JP2017031351A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent in flame retardancy, excellent inherent physical properties of a resin and excellent in processing properties.SOLUTION: One or more kind of melamine salt (A) selected from a group of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate and one or more kind of piperazine salt selected from piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate as flame retardant components and further a phosphorous spiro compound (C) as a processability improver are contained.SELECTED DRAWING: None

Description

  The present invention relates to a highly workable flame retardant resin composition having excellent flame retardancy and processing characteristics without impairing the original physical properties of the resin.

Synthetic resins are excellent in molding processability, heat resistance and mechanical properties, and have the advantages of low specific gravity and light weight, and are widely used in various molded products such as films, sheets and structural parts. . 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 add a flame retardant to impart flame retardancy to these resins. This flame retardant is mainly composed of polyphosphoric acid, pyrophosphoric acid and a nitrogen-containing compound salt, and by forming a surface expansion layer (Intumescent) during combustion, it suppresses the diffusion and heat transfer of decomposition products and exhibits flame retardancy Intomesent flame retardants have excellent flame retardancy.

  In applications that require extremely severe flame retardancy, mainly for wire applications, a large amount of flame retardant is blended, so air bubbles are mixed in the molded product due to poor dispersion of the flame retardant, deterioration of the molded product surface condition, etc. This causes poor workability. 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 dispersibility of flame retardants. Since it is a problem that the flame retardancy is lowered due to the influence of the processing aid, a resin composition having both high flame retardancy and good workability is required even when the processing aid is contained. It was.

Japanese Patent Laid-Open No. 02-084457 JP 2010-189601 A JP 2007-169444 A

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

Therefore, the present inventors have intensively studied to solve the above-mentioned problems, and as a result, have reached the present invention. That is, this invention provides the flame retardant resin composition which contains the following (A) component and (B) component as a flame retardant component, and contains (C) component as a workability improvement agent.
(A) Component: one or more melamine salts selected from the group of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate (B) Component: one from the group of piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate Piperazine salt (C) component selected above: Phosphorus spiro compound

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

  Moreover, it is preferable that the flame-retardant resin composition of the present invention further contains silicone oil (component (E)) as a processing aid component.

  Moreover, this invention provides the molded object obtained from one of the said flame-retardant resin compositions.

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

Hereinafter, the flame retardant resin composition of the present invention will be described based on preferred embodiments.
First, the synthetic resin component used for the flame retardant resin composition of the present invention will be described. The resin used in the flame retardant resin composition of the present invention is not particularly limited. For example, thermoplastic resin, thermosetting resin, crystalline resin, non-crystalline resin, biodegradable resin, non-biodegradable Resin, synthetic resin, natural resin, general-purpose resin, engineering resin, polymer alloy and the like.

Examples of the synthetic resin include α such as polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene-propylene copolymer. -Olefin homopolymers or copolymers, copolymers of these α-olefins with polyunsaturated compounds such as conjugated or nonconjugated dienes, acrylic acid, methacrylic acid, vinyl acetate, polyethylene terephthalate, polyethylene terephthalate・ Biodegradable resins such as linear polyesters such as isophthalate, polyethylene terephthalate, paraoxybenzoate and polybutylene terephthalate, acid-modified polyesters and aliphatic polyesters, liquid crystalline polyesters, polycaprolactam and polyhexamethylene adipamide Copolymers of lyamide, liquid crystal polyamide, polyimide, polystyrene, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (for example, 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, rubber chloride, 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 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 fiber-based resin; thermosetting resins such as epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, thermosetting polyurethane; natural rubber, 3- Examples include microbial aliphatic polyesters such as hydroxybutyrate, microbial aliphatic polyamides, starch, cellulose, chitin / chitosan, gluten / gelatin, natural resins, general-purpose resins, engineering resins, polymer alloys, etc. Any type of resin can be used without limitation.
The polymer alloy referred to here is a polymer multi-component system, and may be a block polymer by copolymerization or a polymer blend by mixing.

