JP2016003248A - Flame retardant composition and flame-retardant synthetic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant composition that can impart excellent flame retardancy to synthetic resin without impairing its flowability or processability.SOLUTION: A flame retardant composition comprises a phosphate compound represented by formula (1) (component A), a phosphate compound represented by formula (3) (component B), and an acrylic processing aid.

Description

  TECHNICAL FIELD The present invention relates to a flame retardant composition for a synthetic resin and a flame retardant synthetic resin composition containing the flame retardant composition, and a flame retardant composition excellent in processability and flame retardancy and the flame retardant composition. The flame retardant synthetic resin composition.

  Conventionally, synthetic resins have been widely used for building materials, automobile parts, packaging materials, agricultural materials, housing materials for home appliances, toys and the like due to their excellent chemical and mechanical properties. However, many synthetic resins are flammable substances, and flame retardant is indispensable depending on the application. And as a flame retardant method of a synthetic resin, a halogen-based flame retardant, an inorganic phosphorus flame retardant represented by a polyphosphoric flame retardant such as red phosphorus and ammonium polyphosphate, and a triaryl phosphate ester compound are representative. It is widely known to use an organic phosphorus flame retardant, a metal hydroxide or a flame retardant assistant such as antimony oxide or a melamine compound alone or in combination.

However, halogen-based flame retardants have a problem of generating harmful gases during combustion. Therefore, an attempt has been made to use the above-mentioned phosphorus-based flame retardant that does not cause such a problem.
For example, Patent Document 1 discloses a flame retardant synthetic resin composition containing ammonium polyphosphate, a polyvalent hydroxyl group-containing compound, a triazine ring-containing compound, and a metal hydroxide. Patent Documents 2 and 3 disclose a flame retardant synthetic resin composition containing melamine polyphosphate and (penta-tripenta) erythritol. Patent Document 4 discloses a flame retardant synthetic resin composition containing polybutylene terephthalate (PBT), melamine pyrophosphate and an aromatic phosphate oligomer. Furthermore, Patent Document 5 and Patent Document 6 describe that melamine pyrophosphate and other phosphorus compounds are effective for flame-retarding polymers such as PBT.

  Among these, the intumescent flame retardant that exhibits flame retardancy by forming a surface expansion layer (Intumescent) during combustion and suppressing the diffusion and heat transfer of decomposition products has excellent flame retardancy. For example, it is described in Patent Document 7.

  However, since this intumescent flame retardant is a low molecular compound having high polarity, the compatibility and dispersibility in a synthetic resin which is a high molecular compound are not sufficient. For this reason, when an intimescent flame retardant is blended with a synthetic resin, the fluidity of the synthetic resin composition is deteriorated, resulting in a problem in workability. In particular, in order to impart sufficient flame retardancy to the synthetic resin composition, it is necessary to add a high amount of intomesent flame retardant, so both flame retardancy and fluidity and processability of the synthetic resin are achieved. It was difficult.

JP-A-8-176343 U.S. Pat. No. 3,936,416 U.S. Pat. No. 4,010,137 Japanese Patent Laid-Open No. 11-152402 U.S. Pat. No. 4,278,591 US Pat. No. 5,618,865 JP 2003-26935 A

  Accordingly, an object of the present invention is to provide a flame retardant composition capable of imparting excellent flame retardancy to a synthetic resin without impairing its fluidity and workability. Moreover, it is providing the flame-retardant synthetic resin composition which mix | blended this flame retardant composition, was excellent in the flame retardance, and was excellent in the fluidity | liquidity and workability. Moreover, it is providing the molded object which has the flame retardance obtained from this flame retardant synthetic resin composition.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention includes 20 to 50 parts by mass of the following (A) component, 50 to 80 parts by mass of the following (B) component (provided that the total of the (A) and (B) components is 100 parts by mass), and the following ( The flame retardant composition containing 0.1 to 15 parts by mass of component C) is provided.
(A) component: (poly) phosphate compound (B) represented by the following general formula (1) component: (poly) phosphate compound (C) component represented by the following general formula (3): acrylic Processing aids

（式中、ｎは１〜１００の数を表し、Ｘ¹はアンモニアまたは下記一般式（２）で表されるトリアジン誘導体であり、０＜ｐ≦ｎ＋２である。）

(In the formula, n represents a number of 1 to 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and 0 <p ≦ n + 2.)

