WO2022215660A1 - Mechanical property-imparting agent composition, resin composition and molded article - Google Patents

Mechanical property-imparting agent composition, resin composition and molded article Download PDF

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Publication number
WO2022215660A1
WO2022215660A1 PCT/JP2022/016821 JP2022016821W WO2022215660A1 WO 2022215660 A1 WO2022215660 A1 WO 2022215660A1 JP 2022016821 W JP2022016821 W JP 2022016821W WO 2022215660 A1 WO2022215660 A1 WO 2022215660A1
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WIPO (PCT)
Prior art keywords
component
mass
parts
melamine
piperazine
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PCT/JP2022/016821
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French (fr)
Japanese (ja)
Inventor
陽平 稲垣
彩香 三觜
豊 米澤
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株式会社Adeka
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Publication of WO2022215660A1 publication Critical patent/WO2022215660A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/10—Organic materials containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus

Definitions

  • the present invention relates to a mechanical property-imparting agent composition containing an amine phosphate salt and melamine cyanurate, and a resin composition containing the mechanical property-imparting agent composition.
  • intumescent flame retardants which are mainly composed of salts of polyphosphoric acid or pyrophosphoric acid and nitrogen-containing compounds, form an intumescent layer on the surface during combustion, suppressing the diffusion of decomposition products and heat transfer. It is known that flame retardancy is exhibited by As an example of this type of flame retardant, Patent Document 1 proposes a flame retardant containing a specific melamine salt, a specific piperazine salt and melamine cyanurate, which has a high anti-drip effect, It is disclosed to be excellent in flame retardancy.
  • An object of the present invention is to provide a mechanical property-imparting agent composition that imparts excellent flame retardancy and excellent mechanical properties to a resin, and to provide a resin composition containing the mechanical property-imparting agent composition. That's what it is.
  • the present inventors have made intensive studies on a configuration for solving the above problems, and found that by mixing a resin with a mechanical property-imparting agent composition in which an amine phosphate and melamine cyanurate are combined in a specific ratio, the resin The present inventors have completed the present invention by finding that excellent flame retardancy and mechanical properties are imparted to.
  • the present invention is based on the above findings, and includes the following components (A-1) and (A-2): component (A): amine phosphate salt and component (B): melamine cyanurate.
  • the object is to provide a mechanical property-imparting agent composition containing in a specific ratio.
  • A-1) Component: A melamine salt containing at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • A-2) Component Component: a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
  • the present invention also provides a resin composition containing a resin and the mechanical property-imparting agent composition, and a molded article thereof.
  • the present invention also provides a method for imparting mechanical properties to a resin, comprising mixing a resin with a composition containing the (A) component and the (B) component in a specific ratio.
  • the present invention provides use of a mechanical property-imparting agent composition containing the component (A) and the component (B) in a specific ratio as a mechanical property-imparting agent.
  • mechanical properties mean mechanical properties such as impact resistance, rigidity, tensile properties, and in particular, tensile elongation and tensile strength measured in tensile property evaluation in accordance with ISO 527. do.
  • the term "mechanical property imparting agent” means an additive that has the effect of improving the aforementioned mechanical properties when blended with a resin.
  • a mechanical property-imparting agent composition means a composition containing one or more mechanical property-imparting agents.
  • flame retardancy means that a substance is difficult to ignite, and even if it ignites and continues to burn, the speed is very slow, and then it self-extinguishes.
  • the mechanical property-imparting agent composition of the present invention is characterized in that it contains component (A): amine phosphate and component (B): melamine cyanurate in a specific ratio.
  • amine phosphate salt which is the component (A) contained in the mechanical property-imparting agent composition of the present invention.
  • Phosphate amine salts are salts of phosphoric acid and amines.
  • phosphoric acid means an acid formed by hydrating diphosphorus pentoxide, and specifically includes orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid. Each of these phosphoric acids can be used alone, or two or more of them can be used in combination.
  • the amine phosphate salt used as component (A) in the mechanical property-imparting agent composition of the present invention is component (A-1): at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • component (A-1) at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • the melamine salt used as the (A-1) component in the mechanical property-imparting agent composition of the present invention contains at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
  • melamine pyrophosphate is preferably contained from the viewpoint of flame retardancy, handleability and storage stability.
  • the melamine salt is a mixture, it is preferable that the content of melamine pyrophosphate in the mixture is the highest on a mass basis.
  • the content of melamine pyrophosphate in the melamine salt is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
  • These salts of phosphoric acid and melamine can be obtained by reacting the corresponding phosphoric acid or phosphate with melamine or melamine hydrochloride.
  • the phosphate include monobasic sodium phosphate, monobasic potassium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tribasic potassium phosphate, sodium pyrophosphate, pyroline potassium phosphate, sodium polyphosphate, potassium polyphosphate and the like.
  • melamine pyrophosphate and melamine polyphosphate may be obtained by thermally condensing melamine orthophosphate.
  • the melamine salt used in the component (A-1) of the present invention is preferably a melamine salt containing melamine pyrophosphate or melamine polyphosphate as a main component, obtained by thermally condensing melamine orthophosphate.
  • a melamine salt containing melamine pyrophosphate as a main component obtained by thermally condensing acid melamine is preferred.
  • the piperazine salt used as component (A-2) in the mechanical property-imparting agent composition of the present invention contains at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
  • the content of piperazine pyrophosphate in the melamine salt is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
  • These salts of phosphoric acid and piperazine can be obtained by reacting the corresponding phosphoric acid or phosphate with piperazine or piperazine hydrochloride.
  • phosphate those described above can be used.
  • Piperazine pyrophosphate and piperazine polyphosphate may also be obtained by thermally condensing piperazine orthophosphate.
  • the piperazine salt used in the component (A-2) of the present invention is preferably a piperazine salt containing piperazine pyrophosphate or piperazine polyphosphate as a main component obtained by thermally condensing piperazine orthophosphate, particularly orthophosphoric acid.
  • a piperazine salt containing piperazine pyrophosphate as a main component obtained by thermally condensing piperazine is preferred.
  • the (A) component contained in the mechanical property-imparting agent composition of the present invention preferably consists only of the (A-1) component and the (A-2) component.
  • the content of component (A-1) in component (A) is preferably 10 to 50 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of component (A).
  • the content of component (A-2) in component (A) is preferably 90 to 50 parts by mass, more preferably 80 to 50 parts by mass, per 100 parts by mass of component (A).
  • the total amount of component (A) in the mechanical property-imparting agent composition of the present invention is preferably 60 to 90% by mass, more preferably 60 to 83% by mass. It is preferable that the content of component (A) is 60% by mass or more in terms of improving flame retardancy, and that it is 90% by mass or less ensures the amount of component (B) to be blended, and the effect of the present invention is obtained. is preferable in terms of increasing
  • the content of the amine phosphate salt as the component (A) typified by the melamine salt as the component (A-1) and the piperazine salt as the component (A-2) is , can be determined by ion chromatography.