  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, α- such as ethylene and propylene, butene-1 and the like. Copolymer rubbers with olefins, elastomers such as terpolymer rubbers with non-conjugated dienes such as ethylene-α-olefin and ethylidene norbornene, cyclopentadiene, α-olefin elastomers, silicone resins, etc. And / or an elastomer or rubber alloyed or blended can also be used.

  In the present invention, the synthetic resin has a molecular weight, a degree of polymerization, a density, a softening point, a ratio of insoluble matter in a solvent, a degree of stereoregularity, the presence or absence of a catalyst residue, the kind and blending ratio of monomers as raw materials, It can be used regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.).

  Among these synthetic resins, polyolefin resins are particularly preferable. Examples of the polyolefin resin include low density polyethylene, linear low density polyethylene, high density polyethylene, isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly Α-olefin polymer such as -3-methyl-1-butene, poly-3-methyl-1-pentene, poly-4-methyl-1-pentene, ethylene / propylene block or random copolymer, ethylene-methyl methacrylate Examples thereof include α-olefin copolymers such as copolymers and ethylene-vinyl acetate copolymers.

  In the present invention, the synthetic resin is more preferably a polyolefin polymer alloy of a polyolefin resin and a thermoplastic elastomer. Examples of the thermoplastic elastomer used in this polymer alloy include, for example, a styrene thermoplastic elastomer, a polyolefin thermoplastic elastomer, a polyvinyl chloride thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer, and a polyamide thermoplastic. Examples thereof include elastomers, transpolyisoprene thermoplastic elastomers, fluororubber thermoplastic elastomers, and chlorinated polyethylene thermoplastic elastomers. Among these, in the present invention, it is preferable to use a thermoplastic elastomer containing at least one of a styrene-based thermoplastic elastomer and a polyolefin-based thermoplastic elastomer.

Examples of the styrenic thermoplastic elastomer include copolymers of styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.), for example, 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 len-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and styrene-ethylene-butylene in which double bonds of these butadiene or isoprene are hydrogenated -Hydrogenated styrene elastomer resins such as styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin These can be used singly or as a mixture of two or more.
The polyolefin-based thermoplastic elastomer is an α-olefin polymer or copolymer having 2 to 20 carbon atoms, specifically, an ethylene-propylene resin, an ethylene-butene resin, an ethylene-hexene resin, or an ethylene-methylpentene resin. , Ethylene-octene resin, butene resin, butene-methylpentene resin, methylpentene resin, ethylene-vinyl acetate resin, ethylene-methacrylic acid resin, ethylene-methyl methacrylate resin, and the like. It can be used.

  The synthetic resin is more preferably a polypropylene homopolymer and a polyolefin polymer alloy of styrene-ethylene-butadiene-styrene (SEBS) or styrene-butadiene-styrene (SBS) from the viewpoint of resin physical properties.

  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.

  When the thermoplastic elastomer and polyolefin polymer alloy are used for the synthetic resin used in the flame retardant resin composition of the present invention, the resin physical properties are improved. % To 60% by mass, more preferably 20% to 50% by mass, even more preferably 30% to 40% by mass.

Next, the flame retardant component used in the resin composition of the present invention will be described.
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 from the viewpoint of flame retardancy. When these are used in a mixture, the higher the content ratio of melamine pyrophosphate, the better. The molar ratio of melamine pyrophosphate to pyrophosphoric acid to melamine is preferably 1: 1.5 to 1: 2.5, and most preferably 1: 2.
These salts of phosphoric acid and melamine can also be obtained by reacting the corresponding phosphoric acid or phosphate with melamine, respectively. However, the melamine salt used in the component (A) of the present invention is melamine orthophosphate. Preference is given to melamine pyrophosphate or melamine polyphosphate obtained by heat condensation of melamine, in particular melamine pyrophosphate.