（式中、Ｚ¹及びＺ²は同一でも異なっていてもよく、−ＮＲ⁵Ｒ⁶基〔ここでＲ⁵及びＲ⁶は同一または異なって水素原子、炭素原子数１〜６の直鎖もしくは分岐のアルキル基もしくはメチロール基を表す〕、水酸基、メルカプト基、炭素原子数１〜１０の直鎖もしくは分岐のアルキル基、炭素原子数１〜１０の直鎖もしくは分岐のアルコキシ基、フェニル基及びビニル基からなる群より選ばれる基である。）

(In the formula, Z ¹ and Z ² may be the same or different, and —NR ⁵ R ⁶ group [wherein R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a straight chain of 1 to 6 carbon atoms or Represents a branched alkyl group or a methylol group], a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and vinyl. It is a group selected from the group consisting of groups.)

（式中、ｒは１〜１００を表し、Ｙ¹は〔Ｒ¹Ｒ²Ｎ（ＣＨ₂）ｍＮＲ³Ｒ⁴〕、ピペラジンまたはピペラジン環を含むジアミンであり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴はそれぞれ水素原子、炭素原子数１〜５の直鎖もしくは分岐のアルキル基であり、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は同一の基であっても異なる基であってもよく、ｍは１〜１０の整数であり、０＜ｑ≦ｒ＋２である。）

(Wherein r represents 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) mNR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ may be the same group or different groups. M is an integer of 1 to 10, and 0 <q ≦ r + 2.

  In addition, the present invention preferably provides the flame retardant composition further containing 0.01 to 10 parts by mass of zinc oxide as the component (D).

  In addition, the present invention preferably provides the flame retardant composition further containing 0.005 to 5 parts by mass of an anti-drip agent as component (E).

In the present invention, preferably, as the component (A), n in the general formula (1) is 2, p is 2, X ¹ is melamine (Z ¹ and Z ² in the general formula (2) are —NH ₂ ) The above flame retardant composition using melamine pyrophosphate, which is ₂ ), is provided.

In addition, the present invention preferably provides the flame retardant composition using, as the component (B), a piperazine polyphosphate in which q in the general formula (3) is 1 and Y ¹ is piperazine.

  The present invention preferably also provides the flame retardant composition, wherein the piperazine polyphosphate is piperazine pyrophosphate.

  Moreover, this invention provides the flame-retardant synthetic resin composition which mix | blended the said flame retardant composition with the synthetic resin.

  The present invention preferably provides the flame retardant synthetic resin composition, wherein the synthetic resin is a polyolefin resin and a styrene thermoplastic elastomer.

  Moreover, this invention provides the molded object obtained from the said flame-retardant synthetic resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, the flame retardant composition which can provide the outstanding flame retardance without impairing the fluidity | liquidity and workability of a synthetic resin can be provided. Moreover, according to this invention, the flame-retardant synthetic resin composition excellent in the flame retardance and excellent in fluidity | liquidity and workability can be provided. Moreover, according to this invention, the molded object which has a flame retardance can be processed easily and can be provided.

  The (poly) phosphate compound represented by the general formula (1) used as the component (A) in the flame retardant composition of the present invention is represented by phosphoric acid and ammonia or the general formula (2). It is a salt with a triazine derivative.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by Z ¹ and Z ² in the general formula (2) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. , Isobutyl, amyl, isoamyl, tertiary amyl, hexyl, cyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, decyl, etc. Examples of the 10 straight-chain or branched alkoxy groups include groups derived from these alkyl groups. Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R ⁵ and R ⁶ in the —NR ⁵ R ⁶ group that Z ¹ and Z ² can take include, for example, the alkyl groups listed above. The thing of 1-6 carbon atoms is mentioned.

  Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, and 2,4-diamino-6-hydroxy-1. , 3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino- 6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2 , 4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.

Examples of the (poly) phosphate compound represented by the general formula (1) preferably used as the component (A) include a salt of phosphoric acid and melamine or an ammonium polyphosphate compound.

Examples of the salt of phosphoric acid and melamine that are preferably used as the component (A) include melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate. Among these, n in the general formula (1) is Particularly preferred is melamine pyrophosphate, wherein 2, p is 2, and X ¹ is melamine.
The salt of phosphoric acid and melamine can be obtained by the following method. For example, in the case of melamine pyrophosphate, sodium pyrophosphate and melamine can be reacted by adding hydrochloric acid at an arbitrary reaction ratio, and neutralized with sodium hydroxide to obtain melamine pyrophosphate.

  The ammonium polyphosphate compound is a compound containing ammonium polyphosphate alone or ammonium polyphosphate as a main component. Commercially available products can be used as the ammonium polyphosphate alone. Examples of commercially available products include Clariant Exolit-422, Exolit-700, Monsanto Foschek-P / 30, Foschek-P / 40, Sumitomo Chemical. Examples include SUMI SAFE-P manufactured by Co., Ltd., TERRAGE-S10 and TELLAGE-S20 manufactured by Chisso Corporation.