  • Melamine cyanurate which is the component (B) in the agent composition for imparting mechanical properties of the present invention, is an organic salt of melamine and cyanuric acid.
  • a commercially available product can be used as the melamine cyanurate.
  • Examples of commercial products of melamine cyanurate include MC-4000, MC-4500 and MC-6000 manufactured by Nissan Chemical Industries, Ltd.
  • the content of the component (B) is 10 parts by mass or more with respect to 100 parts by mass of the total content of the components (A-1) and (A-2). 40 parts by mass or less, preferably over 20 parts by mass and 40 parts by mass or less, more preferably over 20 parts by mass and 38 parts by mass or less, particularly preferably over 20 parts by mass and 30 parts by mass or less .
  • setting the content of the component (B) to 10 parts by mass or more there is an advantage of improving the mechanical properties when blended with the resin.
  • setting the content of component (B) to 40 parts by mass or less is advantageous in terms of flame retardancy.
  • the content of the component (B) can be measured, for example, by infrared spectroscopy, gas chromatography, gas chromatography-mass spectrometry, or the like.
  • the mechanical property-imparting agent composition of the present invention can further contain zinc oxide (ZnO) (hereinafter, this component is also referred to as "(C) component").
  • ZnO zinc oxide
  • the zinc oxide functions as a flame retardant aid.
  • the zinc oxide may be surface-treated.
  • Commercially available zinc oxide can be used. 0.02 ⁇ m ultrafine zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd.), Nanofine K (superfine zinc oxide coated with zinc silicate with an average particle size of 0.02 ⁇ m: manufactured by Sakai Chemical Industry Co., Ltd.), and the like. .
  • the content of zinc oxide as the component (C) is 0.01 to 10 mass parts per 100 parts by mass of the component (A) from the viewpoint of flame retardancy. parts, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 7 parts by mass.
  • the content of zinc oxide is 0.01 part by mass or more, the flame retardancy becomes better.
  • the content of zinc oxide is less likely to be adversely affected.
  • the mechanical property-imparting agent composition of the present invention prevents the mechanical property-imparting agent powder from agglomerating, improves storage stability, and improves dispersibility in synthetic resins. It preferably contains at least one selected from coupling agents, hydrotalcite and lubricants (hereinafter, this component is also referred to as “component (D)").
  • silicone oils include dimethylsilicone oil in which the side chains and terminals of polysiloxane are all methyl groups, and methylphenyl, in which the side chains and terminals of polysiloxane are methyl groups and part of the side chains are phenyl groups.
  • examples thereof include silicone oil, methylhydrogensilicone oil in which the side chains and terminals of polysiloxane are methyl groups and part of the side chains are hydrogen, and copolymers thereof.
  • silicone oil examples include KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-965 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.) as dimethyl silicone oil.
  • methyl hydrogen silicone oils examples include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), HMS-151 (manufactured by Gelest), HMS-071 (manufactured by Gelest ), HMS-301 (manufactured by Gelest), DMS-H21 (manufactured by Gelest), etc.
  • methylphenyl silicone oils examples include KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-54 (Shin-Etsu Chemical Co., Ltd.), KF-56 (Shin-Etsu Chemical Co., Ltd.), etc.
  • Examples of epoxy-modified products include X-22-343 ( Shin-Etsu Chemical Co., Ltd.), X-22-2000 (Shin-Etsu Chemical Co., Ltd.), KF-101 (Shin-Etsu Chemical Co., Ltd.), KF-102 (Shin-Etsu Chemical Co., Ltd.), KF-1001 ( Shin-Etsu Chemical Co., Ltd.), carboxyl-modified products such as X-22-3701E (Shin-Etsu Chemical Co., Ltd.), carbinol-modified products such as X-22-4039 (Shin-Etsu Chemical Co., Ltd.) (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.), and amine-modified products include, for example, KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • the mechanical property-imparting agent powder is prevented from agglomerating, the storage stability is improved, and the dispersibility in the synthetic resin is improved.
  • Jen silicone oil is preferred.
  • Epoxy coupling agents include, for example, compounds represented by the general formula A—(CH 2 ) k —Si(OR) 3 and having an epoxy group.
  • A is a group having an epoxy ring
  • k represents a number from 1 to 3
  • R represents a methyl group or an ethyl group.
  • the group having an epoxy ring as used herein includes a glycidoxy group and a 3,4-epoxycyclohexyl group.
  • epoxy coupling agents include silane coupling agents having an epoxy group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane and the like.
  • silane coupling agents having an epoxy group such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane and the
  • Hydrotalcite is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and optional water of crystallization, which are known as natural or synthetic products. Substituted ones and those in which hydroxyl groups and carbonate groups are substituted with other anionic groups can be mentioned. Specifically, for example, hydrotalcite represented by the following formula (3) and hydrotalcite represented by the following formula (3) in which the metal is replaced with an alkali metal can be mentioned. A compound represented by the formula (4) can also be used as the Al—Li-based hydrotalcite.
  • x1 and x2 represent numbers satisfying 0 ⁇ x2/x1 ⁇ 10 and 2 ⁇ x1+x2 ⁇ 20, respectively, and p represents 0 or a positive number.
  • a q- represents a q-valent anion
  • p represents 0 or a positive number.
  • carbonate anions in the hydrotalcite may be partly replaced with other anions.
  • the hydrotalcite may be obtained by dehydrating the water of crystallization, and includes higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with salt, higher fatty acid amide, higher fatty acid ester, wax, or the like.
  • Lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, 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 lubricants such as bis fatty acid amides; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, ester lubricants such as fatty alcohol esters of fatty acids (ester wax); metal soaps , fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester lubricant of polyglycerol, silicone oil, mineral oil, and the like. Lubricants may be used individually by 1 type, and may use 2 or more types together.
  • the mechanical property imparting agent composition of the present invention contains at least one selected from silicone oil, epoxy coupling agent, hydrotalcite and lubricant (component (D)) from the viewpoint of improving flame retardancy.
  • component (D) is, from the viewpoint of effectively exhibiting the effect of containing component (D), relative to 100 parts by mass of component (A). 0.01 to 5 parts by mass is preferable, and 0.01 to 3 parts by mass is more preferable.
  • the mechanical property-imparting agent composition of the present invention contains a silicone oil
  • the content of the silicone oil is 100 parts by mass of the component (A) from the viewpoint of enhancing the above-mentioned effects due to the inclusion of the silicone oil.