The piperazine salt of component (B) used as the flame retardant component of the present invention is selected from the group of piperazine orthophosphate, piperazine pyrophosphate, 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 when used in a mixture, the higher the content ratio of piperazine pyrophosphate, the more preferable. Further, the ratio of pyrophosphoric acid to piperazine in piperazine pyrophosphate is preferably 1: 0.5 to 1: 1.5 in molar ratio, and more preferably 1: 1.
These salts of phosphoric acid and piperazine can be obtained by reacting the corresponding phosphoric acid or phosphate and piperazine, respectively, but the piperazine salt used in the component (B) of the present invention is diorthophosphoric acid. Piperazine pyrophosphate or piperazine polyphosphate obtained by heat condensation of 1 piperazine is preferable, and piperazine pyrophosphate is particularly preferable.

  The blending amount of the component (A) is preferably 3 to 29% by mass, more preferably 5 to 24% by mass, and even 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) exhibits excellent flame retardancy and does not impair the physical properties of the resin. In the flame retardant resin composition of the present invention, 20 mass%-60 mass% are preferable, 30 mass%-50 mass% are more preferable, and 35 mass%-45 mass% are still more preferable. If it is less than 20% by mass, sufficient flame retardancy may not be obtained. If it exceeds 60% by mass, the physical properties of the resin may be impaired.

  The content ratio (mass basis) of the component (A) and the component (B) is preferably (A) / (B) = 20/80 to 50/50, and (A) / (B ) = 30/70 to 50/50 is more preferable.

Next, the processability improver used in the flame retardant resin composition of the present invention will be described.
The phosphorus-based spiro compound (C) used as the processability improver of the present invention is not limited as long as it is a spiro compound containing a phosphorus atom, but in terms of both high workability and high flame retardancy, A compound represented by the general formula [1] is more preferable.

（Ａ¹、Ａ²、Ａ³、Ａ⁴はそれぞれ独立して、酸素原子又は硫黄原子を表し、ｋ、ｍ、ｎ、ｒはそれぞれ独立して０又は１であり、Ｒ¹、Ｒ²はそれぞれ独立して炭素数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いずれかの基を表す。）

(A ¹ , A ² , A ³ , A ⁴ each independently represents an oxygen atom or a sulfur atom, k, m, n, and r are each independently 0 or 1, and R ¹ , R ² are Each independently 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. Represents any group.)

  Examples of the alkyl group constituting the phosphorus spiro compound represented by the general formula [1] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, and an 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-methylbutyryl Group, 2-ethylhexyl group, 3,3,5-trimethylhexyl group, 2-butyloctyl group, 2-butyldecyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-hexyldecyl group Group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, monomethyl branched-isooctadecyl group and the like. Examples of the alkenyl group include 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. , Tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecel group, eicosenyl group, dococenyl group, tetracocenyl group, hexacocenyl group, octacocenyl group, triaconenyl group and the like. As the aryl group, for example, 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 thereof include a tri (1,1-dimethylethyl) phenyl group and a di (1,1-dimethylethyl) phenyl group. Examples of the cycloalkyl group and the cycloalkenyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a tetramethylcyclohexyl group, a pentamethylcyclohexyl group, and an ethylcyclohexyl group. Group, methylcycloheptyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, methylcyclopentenyl group, methylcyclohexenyl group, methylcycloheptenyl group and the like. Carbon number of an alkyl group is 1-30, and 1-18 are preferable. The alkenyl group has 2 to 30 carbon atoms, preferably 2 to 18 carbon atoms. The aryl group has 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. Carbon number of a cycloalkyl group and a cycloalkenyl group is 4-22, and 6-20 are preferable.

  The phosphorous spiro compound represented by the formula [1] used in the present invention is a phosphoric acid type spiro compound, a phosphorous acid type spiro compound, a phosphonic acid type spiro compound, a phosphonous acid type spiro compound, or a sulfur-containing phosphorous type. There are spiro compounds and mixed phosphorus spiro compounds, but these may be used alone or in the form of a mixture of two or more.