Examples of the compound mainly composed of ammonium polyphosphate include those obtained by coating or microencapsulating ammonium polyphosphate with a thermosetting resin, or those obtained by coating the surface of ammonium polyphosphate with a melamine monomer or other nitrogen-containing organic compound. , Surfactants and silicon-treated ones, and melamine or the like added in the process of producing ammonium polyphosphate to make them insoluble.
Commercially available compounds having ammonium polyphosphate as a main component include Exolite-462 manufactured by Clariant Co., Sumisafe-PM manufactured by Sumitomo Chemical Co., Ltd., Terrage-C60 manufactured by Chisso Co., Ltd., and Terrage-C70. , Terrage-C80 and the like.
The component (A) may be a single type or a mixture of two or more types.

The (poly) phosphate compound represented by the general formula (3) used as the component (B) in the flame retardant composition of the present invention is composed of (poly) phosphoric acid and a diamine represented by Y ¹ ([R ¹ R ² N (CH ₂ ) mNR ³ R ⁴ ] and a salt with a piperazine or a diamine containing a piperazine ring. Examples of the linear or branched alkyl group having 1 to 5 carbon atoms represented by R ^{1 to} R ⁴ include those described above as specific examples of the alkyl group represented by Z ¹ and Z ² . The thing of 1-5 carbon atoms is mentioned.

Specific examples of the diamine represented by Y ¹ in the general formula (3) include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, and N, N. '-Diethylethylenediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N, N ', N'-diethylethylenediamine, tetramethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10- Diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1,4 -Bis (2-aminoethyl) piperazine, 1,4-bis (3-aminopropyl) piperazine and the like can be mentioned, and all commercially available products can be used.

Examples of the (poly) phosphate compound represented by the general formula (3) preferably used as the component (B) include a salt of phosphoric acid and piperazine. Specific examples of the salt of phosphoric acid and piperazine include piperazine orthophosphate, piperazine pyrophosphate, and piperazine polyphosphate. Among these, piperazine polyphosphate, in which q in the general formula (3) is 1 and Y ¹ is piperazine, particularly piperazine pyrophosphate is preferable.
The salt of phosphoric acid and piperazine can be obtained by the following method. For example, in the case of piperazine pyrophosphate, piperazine and pyrophosphoric acid are reacted in water or an aqueous methanol solution to easily obtain a poorly water-soluble precipitate. However, in the case of piperazine polyphosphate, a salt obtained from polyphosphoric acid and piperazine made of a mixture of orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid and other polyphosphoric acids may be used, and the constitution of the raw material polyphosphoric acid is not particularly limited.
The component (B) may be a single type or a mixture of two or more types.

  Content of (A) component and (B) component in the flame retardant composition of this invention makes the sum total of (A) component and (B) component 100 mass parts, and (A) component is 20-50 mass parts. , (B) component is 50-80 mass parts.

As the acrylic processing aid used as the component (C) in the flame retardant composition of the present invention, one obtained by polymerizing one kind of (meth) acrylic acid ester or copolymerizing two or more kinds can be used. Examples of the (meth) acrylic acid ester to be polymerized or copolymerized include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, isobutyl Examples include (meth) acrylic acid esters such as acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, and tridecyl methacrylate. In addition to the above, (meth) acrylic acid and (meth) acrylic acid ester containing a hydroxy group are also included.
Examples of commercially available acrylic processing aids include, for example, Metablene P-531A, Metabrene P-530A, Metabrene P-540A, Metabrene P-551A, Metabrene P-570A, and Metabrene P-700 manufactured by Mitsubishi Rayon Co., Ltd. , Metabrene P-710, Metabrene P-1030, Metabrene P-1050, Metabrene L-1000, Kaneace PA-20, Kaneace PA-60, Kaneace PA-100 manufactured by Kaneka Corporation.
Component (C) may be a single type or a mixture of two or more types.

  Content of (C) component in the flame retardant composition of this invention is 0.1-15 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, From the viewpoint of fluidity and workability of the synthetic resin, the amount is preferably 0.25 to 12.5 parts by mass, more preferably 2.5 to 7.5 parts by mass.

The flame retardant composition of the present invention preferably further contains zinc oxide, which is a flame retardant aid, as 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 Co., Ltd.), partially coated zinc oxide (manufactured by Mitsui Kinzoku Kogyo 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. .
In the flame retardant composition of the present invention, the content of zinc oxide as the component (D) is usually 0.01 to 10 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). It is 0.5-10 mass parts, More preferably, it is 1.2-5 mass parts.