  • 0.01 to 3 parts by mass is preferable, and 0.1 to 1 part by mass is more preferable.
  • the content of the epoxy coupling agent is It is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 1.5 parts by mass, per 100 parts by mass of component (A).
  • the content of hydrotalcite is 100% of component (A) from the viewpoint of enhancing the above-mentioned effects due to the inclusion of hydrotalcite. It is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 0.5 parts by mass.
  • the content of the lubricant is preferably It is 0.01 to 3 parts by mass, more preferably 0.1 to 0.5 parts by mass.
  • the mechanical property-imparting agent composition used in the present invention may optionally contain a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, other antioxidants, a nucleating agent, and an ultraviolet absorbing agent. agents, light stabilizers, plasticizers, fillers, fatty acid metal salts, antistatic agents, pigments, dyes and the like can be blended. These components can be blended in advance in the mechanical property-imparting agent composition of the present invention, and by blending the mechanical property-imparting agent composition into the resin, these components can be blended into the resin composition. It is preferable to stabilize the resin composition by blending these.
  • phenolic antioxidant examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6 -dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2' -thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidene Bis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3, 5-
  • the amount of these phenolic antioxidants used is preferably 0.001 to 5 parts by mass in 100 parts by mass of the resin composition when blended in the resin, and 0.01 to 1.0 parts by mass. is more preferred.
  • phosphite-based antioxidant examples include triphenylphosphite, diisooctylphosphite, heptakis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, and diisooctylphenylphosphite.
  • the amount of these phosphite-based antioxidants used is preferably 0.001 to 5 parts by mass, preferably 0.01 to 1.0 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. is more preferable.
  • thioether antioxidant examples include 3,3′-thiodipropionic acid, alkyl(C 12-14 )thiopropionic acid, di(lauryl)-3,3′-thiodipropionate, 3,3 '-ditridecyl thiobispropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3,3'-thiodipropionate pionate, lauryl stearyl thiodipropionate, tetrakis[methylene-3-(dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propionate) , 2,2′-thiodiethylenebis(3-aminobutenoate), 4,6
  • the amount of these thioether-based antioxidants used is preferably 0.001 to 5 parts by mass in 100 parts by mass of the resin composition when blended in the resin, and 0.01 to 1.0 parts by mass. is more preferred.
  • antioxidants examples include N-benzyl- ⁇ -phenyl nitrone, N-ethyl- ⁇ -methyl nitrone, N-octyl- ⁇ -heptyl nitrone, N-lauryl- ⁇ -undecyl nitrone, N- Tetradecyl- ⁇ -tridecyl nitrone, N-hexadecyl- ⁇ -pentadecyl nitrone, N-octyl- ⁇ -heptadecyl nitrone, N-hexadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -pentadecyl nitrone, N- Nitrone compounds such as heptadecyl- ⁇ -heptadecyl nitrone, N-octadecyl- ⁇ -heptadecyl nitrone, 3-arylbenzofuran-2(3
  • the amount of these other antioxidants used is preferably 0.001 to 5 parts by mass, and 0.01 to 1.0 parts by mass in 100 parts by mass of the resin composition when blended in the resin. quantity is more preferred.
  • nucleating agent examples include carboxylic acid metals such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate.
  • the amount of these nucleating agents to be used is preferably 0.001 to 5 parts by mass, and preferably 0.01 to 1.0 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. more preferred.
  • Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone), 2-hydroxy-4-normal octoxybenzophenone, 2-hydroxy-4- Benzophenones such as methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2- hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl- 5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2′-methylenebis(4-tert-octyl-6-benzo
  • the amount of these ultraviolet absorbers used is preferably an amount of 0.001 to 5 parts by mass, and an amount of 0.05 to 0.5 parts by mass in 100 parts by mass of the resin composition when blended in the resin. is more preferred.
  • Examples of the 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-piperidyl benzoate, bis(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-butanetetrac
  • the amount of these light stabilizers to be used is preferably an amount of 0.001 to 5 parts by mass, and an amount of 0.005 to 0.5 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. is more preferred.
  • plasticizer examples include epoxy-based soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester and the like; methacrylate-based; polycondensates of dicarboxylic acid and polyhydric alcohol; Polyesters such as polycondensates with polyhydric alcohols, polycondensates of dicarboxylic acids, polyhydric alcohols and alkylene glycol, polycondensates of dicarboxylic acids, polyhydric alcohols and arylene glycol, polyether esters such as polycondensates of a polyhydric alcohol and an alkylene glycol, polycondensates of a polyhydric carboxylic acid, a polyhydric alcohol and an arylene glycol; aliphatic esters such as adipic acid esters and succinic acid esters; Aromatic esters such as phthalate, terephthalate, trimellitate, pyromellitate, benzoate and the like are included. These plasticizers may be
  • the amount of these plasticizers used is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
  • Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, montmorillonite, etc. can be mentioned, and the particle size (in the fibrous form, the fiber diameter, fiber length and aspect ratio) can be selected appropriately. can be used These fillers may be used individually by 1 type, and may use 2 or more types together.
  • the amount of these fillers used is preferably 1 to 100 parts by mass, more preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
  • fatty acid of the fatty acid metal salt examples include capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, Heicosylic acid, behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanic acid, saturated fatty acids such as melissic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, ⁇ -linolenic acid, linoleic acid, ⁇ -linolenic acid , stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaeno
  • Examples of the metal of the fatty acid metal salt include alkali metals, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium or hafnium, and particularly sodium, lithium, Alkali metals such as potassium are preferred.
  • alkali metals magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium or hafnium, and particularly sodium, lithium, Alkali metals such as potassium are preferred.
  • One of these fatty acid metal salts may be used alone, or two or more thereof may be used in combination.
  • the amount of these fatty acid metal salts used is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. preferable.
  • antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts, higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic antistatic agents.
  • cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts, higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic antistatic agents.
  • Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates, polyhydric alcohol fatty acid esters, polyglycol phosphate esters , polyoxyethylene alkylallyl ether and other nonionic antistatic agents, amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric antistatic agents such as imidazoline type amphoteric surfactants.
  • One of these antistatic agents may be used alone, or two or more thereof may be used in combination.
  • the amount of these antistatic agents used is preferably 0.01 to 20 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
  • pigments can also be used as the pigment, for example Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112 , 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 and pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180,185 and pigment green 7,
  • the amount of these pigments to be used is preferably 0.0001 to 10 parts by mass in 100 parts by mass of the resin composition when mixed with the resin.
  • dyes can also be used as the dyes. Examples include dyes such as nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These dyes may be used individually by 1 type, and may use 2 or more types together.