Specific examples of phosphoric acid type spiro compounds include 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dimethoxy-, 3,9-dioxide, 2,4, 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (1,1-dimethylethoxy)-, 3,9-dioxide, 2,4,8,10-tetraoxa-3 , 9-diphosphaspiro [5.5] undecane, 3,9-dioctadecyloxy-, 3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3, 9-diphenoxy-, 3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (4-nonylphenoxy) , 3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,6-bis (1,1-dimethylethyl) -4 -Methylphenoxy]-, 3,9-dioxide and the like,
Phosphorous acid type spiro compounds include 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dimethoxy-, 2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3,9-diethoxy-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (isodecyloxy)- 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (isotridecyloxy)-, 2,4,8,10-tetraoxa-3,9- Diphosphaspiro [5.5] undecane, 3,9-bis (tridecyloxy)-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bi (Octadecyloxy)-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [(3,3,4,5,5-pentamethylcyclohexyl) oxy ], 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-diphenoxy-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] Undecane, 3,9-bis (4-nonylphenoxy)-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,4-bis (1,1-dimethylethyl) phenoxy]-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,4,6-tris (1, 1 Dimethylethyl) phenoxy]-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,4-bis (1-methyl-1-phenylethyl) Phenoxy]-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,6-bis (1,1-dimethylethyl) -4-methylphenoxy ] Etc.
As the phosphonic acid type spiro compound, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dimethyl-, 3,9-dioxide, 2,4,8,10 -Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-dioctadecyl-, 3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane , 3,9-dinonylphenyl-, 3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (phenylmethyl) -3, , 9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,6-bis (1,1-dimethylethyl)- - methylphenyl] -, 3,9-dioxide and the like,
Examples of phosphonous acid type spiro compounds include 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-didecyl-, 2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3,9-dioctadecyl-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-phenyl-, 2,4 , 8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,6-bis (1,1-dimethylethyl) -4-methylphenyl]-and the like,
As the sulfur-containing phosphorus-based spiro compound, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [2,4-bis (1,1-dimethylethyl) Phenoxy] -3,9-sulfide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis [(diphenylmethyl) thio] -3,9-sulfide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (cyclohexylthio) -3,9-sulfide, 2,4,8,10-tetraoxa-3, 9-Diphosphaspiro [5.5] undecane, 3,9-bis (octylthio)-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9 Bis (decylthio)-, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis (phenylthio)-, 2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, 3,9-dimethyl-3,9-disulfide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-bis ( Methylthio) -3,9-disulfide and the like,
Examples of mixed phosphorus spiro compounds include 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-methyl-9-phenoxy-3,9-dioxide, 2,4,8 , 10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3-octadecyl-9- (octadecyloxy) -3-oxide and the like.

  As the phosphorus-based spiro compound of component (C), a phosphite-type spiro compound, a phosphonic acid-type spiro compound, and a sulfur-containing phosphorus-based spiro compound are preferable from the viewpoint of flame retardancy and processing characteristics. More preferred are spiro compounds and phosphonic acid type spiro compounds.

  In addition, the content of the phosphorus spiro compound (C) in the flame retardant resin composition of the present invention is preferably 0.01% by mass to 10% by mass, and 0.05% by mass to 7% by mass. More preferably, 0.1% by mass to 5% by mass is even more preferable.

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 the flame retardant component (D).
The zinc oxide may be surface-treated. Commercially available zinc oxide can be used, for example, one type of zinc oxide (manufactured by Mitsui Kinzoku Mining Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Kinzoku Mining Co., Ltd.), Nano Fine 50 (average particle size) 0.02 μm ultrafine zinc oxide (manufactured by Sakai Chemical Industry Co., Ltd.), Nanofine K (ultrafine zinc oxide coated with zinc silicate having an average particle size of 0.02 μm: Sakai Chemical Industry Co., Ltd.), etc. .

