi Substituted oxanilides such as zanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3- Cyanoacrylates such as ethyl 3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-di-tert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,2, Triaryl triazines such as 4-di-tert-butylphenyl) -s-triazine are mentioned.
0.001-30 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these ultraviolet absorbers, 0.05-10 mass parts is more preferable.

Examples of the above-mentioned hindered amine light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,3, 6,6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-tetramethyl-4-piperidyl) Sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 -Butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,2 6,6-Tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert) Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2, 2,6,6-Tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl- 4-piperidyl amino) Xane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6) , 6-Tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis ( N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12-tetraazadodecane, 1,6 11-Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, 1,6 , 11-tris [2,4-bis (N-butyl-N- (1,2,2) 6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] hindered amine compounds such as aminoundecanoic the like.
0.001-30 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these hindered amine light stabilizers, 0.05-10 mass parts is more preferable.

  Examples of the above-mentioned anti-aging agents include anti-aging agents such as naphthylamines, diphenylamines, p-phenyldiamines, quinolines, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols and phosphite esters. Be 0.001-10 mass parts is preferable with respect to 100 mass parts of synthetic resin components in a flame-retardant resin composition, and, as for the compounding quantity of these anti-aging agents, 0.05-5 mass parts is preferable.

  In the flame retardant resin composition of the present invention, a reinforcing material may be blended as an optional component within the range not impairing the effects of the present invention. As the reinforcing material, fibrous, plate-like, granular or powdery ones usually used for reinforcing synthetic resins can be used. Specifically, glass fibers, asbestos fibers, carbon fibers, graphite fibers, metal fibers, potassium titanate whiskers, aluminum borate whiskers, magnesium whiskers, silicon whiskers, warasteite, sepiolite, asbestos, slag fibers, zonolites, Inorganic fibrous reinforcements such as elastadite, gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, Kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila, sugar cane, wood pulp, paper waste, organic fibrous reinforcement such as waste paper and wool, glass flakes, non-swelling mica, graphite, metal foil ,ceramic , Clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely powdered silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, Examples thereof include plate-like and granular reinforcements such as titanium dioxide, aluminum silicate, gypsum, novaculite, dawsonite and white clay. These reinforcing materials may be coated or treated with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin, and may be treated with a coupling agent such as aminosilane or epoxysilane. It may be processed.

  In the flame retardant resin composition of the present invention, a layered silicate may be blended as an optional component as long as the effects of the present invention are not impaired. Layered silicates include montmorillonite, saponite, hectorite, beidellite, stevensite, smectite clay minerals such as nontronite, vermiculite, halloysite, swelling mica, talc, etc. And quaternary ammonium cations and phosphonium cations may be intercalated.

  A crystal nucleating agent may be further added as an optional component to the flame retardant resin composition of the present invention as long as the effects of the present invention are not impaired. As the crystal nucleating agent, one generally used as a polymer crystal nucleating agent can be appropriately used, and in the present invention, any of an inorganic crystal nucleating agent and an organic crystal nucleating agent can be used.

  Specific examples of the inorganic crystal nucleating agent include kaolinite, synthetic mica, clay, zeolite, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, neodymium oxide. And metal salts such as phenyl phosphonates. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.

  Specific examples of the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, sodium terephthalate, potassium oxalate Calcium, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate Metal salts of organic carboxylic acids such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexane carboxylate, organic sulfonic acid salts such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid amide , Carboxylic acid amides such as ethylene bis lauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), benzylidene sorbitol and derivatives thereof, sodium-2,2'-methylenebis (4 And phosphorus compound metal salts such as, 6-di-t-butylphenyl) phosphate and sodium 2,2-methylbis (4,6-di-t-butylphenyl).

  A plasticizer may be added as an optional component to the flame retardant resin composition of the present invention as long as the effects of the present invention are not impaired. As the plasticizer, those generally used as polymer plasticizers can be appropriately used. For example, polyester plasticizers, glycerin plasticizers, polyvalent carboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and the like An epoxy plasticizer etc. can be mentioned.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid and rosin, propylene glycol, 1,3-butanediol, 1,1 Examples thereof include polyesters composed of diol components such as 4-butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.

  Specific examples of the glycerin plasticizer include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin diacetomonooleate, and glycerin monoacetomonomontanate.

  Specific examples of the polyvalent carboxylic acid ester plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate and the like. Trimellitic acid esters such as tributyl mellitate, trioctyl trimellitate, trihexyl trimellitate, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, Adipate esters such as benzylbutyldiglycol adipate, citric acid esters such as triethyl acetyl citrate and tributyl acetyl citrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebaci Dibutyl, and sebacic acid esters such as di-2-ethylhexyl sebacate, and the like.