  • the amount of these dyes used is preferably 0.0001 to 10 parts by mass based on 100 parts by mass of the resin composition when mixed with the resin.
  • the essential components (A), (B), and optionally (C) to (D), and optionally other Any of the optional components may be mixed, and various mixers can be used for mixing. Heat can be applied during mixing.
  • mixers include Turbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like.
  • the mechanical property-imparting agent composition of the present invention has the effect of imparting mechanical properties to resins, and is useful as a resin composition (sometimes referred to as a "resin additive"), particularly as a mechanical property-imparting agent.
  • the mechanical property-imparting agent composition of the present invention is preferably used as a resin composition imparted with mechanical properties (hereinafter also referred to as the resin composition of the present invention) by blending it with a resin.
  • thermoplastic resins include polyolefin resins, biomass-containing polyolefin resins, halogen-containing resins, aromatic polyester resins, linear polyester resins, degradable aliphatics, polyamide resins, cellulose ester resins; polycarbonate resins.
  • thermoplastic resins such as polyurethane resins, polyphenylene oxide resins, polyphenylene sulfide resins, acrylic resins, and blends thereof.
  • thermosetting resins include phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, and the like.
  • thermoplastic elastomers examples include olefinic thermoplastic elastomers, styrene thermoplastic elastomers, polyester thermoplastic elastomers, nitrile thermoplastic elastomers, and nylon thermoplastic elastomers.
  • Elastomers, vinyl chloride-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like can also be used.
  • resins may be used singly or in combination of two or more. Also, the resin may be alloyed.
  • the resin used in the present invention has molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomer, polymerization catalyst. It can be used regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.).
  • polyolefin-based resins or polyurethane-based thermoplastic elastomers are preferable because they can impart excellent mechanical properties.
  • polyolefin resins include 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, and isotactic.
  • Thermoplastic polyurethane resins can also be mentioned as thermoplastic polyurethane elastomers.
  • Thermoplastic polyurethane resin (TPU) is a rubber-like elastic body having a urethane group (-NHCOO-) in its molecular structure. It consists of strong moieties and is generally prepared using polyols, diisocyanates, and chain extenders.
  • thermoplastic polyurethane resin can be divided into a casting type in which liquid is poured into a mold and cured, a type in which roll-kneading and press molding is performed as with conventional rubber, and a type that can be processed in the same manner as general thermoplastic resins. Although they can be broadly classified, the present invention does not distinguish between them.
  • thermoplastic polyurethane resin examples include ester (lactone)-based polyurethane copolymers, ester (adipate)-based polyurethane copolymers, ether-based polyurethane copolymers, carbonate-based polyurethane copolymers, and ether/ester-based polyurethanes. Copolymers are included, and these thermoplastic polyurethane resins (TPU) can be used alone or in combination.
  • TPU thermoplastic polyurethane resins
  • the resin content is preferably 50 to 99.9% by mass, more preferably 60 to 90% by mass.
  • the resin composition of the present invention preferably contains 10 to 400 parts by mass, more preferably 20 to 80 parts by mass, of the mechanical property imparting agent composition per 100 parts by mass of the resin.
  • the molding method is not particularly limited, and includes extrusion, calendering, injection molding, roll molding, compression molding, blow molding, etc., and molded products of various shapes such as resin plates, sheets, films, irregular shaped products, etc. can be manufactured.
  • the resin composition of the present invention and its molded product are used in electrical/electronic/communication, electronic & engineering, 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.
  • the resin composition of the present invention and its molded product can be used for seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers. , airbags, insulating materials, straps, straps, wire coating materials, electrical insulating materials, paints, coating materials, covering materials, floor materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials , roofing materials, decking materials, wall materials, pillar materials, decking boards, fence materials, frames and moldings, window and door profiles, shingles, siding, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc.
  • automobiles hybrid cars, electric vehicles, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers , eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments and other daily necessities, and sports goods.
  • the purities of the above melamine salts and piperazine salts were measured using an ion chromatograph ICS-2100 (Thermo Fisher Scientific Co., Ltd.), a Dionex IonPac AS-19 column (Thermo Fisher Scientific Co., Ltd.), and an electrical conductivity detector. was measured using
  • component (D) As the melamine salt and piperazine salt, those produced in Production Examples 1 and 2 above were used.
  • Thermoplastic polyurethane resin (BASF Elastollan 1185A) 100 parts by weight calcium stearate 0.1 parts by weight, glycerin monostearate 0.3 parts by weight, tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl ) 0.1 part by mass of methyl propionate]methane and 0.1 part by mass of 2,2′-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite were blended, and preliminarily mixed with a Henschel mixer.
  • BASF Elastollan 1185A 100 parts by weight calcium stearate 0.1 parts by weight, glycerin monostearate 0.3 parts by weight, tetrakis [3-(3,5-di-tert-butyl-4
  • thermoplastic polyurethane resin composition X was obtained by mixing.
  • the components shown in Table 1 or 2 were added to the obtained thermoplastic polyurethane resin composition X in parts by weight shown in the table, and mixed with a Henschel mixer to obtain a resin composition.
  • Pellets were produced from each resin composition obtained above by the following method.
  • the resin compositions of Examples 1 to 15 containing a thermoplastic polyurethane resin and the resin compositions of Comparative Examples 1 to 4 were extruded into cylinders using a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.; TEX-30 ⁇ ). Melt-kneading was performed at a temperature of 170 to 200° C. and a screw speed of 150 rpm. The strand discharged from the die was cooled in a cooling bath and cut with a pelletizer to prepare pellets of the resin composition.
  • the resin compositions of Examples 16 to 20 and the resin compositions of Comparative Examples 5 to 8 containing polypropylene resin were extruded at a cylinder temperature of 220 using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.; TEX-30 ⁇ ). Melt-kneading was carried out under conditions of ⁇ 230°C and a screw speed of 150 rpm. The strand discharged from the die was cooled in a cooling bath and cut with a pelletizer to prepare pellets of the resin composition.
  • the pellets of the resin composition obtained above were injection molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.; NEX-80), and an ISO Type-A dumbbell piece for tensile property evaluation and a length of 127 mm, A test piece for flame retardancy evaluation having a width of 12.7 mm and a thickness of 1.6 mm was obtained.
  • the set screw temperature was 190°C and the mold temperature was 50°C.
  • the set screw temperature was 230°C and the mold temperature was 40°C.
  • the mechanical property-imparting agent composition of the present invention can impart high flame retardancy and good mechanical properties to resins, and is excellent as a mechanical property-imparting agent.