  The content of zinc oxide as the component (D) in the flame retardant resin composition of the present invention is 0.01% from the viewpoint of flame retardancy with respect to 100 parts by mass in total of the components (A) and (B). -10 mass parts is preferable, More preferably, it is 0.5-10 mass parts, More preferably, it is 1.0-7.5 mass parts.

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

Next, (E) component of this invention is demonstrated.
In order to improve processability, the flame retardant resin composition of the present invention preferably contains a silicone oil processing aid as the component (E).

  Examples of silicone oils include polysiloxane side chains, dimethyl silicone oils whose terminals are all methyl groups, methyl phenyl silicone oils whose polysiloxane side chains are partially phenyl groups, and part of polysiloxane side chains. Methyl hydrogen silicone oil and the like, and copolymers thereof, and an organic group introduced into a part of the side chain and / or terminal thereof, an amine modification, an epoxy modification, an alicyclic epoxy modification, Carboxol 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 May be used.

  Specific examples of the silicone oil include KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.) as dimethyl silicone oil. As silicone oil having a methyl hydrogen silicone oil or a methyl hydrogen polysiloxane structure, KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (Shin-Etsu Chemical Co., Ltd.), HMS-151 ( Gelest), HMS-071 (Gelest), HMS-301 (Gelest), DMS-H21 (Gelest), and the like. Examples of methylphenyl silicone oil 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.) and the like, and epoxy modified products include, for example, X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2000 (manufactured by Shin-Etsu Chemical Co., Ltd.), 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.) and the like. Examples of carboxyl-modified products include X-22- Examples of 3701E (manufactured by Shin-Etsu Chemical Co., Ltd.) and carbinol modified products include X-22-4039 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Examples of the amine-modified product include KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  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% by mass to 10% by mass, more preferably 0.05% by mass to 7% by mass. Preferably, 0.1% by mass to 5% by mass is even more preferable.

Furthermore, it is also preferable to mix | blend a lubricant with the flame-retardant resin composition of this invention as needed. Examples of such lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, micro wax, synthetic paraffin, low molecular weight polyethylene and polyethylene wax; halogenated hydrocarbon lubricants; fatty acid lubricants such as higher fatty acids and oxy fatty acids. Fatty acid amide type lubricants such as fatty acid amides and bis fatty acid amides; ester type lubricants such as lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, fatty alcohol esters of fatty acids (ester waxes) ; Metal soap, fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, fatty acid and polyhydric alcohol partial ester, fatty acid and polyglycol, polyglycerol partial ester lubricant, silicone oil, mineral oil, 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 lubricants, 0.3-3 mass parts is more preferable.

  In the flame-retardant resin composition of the present invention, one or more organic or inorganic flame retardants or flame retardant aids that do not contain halogen are used as necessary, as long as the effects of the present invention are not impaired. can do. These flame retardants and flame retardant aids include triazine ring-containing compounds, metal hydroxides, phosphate ester flame retardants, condensed phosphate ester flame retardants, phosphate flame retardants, inorganic phosphorus flame retardants, dialkylphosphinic acids Examples include salts, silicone flame retardants, metal oxides, boric acid compounds, expansive graphite, other inorganic flame retardant aids, and other organic flame retardants.

  Examples of the triazine ring-containing compound include ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimer Examples include melamine, hexamethylene dimelamine, and 1,3-hexylene dimelamine.

  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, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl Phosphate, trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropyl phenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t -Butylphenyl) phosphate, isopropylphenyldiphenylphosphate, bis- (isopropylphosphate) Le) diphenyl phosphate, tris - (isopropylphenyl) phosphate, and the like.

Examples of the condensed phosphate ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
Examples of the inorganic phosphorus flame retardant include red phosphorus.

  Examples of the dialkyl phosphinate include aluminum diethylphosphinate and zinc diethylphosphinate.