  Specific examples of the polyalkylene glycol plasticizer include polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenol, bisphenol End-capping compounds such as polyalkylene glycols such as propylene oxide addition polymers of the above, tetrahydrofuran addition polymers of bisphenols, or terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds thereof .

  The above-mentioned epoxy plasticizer generally refers to epoxy triglyceride and the like consisting of alkyl epoxy stearate and soybean oil, and in addition, so-called epoxy resin mainly composed of bisphenol A and epichlorohydrin. Can also be used.

  Specific examples of other plasticizers include neopentyl glycol dibenzoate, diethylene glycol dibenzoate, benzoic acid esters of aliphatic polyols such as triethylene glycol di-2-ethyl butyrate, fatty acid amides such as stearic acid amide, oleic acid Aliphatic carboxylic acid esters such as butyl, oxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters and paraffins can be mentioned.

  When a plasticizer is used in the present invention, only one type may be used, or two or more types may be used in combination.

  In the flame-retardant resin composition of the present invention, an acrylic processing aid may be further added as an optional component, as long as the effects of the present invention are not impaired. As the acrylic processing aid, one obtained by polymerizing one type of (meth) acrylic acid ester or copolymerizing two or more types can be used.

  Although it is possible to add a drip inhibitor to the flame retardant resin composition of the present invention as long as the effects of the present invention are not impaired, the incorporation of a fluorine based drip inhibitor causes environmental impact. It is not preferable from the viewpoint of the non-halogen considered, and furthermore, it is not preferable because the physical properties of the random copolymer polypropylene may be lowered. Examples of fluorine-based anti-drip agents include, for example, fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride and polyhexafluoropropylene, sodium salts of perfluoromethanesulfonic acid, potassium salts of perfluoro-n-butanesulfonic acid, Perfluoroalkanesulfonic acid alkali metal salt compounds such as perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, and perfluoro-2-ethylhexanesulfonic acid calcium salt or alkaline earths of perfluoroalkanesulfonic acid Metal salts etc. may be mentioned.

  In addition, the flame retardant resin composition of the present invention may contain, if necessary, additives commonly used in synthetic resins, such as crosslinking agents, antistatic agents, metal soaps, filling agents, antifogging agents, and plate outs. Containing an inhibitor, a surface treatment agent, a fluorescent agent, an antifungal agent, a germicide, a foaming agent, a metal deactivator, a mold release agent, a pigment, a processing aid, etc. within the range not impairing the effects of the present invention. Can.

  When the optional component other than the synthetic resin and the components (A) to (E) is blended in the present invention, the blending amount is not particularly limited as long as the effect of the present invention is not impaired. The total amount is preferably 40 parts by mass or less, and more preferably 20 parts by mass or less.

In the production of the flame-retardant resin composition of the present invention, the timing at which the components (A), (B) and (C) and, if necessary, the components (D) and (E) are added to the synthetic resin is particularly limited. I will not. For example, two or more of the components (A) to (E) may be prepacked and then blended into the synthetic resin, or each component may be blended into the synthetic resin .
When it is made into a one-pack, each component may be previously crushed and then mixed, or each component may be previously mixed and then crushed. The same applies to the case where a resin other than the synthetic resin and other optional components are blended.

  The molded article of the present invention is obtained by molding the flame retardant resin composition of the present invention. The molding method of the molded body is not particularly limited, and extrusion, calendering, injection molding, roll molding, compression molding, blow molding, etc. may be mentioned, and various methods such as resin plate, sheet, film, profiled article etc. Shaped articles can be produced.

  The flame retardant resin composition of the present invention and the molded article thereof are used in electric / electronic / communication, agriculture, forestry and fishery, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood It can be used in a wide range of industrial fields such as construction materials, civil engineering, furniture, printing and musical instruments. More specifically, printers, personal computers, word processors, keyboards (PDAs), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc. Office work, OA equipment, washing machine, refrigerator, vacuum cleaner, microwave oven, lighting equipment, game machine, iron, home appliances such as iron, TV, VTR, video camera, radio cassette player, tape recorder, mini disc, CD player, speaker, AV devices such as liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, LED sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, electric and electronic parts such as watches And communication equipment, housings (frames, cases, covers, exteriors) and parts of office automation equipment etc. It used to Paneling of applications.