Moreover, it is preferable that the flame retardant composition of this invention contains an anti-drip agent as (E) component further. Examples of the anti-drip agent include a fluorine-based anti-drip agent, silicone rubbers, layered silicates, and the like.
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 anti-drip agent of component (E) is particularly preferably a fluorine-based anti-drip agent, and specific examples of the fluorine-based anti-drip agent include fluorine-based compounds such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene. Resin and sodium perfluoromethanesulfonate, potassium perfluoro-n-butanesulfonate, potassium perfluoro-t-butanesulfonate, sodium perfluorooctanesulfonate, calcium perfluoro-2-ethylhexanesulfonate Examples thereof include alkali metal salt of perfluoroalkanesulfonic acid such as salt or alkaline earth metal salt of perfluoroalkanesulfonic acid. Among the anti-drip agents, polytetrafluoroethylene is most preferable from the viewpoint of anti-drip properties.
The content of the anti-drip agent of the component (E) in the flame retardant composition of the present invention is usually 0.005 to 5 parts by mass, preferably 100 parts by mass of the total of the components (A) and (B). Is 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 1 part by mass. If the content of the anti-drip agent of component (E) is less than 0.005 parts by mass, the anti-drip effect is not sufficient, and if it exceeds 5 parts by mass, the resin properties may be deteriorated.

  Silicone oil may be blended with the flame retardant composition of the present invention in order to suppress secondary aggregation during blending and to improve water resistance. 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 etc. in which is hydrogen, and copolymers thereof, and amine-modified, epoxy-modified, alicyclic epoxy-modified, in which an organic group is introduced into a part of these side chains and / or terminals, 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 oils 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- 6 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as epoxy-modified products, for example, X-22-343 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-2000 (manufactured by Shin-Etsu Chemical Co., Ltd.), Examples of 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 carboxyl-modified products include, for example, X-22-3701E ( For example, X-22-4039 (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.), and amine-modified products Examples thereof include KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Moreover, you may mix | blend a silane coupling agent with the flame retardant composition of this invention. The silane coupling agent is a compound having a hydrolyzable group with an organic functional group, for example, represented by the general formula _{A- (CH 2) k -Si (} OR) 3. A is an organic functional group, k represents a number of 1 to 3, and R represents a methyl group or an ethyl group. Examples of the organic group of A include an epoxy group, a vinyl group, a methacryl group, an amino group, and a mercapto group. As a silane coupling agent used by this invention, what has an epoxy group is especially preferable.

  Moreover, you may mix | blend a polyhydric alcohol compound with the flame retardant composition of this invention as a flame retardant adjuvant. The polyhydric alcohol compound is a compound in which a plurality of hydroxyl groups are bonded. For example, pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, 1, 3,5-tris (2-hydroxyethyl) isocyanurate (THEIC), polyethylene glycol, glycerin, diglycerin, mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, xylose, sucrose (sucrose), trehalose, inositol, Fructose, maltose, lactose, etc. Among these polyhydric alcohol compounds, one or more selected from the group of pentaerythritol and pentaerythritol condensates such as pentaerythritol, dipentaerythritol, tripentaerythritol, and polypentaerythritol are preferred, and dipentaerythritol, pentaerythritol Condensates are particularly preferred and dipentaerythritol is most preferred. Moreover, THEIC and sorbitol can also be used conveniently.

  The condensate of pentaerythritol may be a mixture of a condensate of pentaerythritol and pentaerythritol (in the present invention, this is called a (poly) pentaerythritol mixture), and this (poly) pentaerythritol mixture has a degree of condensation of pentaerythritol of n. The total content of n = 1-3 pentaerythritol and its condensate is 5-40% by mass with respect to the total amount of the (poly) pentaerythritol mixture (provided that , N = 1-3 pentaerythritol and its condensate and n ≧ 4 pentaerythritol condensate are 100% by mass).

  From the viewpoint of flame retardancy, the (poly) pentaerythritol mixture includes the total of pentaerythritol of n = 1 to 3 and the condensate thereof with respect to the total amount of the mixture when the degree of condensation of pentaerythritol is represented by n. The amount is preferably 10 to 30% by mass, the content of pentaerythritol with n = 1 is 0 to 10% by mass, and the total content of pentaerythritol with n = 1 to 3 and its condensate is More preferably, the content is 5-30% by mass, the content of pentaerythritol with n = 1 is 0-5% by mass, and the total content of pentaerythritol with n = 1-3 and its condensate is 10%. Most preferred is -30% by weight.

  As said pentaerythritol and its condensate, the compound shown by following General formula (4) is mentioned.

（式中、ｔは１以上の整数である。）

(In the formula, t is an integer of 1 or more.)