  Examples of the other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, titanium dioxide, hydrotalcite, and surface-treated products thereof. Specific examples thereof include, for example, TIPAQUE R-680 (trademark of titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), Kyowa Mag 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.) can be used.

  The flame retardant resin composition of the present invention contains a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, etc., if necessary. May be.

Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-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-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-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-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) ) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert Tributyl-4-hydroxyphenyl) propionate, tetrakis [methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [ 3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditertiarybutyl-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-ditert-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 , 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 phenolic antioxidants, 0.05-5 mass parts is more preferable.

Examples of the 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, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2- Tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di Tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2′-methylenebis (4,6- Tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis (4,6-ditert-butylphenyl) fluorophosphite, 2-ethyl-2-butylpropylene glycol and 2,4,6-tri Examples include tributylphenol phosphite, 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 antioxidant, 0.05-5 mass parts is more preferable.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionate esters). Is 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 | system | group antioxidant, 0.05-5 mass parts is more preferable.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert. Octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis ( 2- (2′-hydroxyphenyl) such as tert-octyl-6- (benzotriazolyl) phenol) and 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole Benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-di Benzoates such as tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanylide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3- Cyanoacrylates such as til-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s- Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2, And triaryltriazines such as 4-ditertiarybutylphenyl) -s-triazine.
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 hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 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 -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (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-ditertiary 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-piperidylamino) Xanthane / 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 antiaging agent include naphthylamine, diphenylamine, p-phenyldiamine, quinoline, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols, and phosphites. 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.

  You may mix | blend a reinforcing material with the flame-retardant resin composition of this invention as an arbitrary component in the range which does not impair the effect of this invention. As the reinforcing material, a fibrous, plate-like, granular or powdery material usually used for reinforcing a synthetic resin can be used. Specifically, glass fiber, asbestos fiber, carbon fiber, graphite fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, Elastadite, gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and other inorganic fibrous reinforcements, polyester fiber, nylon fiber, acrylic fiber, regenerated cellulose fiber, acetate fiber, Organic fiber reinforcements such as kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper waste, waste paper and wool, glass flakes, non-swellable mica, graphite, metal foil ,ceramic Zeolite, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, Examples thereof include plate-like and granular reinforcing materials such as titanium dioxide, aluminum silicate, gypsum, novaculite, dosonite and clay. These reinforcing materials may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, or 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. Examples of layered silicates include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, swellable mica, talc, etc. In addition, quaternary ammonium cations and phosphonium cations may be intercalated.

  The flame retardant resin composition of the present invention may further contain a crystal nucleating agent as an optional component as long as the effects of the present invention are not impaired. As the crystal nucleating agent, those generally used as a polymer crystal nucleating agent can be appropriately used. In the present invention, either an inorganic crystal nucleating agent or 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, and neodymium oxide. And metal salts such as phenylphosphonate. These inorganic crystal nucleating agents may be modified with an organic substance in order to enhance the dispersibility in the composition.

  Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, etc., organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearic acid amide , Carboxylic acid amides such as ethylenebislauric acid amide, palmitic acid amide, hydroxystearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), benzylidenesorbitol and its derivatives, sodium-2,2′-methylenebis (4 , 6-di-t-butylphenyl) phosphate, phosphorus compound metal salts, and 2,2-methylbis (4,6-di-t-butylphenyl) sodium.

  In the flame-retardant resin composition of the present invention, a plasticizer may be blended as an optional component 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, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers and epoxies. Examples thereof include plasticizers.

  Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, propylene glycol, 1,3-butanediol, 1,4 Examples thereof include polyesters composed of diol components such as butanediol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acids such as polycaprolactone. These polyesters may have their ends blocked with a monofunctional carboxylic acid or a monofunctional alcohol, and may be blocked 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 polyvalent carboxylic acid ester plasticizers include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, trimellit Trimellitic acid ester such as tributyl acid, trioctyl trimellitic acid, trihexyl trimellitic acid, diisodecyl adipate, n-octyl-n-decyl adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, adipine Adipic acid esters such as benzylbutyl diglycol acid, citrate esters such as triethyl acetylcitrate and tributyl acetylcitrate, azelaic acid esters such as di-2-ethylhexyl azelate, sebacic acid Butyl, 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 bisphenols, and bisphenols. And end-capped compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds.