Abstract

The purpose of the present invention is to provide: a mechanical property-imparting agent composition which can impart a resin with excellent flame retardancy and excellent mechanical properties; a resin composition that contains this mechanical property-imparting agent composition.　The present invention is a mechanical property-imparting agent composition that contains: a component (A), a phosphoric acid amine salt; and a component (B), melamine cyanurate. Component (A) contains a component (A-1) and a component (A-2). The content of component (B) is 10-40 parts by mass relative to a total of 100 parts by mass of component (A-1) and component (A-2).　Component (A-1): A melamine salt including at least one type selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.　Component (A-2): A piperazine salt including at least one type selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.

Description

機械物性付与剤組成物、樹脂組成物および成形品Mechanical property imparting agent composition, resin composition and molded article
　本発明は、リン酸アミン塩およびメラミンシアヌレートを含有する機械物性付与剤組成物、および該機械物性付与剤組成物を配合した樹脂組成物に関する。 The present invention relates to a mechanical property-imparting agent composition containing an amine phosphate salt and melamine cyanurate, and a resin composition containing the mechanical property-imparting agent composition.
　従来、合成樹脂は優れた化学的、機械特性により、様々な用途に広く用いられている。しかし、多くの合成樹脂は可燃性物質であり、用途によっては難燃化が不可欠であった。難燃化方法としては、合成樹脂に難燃剤を配合する手法が広く知られており、これまでに種々の難燃剤が提案されている。 Conventionally, synthetic resins have been widely used for various purposes due to their excellent chemical and mechanical properties. However, many synthetic resins are combustible substances, and depending on the application, it was essential to make them flame-retardant. As a flame retardant method, a method of blending a flame retardant with a synthetic resin is widely known, and various flame retardants have been proposed so far.
　例えば、ポリリン酸やピロリン酸と窒素含有化合物の塩を主成分とするイントメッセント系難燃剤は、燃焼時に表面膨張層（Intumescent）を形成し、分解生成物の拡散や伝熱を抑制することにより難燃性を発揮させることが知られている。この種の難燃剤の一例として、特許文献１では、特定のメラミン塩、特定のピペラジン塩およびメラミンシアヌレートを含有する難燃剤が提案されており、この難燃剤が高いドリップ防止効果を有し、難燃性に優れることが開示されている。 For example, intumescent flame retardants, which are mainly composed of salts of polyphosphoric acid or pyrophosphoric acid and nitrogen-containing compounds, form an intumescent layer on the surface during combustion, suppressing the diffusion of decomposition products and heat transfer. It is known that flame retardancy is exhibited by As an example of this type of flame retardant, Patent Document 1 proposes a flame retardant containing a specific melamine salt, a specific piperazine salt and melamine cyanurate, which has a high anti-drip effect, It is disclosed to be excellent in flame retardancy.
ＵＳ２０２０／０２２４１００　Ａ１US2020/0224100 A1
　樹脂材料を使用する種々の用途において、防火性への要求とともに、優れた機械物性を有する樹脂組成物が求められてきた。しかしながら、特許文献１の難燃剤においては、各成分の含有比率によっては、樹脂に配合した際の難燃性と機械物性の両立が困難な場合があった。 In various applications where resin materials are used, there has been a demand for resin compositions with excellent mechanical properties along with the demand for fire resistance. However, in the flame retardant of Patent Document 1, depending on the content ratio of each component, it may be difficult to achieve both flame retardancy and mechanical properties when blended in a resin.
　本発明の課題は、樹脂に優れた難燃性および優れた機械物性を付与する機械物性付与剤組成物を提供すること、および、該機械物性付与剤組成物を配合した樹脂組成物を提供することにある。 An object of the present invention is to provide a mechanical property-imparting agent composition that imparts excellent flame retardancy and excellent mechanical properties to a resin, and to provide a resin composition containing the mechanical property-imparting agent composition. That's what it is.
　本発明者らは、前記課題を解決する構成を鋭意検討したところ、アミンのリン酸塩とメラミンシアヌレートとを特定の比率で組み合わせた機械物性付与剤組成物を樹脂に混合することにより、樹脂に優れた難燃性および機械物性が付与されることを見出し、本発明を完成させた。 The present inventors have made intensive studies on a configuration for solving the above problems, and found that by mixing a resin with a mechanical property-imparting agent composition in which an amine phosphate and melamine cyanurate are combined in a specific ratio, the resin The present inventors have completed the present invention by finding that excellent flame retardancy and mechanical properties are imparted to.
　本発明は、前記の知見に基づくものであり、下記（Ａ－１）成分および下記（Ａ－２）成分を含む（Ａ）成分：リン酸アミン塩と（Ｂ）成分：メラミンシアヌレートとを特定の比率で含有する機械物性付与剤組成物を提供するものである。
　（Ａ－１）成分：オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含むメラミン塩。
　（Ａ－２）成分：オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含むピペラジン塩。 The present invention is based on the above findings, and includes the following components (A-1) and (A-2): component (A): amine phosphate salt and component (B): melamine cyanurate. The object is to provide a mechanical property-imparting agent composition containing in a specific ratio.
(A-1) Component: A melamine salt containing at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
(A-2) Component: a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
　また本発明は、樹脂および前記機械物性付与剤組成物を含有する樹脂組成物、ならびにその成形体を提供するものである。 The present invention also provides a resin composition containing a resin and the mechanical property-imparting agent composition, and a molded article thereof.
　また本発明は、前記（Ａ）成分および前記（Ｂ）成分を特定の比率で含有する組成物を樹脂と混合する、樹脂の機械物性付与方法を提供するものである。 The present invention also provides a method for imparting mechanical properties to a resin, comprising mixing a resin with a composition containing the (A) component and the (B) component in a specific ratio.
　さらに本発明は、前記（Ａ）成分および前記（Ｂ）成分を特定に比率で含有する機械物性付与剤組成物の機械物性付与剤としての使用を提供するものである。 Further, the present invention provides use of a mechanical property-imparting agent composition containing the component (A) and the component (B) in a specific ratio as a mechanical property-imparting agent.
　本発明によれば、樹脂に優れた難燃性および優れた機械物性を付与できる機械物性付与剤組成物を提供することができ、また該機械物性付与剤組成物を樹脂に配合することにより優れた難燃性および優れた機械物性を有する樹脂組成物を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a mechanical property-imparting agent composition capable of imparting excellent flame retardancy and excellent mechanical properties to a resin. It is possible to provide a resin composition having excellent flame retardancy and excellent mechanical properties.
　以下、本発明をその好ましい実施形態に基づき詳細に説明する。
　なお、以下の説明において、機械物性とは、耐衝撃性、剛性、引張特性等の機械的性質を意味し、特に、ＩＳＯ　５２７に準拠した引張特性評価において測定される引張伸びおよび引張強度を意味する。機械物性付与剤とは、樹脂に配合することにより前記の機械物性を向上させる効果を有する添加剤を意味する。機械物性付与剤組成物とは、機械物性付与剤の１種以上を含有する組成物を意味する。 Hereinafter, the present invention will be described in detail based on its preferred embodiments.