  Furthermore, the flame-retardant resin composition of the present invention and the molded article thereof can be used in a seat (filler, outer fabric, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover , Mattress cover, air bag, insulation material, hanging hand, hanging band, electric wire coating material, electric insulation material, paint, coating material, covering material, floor material, corner material, carpet, wallpaper, wall covering material, exterior material Interior materials, roofing materials, decking materials, wall materials, pillars, floor boards, materials for fences, frameworks and moldings, windows and door profiles, shingles, crosses, terraces, balconies, soundproofing boards, insulation boards, windows Materials such as cars, hybrid cars, electric cars, vehicles, ships, aircraft, buildings, houses and building materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets , Bucket, hose, container, glasses, bags, cases, goggles, skis, rackets, tents, household goods of the musical instrument or the like, and is used in sporting goods, various applications and the like.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited at all by the following examples. The formulations in Tables 2 and 3 below are all based on parts by mass.

[Examples 1 to 20 and Comparative Examples 1 to 12]
The structure of the phosphate ester compound used for the test is described in Table 1 below. The flame retardant resin composition of the example is prepared by using the phosphoric acid ester compound described in the following Table 1 by the component combination described in the following Table 2 or 3, and then the flame retardant resin composition is obtained at 210 to 230 ° C. It extruded and manufactured the 2.0 mm diameter strand and pellet.
The combustion test was implemented by the following strand combustion test method using the obtained strand.
Moreover, the processing test was implemented by the following spiral flow test method using the obtained pellet. These results are shown in Tables 2 and 3 below.
Similarly, the flame retardant resin composition of the comparative example was prepared with the composition described in the following Table 2 or 3, and the same evaluation was performed.

<Combustion test: Strand combustion test method>
The obtained 2.0 mm diameter strand was used as a test piece of 20 cm in length, this test piece was kept vertical, the flame of the burner was indirectly heated for 5 seconds at the lower end, the flame was removed, and the test piece was ignited The time when the fire went out was measured. Next, a second application of flame was performed for 5 seconds as soon as the fire went out, and the time for which the ignited fire went out was measured in the same manner as the first fire. The same operation as above was carried out for a total of 5 times, and the flame retardancy was evaluated by observing whether or not the strand burns out during the test. (The burner flame was adjusted in the same manner as the UL-94 V standard.)
The combustion ranks were assigned based on the first to fifth combustion time and the presence or absence of cotton ignition. The combustion rank is the highest at 5 points, and the flame retardancy decreases as it becomes 4 points, 3 points, 2 points, 1 point and 0 points.
5 points: If the fire goes out within 20 seconds after the fifth ignition.
4 points: When the fire did not go off within 20 seconds after the fifth ignition, or when the cotton was ignited.
3 points: When the fire did not go out within 20 seconds after the fourth ignition, or when the cotton was ignited.
2 points: When the fire did not go out within 20 seconds after the third ignition, or when the cotton was ignited.
1 point: When the fire did not go out within 20 seconds after the second ignition, or when the cotton was ignited.
0 point: The fire did not go out within 20 seconds after the first ignition, or when the cotton was ignited.

<Processability test: Spiral flow test>
Melting temperature: 200 ° C using an injection molding machine (Hyperlink "http://www.nisseijushi.co.jp/" manufactured by Nissei Resin Co., Ltd.) on a spiral flow mold (width 10 mm x thickness 0.1 mm) The pellets obtained above were injected under the condition of injection pressure 100 Ma, and the spiral flow length (mm) was measured.
The longer the spiral flow length, the better the fluidity.

Claims (5)

The flame retardant resin composition which contains the following (A) component and (B) component as a flame retardant component, and also contains (C) component as a processability improvement agent.
Component (A): One or more melamine salts selected from the group of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate Component (B): One kind from the group of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate Piperazine salt (C) component selected as above: phosphate ester compound represented by the following general formula [1]

(R is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 4 to 22 carbon atoms and a cycloalkenyl group A represents an alkylene group having 2 to 4 carbon atoms, and X represents a hydrogen atom, an alkali metal, or a quaternary ammonium cation of ammonium, an alkylamine or an alkanolamine, n represents 0. And is an integer of 100 and m is 1 or 2.) 2. The flame retardant resin composition according to claim 1, wherein the contents of the components (A), (B) and (C) in the flame retardant resin composition are as follows.
(A) Component: 3 to 29% by mass
(B) Component: 9 to 46% by mass
Component (C): 0.01 to 10% by mass   The flame retardant resin composition according to any one of claims 1 to 2, further comprising zinc oxide (D) as a flame retardant component.   The flame retardant resin composition according to any one of claims 1 to 3, further comprising a silicone oil (E) as a processing aid component.   The molded object obtained from the flame-retardant resin composition as described in any one of Claims 1-4.