  Examples of the (poly) pentaerythritol mixture include those in which the condensate of pentaerythritol represented by the general formula (4) is ether-bonded in the molecule, intermediate methylol groups are ether-bonded to other molecules, and network-like Those that are connected to each other, and molecules that are further connected and become macrocyclic ether structures in various places may be included.

  The (poly) pentaerythritol mixture is not particularly limited and can be produced by a known method. For example, pentaerythritol and / or pentaerythritol condensate can be produced by heat dehydration condensation reaction as it is or in the presence of a suitable catalyst and solvent.

Examples of the catalyst used for the production of the (poly) pentaerythritol mixture include inorganic acids and organic acids that are usually used in the dehydration condensation reaction of alcohols. Examples of inorganic acids include mineral acids such as phosphoric acid and sulfuric acid; acidic salts of these mineral acids; solid acid catalysts such as clay minerals (for example, montmorillonite), silica / alumina, and zeolite. Examples of the organic acid include formic acid and p-toluenesulfonic acid.
The amount of the catalyst used is not particularly limited, but when a water-soluble acid catalyst is used, it may be an amount that can maintain the pH in the reaction system during the reaction below 7, preferably 5 or less. Moreover, when using a solid acid catalyst, the usage-amount of 0.1-100 mass% may be sufficient with respect to a pentaerythritol normally.

  Examples of the solvent used for the production of the (poly) pentaerythritol mixture include hydrocarbons such as benzene, xylene, decalin, tetralin, dioxane, tetrahydrofuran, ethyl ether, anisole, phenyl ether, diglyme, tetraglyme, 18- Ethers such as crown-6, ketones such as methyl acetate, ethyl butyrate, methyl benzoate and γ-butyrolactone, N-methylpyrrolidin-one, N, N-dimethylacetamide, N-methylpiperidone, hexamethylphosphoric triamide N-substituted amides such as N, N-diethylaniline, N-methylmorpholine, tertiary amines such as pyridine and quinoline, sulfones such as sulfolane, sulfoxides such as dimethyl sulfoxide, 1,3-dimethyl -2-Imidazolid Urea derivatives such as down, phosphine oxides such as tributylphosphine oxide, and silicone oil and the like, also may be a water-containing product which was dehydrated.

  The reaction temperature of the heat dehydration condensation in the production of the (poly) pentaerythritol mixture is usually about 100 to 280 ° C., more preferably 150 to 240 ° C. If the reaction temperature is lower than 100 ° C, the reaction may be slow, and if it is higher than 280 ° C, it may be difficult to control the condensation reaction.

  The content of the polyhydric alcohol compound in the flame retardant composition of the present invention is preferably 0.5 to 15 parts by mass, more preferably 100 parts by mass in total of the component (A) and the component (B). Is 2 to 12 parts by mass, more preferably 5 to 10 parts by mass.

Furthermore, it is also preferable to mix | blend a lubricant with the flame retardant 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. Two or more lubricants may be used.
The content of the lubricant in the flame retardant composition of the present invention is preferably 0.05 to 10 parts by mass, more preferably 0. 0 to 10 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). 1-5 mass.

  In the flame retardant composition of the present invention, one or more organic or inorganic flame retardants or flame retardant aids that do not contain halogen are further used as necessary within the range not impairing the effects of the present invention. 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 melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, butylene diguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene dimelamine, tetra Examples include methylene dimelamine, 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 - (isopropyl phenyl) 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 dialkylphosphinic acid salts 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, 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 composition used in the present invention contains, as necessary, a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, etc. You may mix | blend. These components may be blended in advance with the flame retardant composition of the present invention, or may be blended with the synthetic resin when the flame retardant composition of the present invention is blended with the synthetic resin. It is preferable to stabilize the synthetic resin by blending these.

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.
The amount of these phenolic antioxidants used is preferably 0.001 to 5% by mass, and 0.05 to 3% by mass in the synthetic resin composition when blended in the synthetic resin. More preferred.

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, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol 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) butane triphosphite, tetrakis (2,4-ditert-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′-ethylidenebis (4,6- Tert-butylphenyl) fluorophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) Oxy] ethyl) amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, and the like.
The amount of these phosphorus-based antioxidants used is preferably 0.001 to 5% by mass, and 0.05 to 3% by mass in the synthetic resin composition when blended in the synthetic resin. More preferred.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylmercaptopropionate). Kind.
The amount of these thioether-based antioxidants used is preferably 0.001 to 5% by mass, and 0.05 to 3% by mass in the synthetic resin composition when blended in the synthetic resin. More preferred.

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 methyl-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.
The amount of these ultraviolet absorbers used is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass in the synthetic resin composition when blended in the synthetic resin. .