In the following description, mechanical properties mean mechanical properties such as impact resistance, rigidity, tensile properties, and in particular, tensile elongation and tensile strength measured in tensile property evaluation in accordance with ISO 527. do. The term "mechanical property imparting agent" means an additive that has the effect of improving the aforementioned mechanical properties when blended with a resin. A mechanical property-imparting agent composition means a composition containing one or more mechanical property-imparting agents.
　また、以下の説明において、難燃性とは、物質が着火しにくく、また着火して燃焼が持続してもその速度が非常に遅かったり、その後、自己消火したりする性質であること、好ましくは実施例に記載されているＵＬ９４　Ｖ規格に従った燃焼ランクのうち、少なくともＶ－１のランクを有することを意味し、より好ましくはＶ－０のランクを有することを意味する。 In the following description, flame retardancy means that a substance is difficult to ignite, and even if it ignites and continues to burn, the speed is very slow, and then it self-extinguishes. means having at least a rank of V-1, more preferably a rank of V-0, among the combustion ranks according to the UL94 V standard described in the examples.
　本発明の機械物性付与剤組成物は、（Ａ）成分：リン酸アミン塩および（Ｂ）成分：メラミンシアヌレートを特定の比率で含有している点に特徴の一つを有する。 The mechanical property-imparting agent composition of the present invention is characterized in that it contains component (A): amine phosphate and component (B): melamine cyanurate in a specific ratio.
　まず、本発明の機械物性付与剤組成物に含まれる（Ａ）成分であるリン酸アミン塩について説明する。リン酸アミン塩とは、リン酸とアミンとの塩である。 First, the amine phosphate salt, which is the component (A) contained in the mechanical property-imparting agent composition of the present invention, will be described. Phosphate amine salts are salts of phosphoric acid and amines.
　本発明においてリン酸とは、五酸化二リンが水和してできる酸を意味し、具体的には、オルトリン酸、ピロリン酸およびポリリン酸が挙げられる。これらのリン酸はそれぞれ単独で用いることができ、あるいは２種以上を組み合わせて用いることができる。 In the present invention, phosphoric acid means an acid formed by hydrating diphosphorus pentoxide, and specifically includes orthophosphoric acid, pyrophosphoric acid and polyphosphoric acid. Each of these phosphoric acids can be used alone, or two or more of them can be used in combination.
　本発明の機械物性付与剤組成物において（Ａ）成分として用いられるリン酸アミン塩は、（Ａ－１）成分：オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含むメラミン塩と（Ａ－２）成分：オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含むピペラジン塩とを含有する。 The amine phosphate salt used as component (A) in the mechanical property-imparting agent composition of the present invention is component (A-1): at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate. A melamine salt containing seeds and component (A-2): a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
　本発明の機械物性付与剤組成物において（Ａ－１）成分として用いられるメラミン塩は、オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含む。これらの中でも、難燃性、ハンドリング性および保存安定性の点からピロリン酸メラミンを含むことが好ましい。メラミン塩が混合物である場合は、該混合物中でのピロリン酸メラミンの質量基準での含有割合が最も高いことが好ましい。メラミン塩中のピロリン酸メラミンの含有量は、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることが特に好ましい。 The melamine salt used as the (A-1) component in the mechanical property-imparting agent composition of the present invention contains at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate. Among these, melamine pyrophosphate is preferably contained from the viewpoint of flame retardancy, handleability and storage stability. When the melamine salt is a mixture, it is preferable that the content of melamine pyrophosphate in the mixture is the highest on a mass basis. The content of melamine pyrophosphate in the melamine salt is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
　これらリン酸とメラミンとの塩は、それぞれ対応するリン酸またはリン酸塩と、メラミンまたはメラミン塩酸塩とを反応させることによって得ることができる。上記リン酸塩としては、例えば、第一リン酸ナトリウム、第一リン酸カリウム、第二リン酸ナトリウム、第二リン酸カリウム、第三リン酸ナトリウム、第三リン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、ポリリン酸ナトリウムおよびポリリン酸カリウム等が挙げられる。 These salts of phosphoric acid and melamine can be obtained by reacting the corresponding phosphoric acid or phosphate with melamine or melamine hydrochloride. Examples of the phosphate include monobasic sodium phosphate, monobasic potassium phosphate, dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tribasic potassium phosphate, sodium pyrophosphate, pyroline potassium phosphate, sodium polyphosphate, potassium polyphosphate and the like.
　また、ピロリン酸メラミンおよびポリリン酸メラミンは、オルトリン酸メラミンを加熱縮合して得てもよい。特に、本発明の（Ａ－１）成分で使用されるメラミン塩は、オルトリン酸メラミンを加熱縮合させて得られた、ピロリン酸メラミンまたはポリリン酸メラミンを主成分とするメラミン塩が好ましく、特にオルトリン酸メラミンを加熱縮合させて得られた、ピロリン酸メラミンを主成分とするメラミン塩が好ましい。 In addition, melamine pyrophosphate and melamine polyphosphate may be obtained by thermally condensing melamine orthophosphate. In particular, the melamine salt used in the component (A-1) of the present invention is preferably a melamine salt containing melamine pyrophosphate or melamine polyphosphate as a main component, obtained by thermally condensing melamine orthophosphate. A melamine salt containing melamine pyrophosphate as a main component obtained by thermally condensing acid melamine is preferred.