  The epoxy plasticizer generally refers to an epoxy triglyceride composed of an alkyl epoxy stearate and soybean oil, but there are other so-called epoxy resins mainly made of bisphenol A and epichlorohydrin. Can be used.

  Specific examples of other plasticizers include benzoic acid esters of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, fatty acid amides such as stearamide, oleic acid Examples thereof include aliphatic carboxylic acid esters such as butyl, oxyacid esters such as methyl acetylricinoleate and butyl acetylricinoleate, pentaerythritol, various sorbitols, polyacrylic acid esters, and paraffins.

  When using a plasticizer in this invention, only 1 type may be used or 2 or more types may be used together.

  The flame retardant resin composition of the present invention may further contain an acrylic processing aid as an optional component within a range not impairing the effects of the present invention. As the acrylic processing aid, one obtained by polymerizing one kind of (meth) acrylic acid ester or copolymerizing two or more kinds can be used.

  In addition, the flame retardant resin composition of the present invention can be blended with an anti-drip agent within a range that does not impair the effects of the present invention. It is not preferable from the viewpoint of non-halogen, and it is not preferable because the physical properties of the random copolymer polypropylene may be deteriorated. Examples of the fluorine-based anti-drip agent include, for example, fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, Perfluoroalkanesulfonic acid alkali metal salt compounds such as perfluoro-t-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt, or perfluoroalkanesulfonic acid alkaline earths A metal salt etc. are mentioned.

In addition, in the flame-retardant resin composition of the present invention, additives that are usually used in synthetic resins as necessary, for example, cross-linking agents, antistatic agents, metal soaps, spotting agents, antifogging agents, plate-outs, etc. Add an inhibitor, surface treatment agent, fluorescent agent, antifungal agent, bactericidal agent, foaming agent, metal deactivator, release agent, pigment, processing aid, etc., as long as the effects of the present invention are not impaired. Can do.
In the present invention, when an optional component other than the synthetic resin and the components (A) to (E) is blended, the blending amount is not particularly limited as long as the effects of the present invention are not impaired. The total amount is preferably 40 parts by weight or less, and more preferably 20 parts by weight or less.

  In the production of the flame retardant resin composition of the present invention, the timing when the components (A), (B), and (C) and, if necessary, the components (D) and (E) are added to the synthetic resin is particularly limited. Not. For example, two or more types selected from the components (A) to (E) may be blended into the resin after making them into one pack, or each component may be blended with the resin.

  In the case of making one pack, each component may be pulverized and mixed in advance, or may be pulverized after mixing each component in advance. The same applies when a resin other than the 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 examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, and various shapes such as resin plates, sheets, films, and odd-shaped products. Can be manufactured.

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

  Further, the flame retardant resin composition and molded product thereof according to the present invention are a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover. , Mattress cover, air bag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring, corner wall, carpet, wallpaper, wall covering material, exterior material , Interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, eaves materials, frames and repetitive shapes, windows and door shapes, slabs, siding, terraces, balconies, soundproofing plates, heat insulating plates, windows Materials such as automobiles, hybrid cars, electric cars, vehicles, ships, aircrafts, buildings, houses and building materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fibers, carpets, doormats, 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 by the following examples. In addition, all the mixing | blendings of Table 1 are a mass% reference | standard.