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.
The amount of these hindered amine light stabilizers used in the synthetic resin is preferably 0.001 to 5% by mass, and 0.05 to 3% by mass when blended in the synthetic resin. More preferred.

Examples of the antiaging agent include naphthylamine, diphenylamine, p-phenyldiamine, quinoline, hydroquinone derivatives, monophenols, thiobisphenols, hindered phenols, and phosphites.
The amount of these anti-aging agents used is preferably 0.001 to 5% by mass, more preferably 0.05 to 3% by mass in the synthetic resin composition when blended in the synthetic resin. .

  You may mix | blend a reinforcing material with the flame retardant composition of this invention as an arbitrary component in the range which does not impair the effect of this invention. These components may be added to the synthetic resin when the flame retardant composition of the present invention is added to the synthetic resin. 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 include plate-like and granular reinforcing materials such as aluminum silicate, silicon oxide, gypsum, nobaclite, 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.

  The flame retardant 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. These components may be added to the synthetic resin when the flame retardant composition of the present invention is added to the synthetic resin.

  Specific examples of the inorganic crystal nucleating agent include kaolinite, synthetic mica, clay, zeolite, silica, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, aluminum oxide, Mention may be made of metal salts such as neodymium oxide and 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 the organic crystal nucleating agent include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, and oxalic acid. Calcium, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearin Barium acid, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate Organic carboxylic acid metal salts such as aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, stearamide , 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.

You may mix | blend a plasticizer as an arbitrary component with the flame retardant composition of this invention in the range which does not impair the effect of this invention. 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.
These components may be added to the synthetic resin when the flame retardant composition of the present invention is added to the synthetic resin.

  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.

In addition, in the flame retardant composition of the present invention, additives that are usually used in synthetic resins as necessary, for example, crosslinking agents, antistatic agents, metal soaps, spotting agents, antifogging agents, and plate-out preventing agents. Surface treatment agents, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, pigments, processing aids other than acrylic processing aids, etc., within the range that does not impair the effects of the present invention And can be blended.
These components may be added to the synthetic resin when the flame retardant composition of the present invention is added to the synthetic resin.

  The flame retardant composition of the present invention is effective in making a synthetic resin flame retardant, and is preferably used as a flame retardant synthetic resin composition by blending with a synthetic resin.

Specific examples of the synthetic resin flame-retarded by the flame retardant composition of the present invention include polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, Α-olefin polymer such as poly-3-methylpentene or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, polyolefin such as ethylene-propylene copolymer, and copolymers thereof, polyvinyl chloride, Polyvinylidene chloride, chlorinated 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 terpolymer, vinyl chloride Halogenated resins such as lauric acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, polymethyl methacrylate, Polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and polytetramethylene Linear polyester such as terephthalate; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene Degradable aliphatic polyesters such as succinate, polylactic acid resin, polymalic acid, polyglycolic acid, polydioxane, poly (2-oxetanone); polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, branched polycarbonate , Thermoplastic resins such as polyacetal, polyphenylene sulfide, polyurethane, and fiber-based resins, and blends thereof, or thermosetting resins such as phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, fluorine resins, Examples include silicone resin, silicone rubber polyethersulfone, polysulfone, polyphenylene ether, polyetherketone, polyetheretherketone, and liquid crystal polymer. Further examples include isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, and silicone rubber.
Specific examples of the flame retardant synthetic resin include olefin thermoplastic elastomer, styrene thermoplastic elastomer, polyester thermoplastic elastomer, nitrile thermoplastic elastomer, nylon thermoplastic elastomer, vinyl chloride thermoplastic elastomer. , Polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like.
These synthetic resins may be used alone or in combination of two or more. The synthetic resin may be alloyed.

The synthetic resin used in the present invention includes molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of monomers as raw materials, polymerization catalyst Regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.), etc. can be used.
Among these synthetic resins, polyolefin resins and / or styrene thermoplastic elastomers are preferable from the viewpoint of flame retardancy, resin fluidity, and processability.

  Examples of polyolefin resins include, for example, polyethylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, homopolypropylene, random copolymer polypropylene, block copolymer polypropylene, impact copolymer polypropylene, high impact copolymer polypropylene, Isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, maleic anhydride modified polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1- Α-olefin polymer such as pentene, poly-4-methyl-1-pentene, ethylene / propylene block or lander Copolymer, ethylene - methyl methacrylate copolymer, ethylene - alpha-olefin copolymer such as vinyl acetate copolymer.