　本発明の機械物性付与剤組成物において（Ａ－２）成分として用いられるピペラジン塩は、オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含む。これらの中でも難燃性、ハンドリング性および保存安定性の点から、ピロリン酸ピペラジンを含むことが好ましく、ピペラジン塩が混合物である場合は、該混合物中でのピロリン酸ピペラジンの質量基準での含有割合が最も高いことが好ましい。メラミン塩中のピロリン酸ピペラジンの含有量は、９０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９８質量％以上であることが特に好ましい。 The piperazine salt used as component (A-2) in the mechanical property-imparting agent composition of the present invention contains at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate. Among these, it is preferable to contain piperazine pyrophosphate from the viewpoint of flame retardancy, handleability and storage stability, and when the piperazine salt is a mixture, the content ratio of piperazine pyrophosphate in the mixture on a mass basis. is the highest. The content of piperazine pyrophosphate in the melamine salt is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
　これらリン酸とピペラジンの塩は、それぞれ対応するリン酸またはリン酸塩と、ピペラジンまたはピペラジン塩酸塩とを反応させることで得ることができる。上記リン酸塩としては、上述したものを用いることができる。また、ピロリン酸ピペラジンおよびポリリン酸ピペラジンは、オルトリン酸ピペラジンを加熱縮合して得てもよい。特に本発明の（Ａ－２）成分で使用されるピペラジン塩は、オルトリン酸ピペラジンを加熱縮合させて得られた、ピロリン酸ピペラジンまたはポリリン酸ピペラジンを主成分とするピペラジン塩が好ましく、特にオルトリン酸ピペラジンを加熱縮合させて得られた、ピロリン酸ピペラジンを主成分とするピペラジン塩が好ましい。 These salts of phosphoric acid and piperazine can be obtained by reacting the corresponding phosphoric acid or phosphate with piperazine or piperazine hydrochloride. As the phosphate, those described above can be used. Piperazine pyrophosphate and piperazine polyphosphate may also be obtained by thermally condensing piperazine orthophosphate. In particular, the piperazine salt used in the component (A-2) of the present invention is preferably a piperazine salt containing piperazine pyrophosphate or piperazine polyphosphate as a main component obtained by thermally condensing piperazine orthophosphate, particularly orthophosphoric acid. A piperazine salt containing piperazine pyrophosphate as a main component obtained by thermally condensing piperazine is preferred.
　本発明の機械物性付与剤組成物に含まれる（Ａ）成分は（Ａ－１）成分および（Ａ－２）成分のみからなることが好ましい。この場合、（Ａ）成分における（Ａ－１）成分の含有量は、（Ａ）成分１００質量部に対して、１０～５０質量部が好ましく、２０～５０質量部がより好ましい。（Ａ）成分における（Ａ－２）成分の含有量は、（Ａ）成分１００質量部に対して、９０～５０質量部が好ましく８０～５０質量部がより好ましい。 The (A) component contained in the mechanical property-imparting agent composition of the present invention preferably consists only of the (A-1) component and the (A-2) component. In this case, the content of component (A-1) in component (A) is preferably 10 to 50 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of component (A). The content of component (A-2) in component (A) is preferably 90 to 50 parts by mass, more preferably 80 to 50 parts by mass, per 100 parts by mass of component (A).
　また、本発明の機械物性付与剤組成物中、（Ａ）成分の合計量が６０～９０質量％であることが好ましく、６０～８３質量％であることがより好ましい。（Ａ）成分の含有量が６０質量％以上であることは、難燃性を高める点で好ましく、９０質量％以下であることが、（Ｂ）成分の配合量を確保して本発明の効果を高める点で好ましい。本発明の機械物性付与剤組成物における、（Ａ－１）成分であるメラミン塩および（Ａ－２）成分であるピペラジン塩に代表される（Ａ）成分であるリン酸アミン塩の含有量は、イオンクロマトグラフィーにより測定することができる。 In addition, the total amount of component (A) in the mechanical property-imparting agent composition of the present invention is preferably 60 to 90% by mass, more preferably 60 to 83% by mass. It is preferable that the content of component (A) is 60% by mass or more in terms of improving flame retardancy, and that it is 90% by mass or less ensures the amount of component (B) to be blended, and the effect of the present invention is obtained. is preferable in terms of increasing In the mechanical property-imparting agent composition of the present invention, the content of the amine phosphate salt as the component (A) typified by the melamine salt as the component (A-1) and the piperazine salt as the component (A-2) is , can be determined by ion chromatography.
　次に本発明の機械物性付与剤組成物の（Ｂ）成分について説明する。
　本発明の機械物性付与剤組成物における（Ｂ）成分であるメラミンシアヌレートは、メラミンとシアヌール酸との有機塩である。 Next, the component (B) of the composition for imparting mechanical properties of the present invention will be described.
Melamine cyanurate, which is the component (B) in the agent composition for imparting mechanical properties of the present invention, is an organic salt of melamine and cyanuric acid.
　メラミンシアヌレートとしては、市販品を用いることができる。メラミンシアヌレートの市販品としては、例えば、日産化学工業（株）のＭＣ－４０００、ＭＣ－４５００、ＭＣ－６０００などが挙げられる。 A commercially available product can be used as the melamine cyanurate. Examples of commercial products of melamine cyanurate include MC-4000, MC-4500 and MC-6000 manufactured by Nissan Chemical Industries, Ltd.
　メラミンシアヌレートの製造方法としては、公知の方法が挙げられる。例えば、特開平７－１８８１９３号公報や特開平７－１４９７３９号公報などに開示されている。 Known methods can be mentioned as methods for producing melamine cyanurate. For example, it is disclosed in Japanese Unexamined Patent Publication No. 7-188193 and Japanese Unexamined Patent Publication No. 7-149739.
　本発明の機械物性付与剤組成物において、前記（Ｂ）成分の含有量は、前記（Ａ－１）成分および（Ａ－２）成分の合計含有量１００質量部に対して、１０質量部以上４０質量部以下であり、好ましくは２０質量部を超えて４０質量部以下、さらにより好ましくは２０質量部を超えて３８質量部以下、特に好ましくは２０質量部を超えて３０質量部以下である。（Ｂ）成分の含有量を１０質量部以上に設定することで、樹脂に配合したときの機械特性向上の利点がある。一方、（Ｂ）成分の含有量を４０質量部以下に設定することで、難燃性の点から利点がある。 In the mechanical property-imparting agent composition of the present invention, the content of the component (B) is 10 parts by mass or more with respect to 100 parts by mass of the total content of the components (A-1) and (A-2). 40 parts by mass or less, preferably over 20 parts by mass and 40 parts by mass or less, more preferably over 20 parts by mass and 38 parts by mass or less, particularly preferably over 20 parts by mass and 30 parts by mass or less . By setting the content of the component (B) to 10 parts by mass or more, there is an advantage of improving the mechanical properties when blended with the resin. On the other hand, setting the content of component (B) to 40 parts by mass or less is advantageous in terms of flame retardancy.
　本発明の機械物性付与剤組成物において、前記（Ｂ）成分の含有量は、例えば、赤外分光法、ガスクロマトグラフィー、ガスクロマトグラフィー－質量分析法などにより測定することができる。 In the mechanical property-imparting agent composition of the present invention, the content of the component (B) can be measured, for example, by infrared spectroscopy, gas chromatography, gas chromatography-mass spectrometry, or the like.
　本発明の機械物性付与剤組成物には、酸化亜鉛（ＺｎＯ）をさらに含有させることができる（以下、この成分を「（Ｃ）成分」ともいう。）。 The mechanical property-imparting agent composition of the present invention can further contain zinc oxide (ZnO) (hereinafter, this component is also referred to as "(C) component").