[Examples 1 to 11 and Comparative Examples 1 to 3]
The flame retardant resin compositions of the examples were prepared with the ingredients shown in Table 1 below, and then the flame retardant resin compositions were extruded at 200 to 230 ° C. to produce pellets, which were used at 220 ° C. A test piece having a length of 20 mm, a width of 2 mm, and a thickness of 2 mm was obtained by molding the sheet at 15 MPa and cutting the sheet. Using this test piece, a flame retardancy test was conducted by the following test method. The results are shown in Table 1.
Moreover, processability evaluation was performed by the following test method using the said pellet. The results are shown in Table 1.
Similarly, a flame retardant resin composition of a comparative example was prepared with the formulation shown in Table 1, and the same evaluation was performed. The comparative example was implemented about the presence or absence of the coupling agent of an Example, the presence or absence of zinc oxide, and the presence or absence of a processing aid. The results are shown in Table 1.

<Flame retardance test method>
A test piece having a length of 20 mm, a width of 2 mm, and a thickness of 2 mm was kept vertical, a burner was fired at the lower end indirectly for 5 seconds, the flame was removed, and the time when the fire ignited the test piece was extinguished was measured. Next, at the same time that the fire was extinguished, the second flame contact was performed for 5 seconds, and the time when the ignited fire extinguished was measured in the same manner as the first time. Repeat these series of operations within 5 times until the fire does not go out. It was also evaluated at the same time whether or not the cotton under the test piece was ignited by the falling fire type.
The combustion rank was given from the 1st to 5th combustion time, the presence or absence of cotton ignition, and the like. The combustion rank is highest at 5 points, and the flame retardance decreases as it becomes 4 points, 3 points, 2 points, 1 point, 0 points.
5 points: When the fire goes out within 20 seconds after the fifth ignition.
4 points: The fire did not go out within 20 seconds after the fifth ignition, or the cotton was ignited.
3 points: If the fire did not go out within 20 seconds after the fourth ignition, or if cotton was ignited.
2 points: If the fire did not go out within 20 seconds after the third ignition, or if cotton was ignited.
1 point: If the fire did not go out within 20 seconds after the second ignition, or if cotton was ignited.
0 points: If the fire did not go out within 20 seconds after the first ignition, or if cotton was ignited.

<Processability evaluation method>
The state of surface roughness of pellets produced by extrusion at 200 to 230 ° C. and the state of bubbles on the cut surface were evaluated by visual observation and given a workability rank. As for the workability rank, A is the highest, and as B, C, and D, the processing stability decreases.
A: No air bubbles are present on the pellet cut surface, and the pellet surface is very smooth.
B: Air bubbles are slightly present on the cut surface of the pellet and the surface of the pellet is slightly rough.
C: A lot of bubbles are present on the pellet cutting surface, and the pellet surface is sticky.
D: A lot of large bubbles exist on the pellet cut surface, and the pellet surface is rough and rough.

Claims (6)

A flame retardant resin composition containing the following component (A) and component (B) as a flame retardant component, and further containing component (C) as a processability improver.
(A) Component: one or more melamine salts selected from the group of melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate (B) Component: one from the group of piperazine orthophosphate, piperazine pyrophosphate, piperazine polyphosphate Piperazine salt (C) component selected above: Phosphorus spiro compound The flame-retardant resin composition according to claim 1, wherein the content of the components (A), (B), and (C) in the flame-retardant resin composition is as follows.
(A) component: 3-29 mass%
(B) component: 9 to 46%
(C) component: 0.01-10 mass% The flame retardant resin composition according to claim 1 or 2, wherein the component (C) is a phosphorus spiro compound represented by the following general formula [1].

(A ¹ , A ² , A ³ , and A ⁴ each independently represents an oxygen atom or a sulfur atom,
k, m, n, and r are each independently 0 or 1,
R ¹ and R ² are each independently 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. Represents any group selected from the group consisting of )   Furthermore, the flame-retardant resin composition of any one of Claims 1-3 containing a zinc oxide (D) as a flame retardant component.   Furthermore, the flame-retardant resin composition of any one of Claims 1-4 which contains a silicone oil (E) as a process adjuvant component.   The molded object obtained from the flame-retardant resin composition as described in any one of Claims 1-5.