  Examples of styrenic thermoplastic elastomers include copolymers of styrene and / or α-methylstyrene and other monomers (eg, 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, acrylonitrile-acrylate-styrene (AAS) resin, styrene-anhydrous malee Acid (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene SIS resin, acrylonitrile-ethylenepropylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene ( BBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin and the like, and further, styrene-ethylene-butylene-styrene (SEBS) resin obtained by hydrogenating double bonds of these butadiene or isoprene, styrene- Examples thereof include hydrogenated styrene thermoplastic elastomer resins such as ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, and styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin. Among styrene thermoplastic elastomers, hydrogenated styrene thermoplastic elastomers are preferable.

  In the flame-retardant synthetic resin composition of the present invention, the total content of the component (A), the component (B), and the component (C) is 10% by mass from the viewpoint of flame retardancy, resin fluidity, and workability. The content is preferably less than 60% by mass, more preferably 20% by mass or more and less than 50% by mass, and even more preferably 25% by mass or more and less than 45% by mass. When the amount is less than 10% by mass of the component (A), the component (B) and the component (C), sufficient flame retardancy may not be exhibited. When the amount is 60% by mass or more, the original physical properties of the resin may be impaired.

By molding the flame retardant synthetic resin composition of the present invention, a molded product having excellent flame retardancy can be obtained. The molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, and the like, and molded products having various shapes such as resin plates, sheets, films, and irregular shaped products. Can be manufactured.
The resin composition can be used for housings (frames, housings, covers, exteriors) and parts of automobiles, machines, electrical / electronic equipment, office automation equipment, etc., automotive interior / exterior materials, etc., and requires UL94 5VA standards. Used for applications.

The flame-retardant synthetic resin composition of the present invention and the molded product thereof are electrical / electronic / communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, It can be used in a wide range of industrial fields such as wood, 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.
Furthermore, the flame-retardant synthetic resin composition and molded product thereof according to the present invention include a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil. Cover, mattress cover, airbag, 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, exterior Materials, interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, eaves materials, frames and repetitive shapes, window and door shapes, slabs, plaids, terraces, balconies, soundproofing plates, heat insulating plates, Automobiles, hybrid cars, electric cars, vehicles, ships, aircraft, buildings, housing and building materials such as window materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fibers, carpets, doormats, Over door, 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 described in detail by way of examples. However, the present invention is not limited by the following examples. In addition, all the mixing | blending of Table 1 and 2 is a mass part reference | standard.
[Examples 1-7 and Comparative Examples 1-6]
(A) component and (B) component were manufactured with the following method.
[Production Example 1]
(A) Component: Melamine pyrophosphate Pyrophosphate and melamine were produced by reacting at a molar ratio of 1: 2.
[Production Example 2]
(B) Component: Piperazine pyrophosphate Pyrophosphate and piperazine were produced by reacting at a molar ratio of 1: 1.

  Examples of the flame retardant composition of the present invention were prepared with the formulations shown in Table 1. Similarly, a comparative example of the flame retardant composition was prepared with the formulation shown in Table 2.

[Examples 8 to 14, Comparative Examples 7 to 12]
35 parts by mass of polypropylene (melt flow rate = 5 g / 10 min) and 35 parts by mass of styrene-ethylene-butylene-styrene (SEBS) resin (manufactured by Asahi Kasei Co., Ltd .: product name Tuftec H1062) are mixed with calcium stearate (lubricant) 0.1. Parts by mass, methyl tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane (phenolic antioxidant) 0.1 parts by mass, tris (2,4-di-tertiary) Example 1 for a polypropylene / SEBS resin composition obtained by blending 0.1 part by weight of (butylphenyl) phosphite (phosphorus antioxidant) and 0.3 part by weight of glycerin monostearate (lubricant) The flame retardant composition obtained in ˜7 is blended so that the ratio in the flame retardant synthetic resin composition is the ratio (mass%) described in Table 3, To obtain a flame-retardant synthetic resin composition 施例 8-14. Incidentally, in the flame retardant composition, the flame retardant composition obtained in Example 1 is designated as flame retardant composition-1, and the flame retardant composition obtained in Example 2 is designated as flame retardant composition-2. Up to the flame retardant composition-7 was used.

  Moreover, the flame retardant composition obtained in Comparative Example 1 is referred to as Comparative Flame retardant Composition-1, the flame retardant composition obtained in Comparative Example 2 is referred to as Comparative Flame retardant Composition-2, and the following comparative flame retardant composition. -6, and these comparative flame retardant compositions were blended with the above polypropylene / SEBS resin composition so that the proportion in the flame retardant synthetic resin composition would be the proportion (mass%) shown in Table 3. The flame retardant synthetic resin compositions of Comparative Examples 7 to 12 were obtained.

The flame retardant synthetic resin compositions obtained in Examples 8 to 14 were extruded at 210 to 230 ° C. to produce strands and pellets having a diameter of 2.0 mm, and the obtained strands were subjected to the following strand combustion test method. A combustion test was performed. The results are shown in Table 3.
Moreover, it extruded at 210 degreeC using the obtained pellet, and manufactured the electric wire of diameter 2.0mm. Using this electric wire, a VW-1 combustion test was performed as a flame retardancy test by the following VW-1 combustion test method. The results are shown in Table 3.
Moreover, the spiral flow test was done with the following spiral flow test method using the obtained pellet. The results are shown in Table 3.
For the flame retardant synthetic resin compositions obtained in Comparative Examples 7 to 12, a combustion test, a combustion test, and a spiral flow test were performed in the same manner as in Examples 8 to 14. The results are shown in Table 3.

<Strand combustion test method>
A test piece having a length of 20 cm and a diameter of 2.0 mm was kept vertical, the flame of the burner was removed after indirect flame was burned at the lower end for 5 seconds, and the time when the fire that 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 was extinguished was measured as in the first time. The same combustion method as described above is carried out 5 times in total, and the flame retardancy is 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-94V standard.)
The case where it did not burn out even at the 5th time was accepted, and otherwise, the number of times when it was burned out was evaluated.

<VW-1 combustion test method>
The vertical flame retardance of the cable was measured according to the applicable standard UL1581 (UL VW-1). Hold the sample vertically, flame with a gas burner at a 20 degree angle for 15 seconds, then extinguish the flame for 15 seconds and repeat 5 times in total to check the degree of burning of the sample. Acceptance criteria are all three points: combustion after the flame does not exceed 60 seconds; upper paper flag does not burn more than 25%; absorbent cotton laid on the bottom does not burn due to fallen combustibles. The case where it cleared was made into the pass.

<Spiral Flow Test>
Using a spiral flow mold (width 10 mm x thickness 0.1 mm) with an injection molding machine (HYPERLINK "http://www.nisseijushi.co.jp/" manufactured by Nissei Plastic Industry Co., Ltd.), melting temperature 200 ° C The pellets obtained above were injected under the conditions of an injection pressure of 100 Ma, and the spiral flow length (mm) was measured.
The longer the spiral flow length, the better the fluidity.

Claims (9)

20-50 parts by mass of the following (A) component, 50-80 parts by mass of the following (B) component (however, the total of the (A) component and the (B) component is 100 parts by mass), and the following (C) component is 0 A flame retardant composition containing 1 to 15 parts by mass.
(A) component: (poly) phosphate compound (B) represented by the following general formula (1) component: (poly) phosphate compound (C) component represented by the following general formula (3): acrylic Processing aids

(In the formula, n represents a number of 1 to 100, X ¹ is ammonia or a triazine derivative represented by the following general formula (2), and 0 <p ≦ n + 2.)

(In the formula, Z ¹ and Z ² may be the same or different, and —NR ⁵ R ⁶ group [wherein R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a straight chain of 1 to 6 carbon atoms or Represents a branched alkyl group or a methylol group], a hydroxyl group, a mercapto group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, a phenyl group, and vinyl. It is a group selected from the group consisting of groups.)

(Wherein r represents 1 to 100, Y ¹ is [R ¹ R ² N (CH ₂ ) mNR ³ R ⁴ ], a piperazine or a diamine containing a piperazine ring, R ¹ , R ² , R ³ and R ⁴ is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ may be the same group or different groups. M is an integer of 1 to 10, and 0 <q ≦ r + 2.   Furthermore, the flame retardant composition described in Claim 1 which contains 0.01-10 mass parts of zinc oxide as (D) component.   The flame retardant composition according to claim 1 or 2, further comprising 0.005 to 5 parts by mass of an anti-drip agent as component (E). As the component (A), melamine pyrophosphate in which n in the general formula (1) is 2, p is 2, and X ¹ is melamine (Z ¹ and Z ² in the general formula (2) are —NH ₂ ) is used. The flame retardant composition according to any one of claims 1 to 3, which is used. The flame retardant composition according to any one of claims 1 to 4, wherein a piperazine polyphosphate whose q in the general formula (3) is 1 and Y ¹ is piperazine is used as the component (B).   The flame retardant composition according to claim 5, wherein the piperazine polyphosphate is piperazine pyrophosphate.   The flame-retardant synthetic resin composition which mix | blended the flame retardant composition as described in any one of Claims 1-6 with the synthetic resin.   The flame retardant synthetic resin composition according to claim 7, wherein the synthetic resin is a polyolefin resin and a styrene thermoplastic elastomer.   The molded object obtained from the flame-retardant synthetic resin composition described in Claim 7 or 8.