　前記酸化亜鉛は、難燃助剤として機能する。該酸化亜鉛は表面処理されている場合がある。酸化亜鉛は市販品を使用することができ、例えば、酸化亜鉛１種（三井金属鉱業（株）製）、部分被膜型酸化亜鉛（三井金属鉱業（株）製）、ナノファイン５０（平均粒径０．０２μｍの超微粒子酸化亜鉛：堺化学工業（株）製）、ナノファインＫ（平均粒径０．０２μｍの珪酸亜鉛被膜した超微粒子酸化亜鉛：堺化学工業（株）製）等が挙げられる。 The zinc oxide functions as a flame retardant aid. The zinc oxide may be surface-treated. Commercially available zinc oxide can be used. 0.02 μm ultrafine zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd.), Nanofine K (superfine zinc oxide coated with zinc silicate with an average particle size of 0.02 μm: manufactured by Sakai Chemical Industry Co., Ltd.), and the like. .
　本発明の機械物性付与剤組成物において、前記（Ｃ）成分である酸化亜鉛の含有量は、難燃性の点から、前記（Ａ）成分１００質量部に対して、０．０１～１０質量部が好ましく、より好ましくは０．５～８質量部、さらに好ましくは１～７質量部である。酸化亜鉛の含有量を０．０１質量部以上に設定することで難燃性がより良好となる。一方、酸化亜鉛の含有量を１０質量部以下に設定することで、加工性に悪影響を生じさせにくい。 In the mechanical property-imparting agent composition of the present invention, the content of zinc oxide as the component (C) is 0.01 to 10 mass parts per 100 parts by mass of the component (A) from the viewpoint of flame retardancy. parts, more preferably 0.5 to 8 parts by mass, still more preferably 1 to 7 parts by mass. By setting the content of zinc oxide to 0.01 part by mass or more, the flame retardancy becomes better. On the other hand, by setting the content of zinc oxide to 10 parts by mass or less, workability is less likely to be adversely affected.
　本発明の機械物性付与剤組成物は、機械物性付与剤粉末が凝集することを防止し、保存安定性の向上と、合成樹脂への分散性の向上を図る点から、さらにシリコーンオイル、エポキシ系カップリング剤、ハイドロタルサイトおよび滑剤から選ばれる少なくとも１種（以下、この成分を「（Ｄ）成分」ともいう。）を含有することが好ましい。 The mechanical property-imparting agent composition of the present invention prevents the mechanical property-imparting agent powder from agglomerating, improves storage stability, and improves dispersibility in synthetic resins. It preferably contains at least one selected from coupling agents, hydrotalcite and lubricants (hereinafter, this component is also referred to as "component (D)").
　シリコーンオイルの例としては、ポリシロキサンの側鎖および末端が全てメチル基であるジメチルシリコーンオイル、ポリシロキサンの側鎖および末端がメチル基であり、その側鎖の一部がフェニル基であるメチルフェニルシリコーンオイル、ポリシロキサンの側鎖および末端がメチル基であり、その側鎖の一部が水素であるメチルハイドロジェンシリコーンオイル等、並びにこれらのコポリマーが挙げられる。またこれらの側鎖および／または末端の一部に有機基を導入した、アミン変性、エポキシ変性、脂環式エポキシ変性、カルボキシル変性、カルビノール変性、メルカプト変性、ポリエーテル変性、長鎖アルキル変性、フロロアルキル変性、高級脂肪酸エステル変性、高級脂肪酸アミド変性、シラノール変性、ジオール変性、フェノール変性およびアラルキル変性シリコーンオイルを使用することができる。 Examples of silicone oils include dimethylsilicone oil in which the side chains and terminals of polysiloxane are all methyl groups, and methylphenyl, in which the side chains and terminals of polysiloxane are methyl groups and part of the side chains are phenyl groups. Examples thereof include silicone oil, methylhydrogensilicone oil in which the side chains and terminals of polysiloxane are methyl groups and part of the side chains are hydrogen, and copolymers thereof. Amine-modified, epoxy-modified, alicyclic epoxy-modified, carboxyl-modified, carbinol-modified, mercapto-modified, polyether-modified, long-chain alkyl-modified Fluoroalkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, silanol-modified, diol-modified, phenol-modified and aralkyl-modified silicone oils can be used.
　前記シリコーンオイルの具体例を挙げると、ジメチルシリコーンオイルとして、ＫＦ－９６（信越化学（株）製）、ＫＦ－９６５（信越化学（株）製）、ＫＦ－９６８（信越化学（株）製）等が挙げられ、メチルハイドロジェンシリコーンオイルとして、ＫＦ－９９（信越化学（株）製）、ＫＦ－９９０１（信越化学（株））、ＨＭＳ－１５１（Ｇｅｌｅｓｔ社製）、ＨＭＳ－０７１（Ｇｅｌｅｓｔ社製）、ＨＭＳ－３０１（Ｇｅｌｅｓｔ社製）、ＤＭＳ－Ｈ２１（Ｇｅｌｅｓｔ社製）等が挙げられ、メチルフェニルシリコーンオイルの例としては、ＫＦ－５０（信越化学（株）製）、ＫＦ－５３（信越化学（株）製）、ＫＦ－５４（信越化学（株）製）、ＫＦ－５６（信越化学（株）製）等が挙げられ、エポキシ変性品としては、例えば、Ｘ－２２－３４３（信越化学（株）製）、Ｘ－２２－２０００（信越化学（株）製）、ＫＦ－１０１（信越化学（株）製）、ＫＦ－１０２（信越化学（株）製）、ＫＦ－１００１（信越化学（株）製）、カルボキシル変性品としては、例えば、Ｘ－２２－３７０１Ｅ（信越化学（株）製）、カルビノール変性品としては、例えば、Ｘ－２２－４０３９（信越化学（株）製）、Ｘ－２２－４０１５（信越化学（株）製）、アミン変性品としては、例えば、ＫＦ－３９３（信越化学（株）製）等が挙げられる。 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.), and KF-968 (manufactured by Shin-Etsu Chemical Co., Ltd.) as dimethyl silicone oil. etc., and examples of methyl hydrogen silicone oils include KF-99 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-9901 (manufactured by Shin-Etsu Chemical Co., Ltd.), HMS-151 (manufactured by Gelest), HMS-071 (manufactured by Gelest ), HMS-301 (manufactured by Gelest), DMS-H21 (manufactured by Gelest), etc. Examples of methylphenyl silicone oils include KF-50 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-54 (Shin-Etsu Chemical Co., Ltd.), KF-56 (Shin-Etsu Chemical Co., Ltd.), etc. Examples of epoxy-modified products include X-22-343 ( Shin-Etsu Chemical Co., Ltd.), X-22-2000 (Shin-Etsu Chemical Co., Ltd.), KF-101 (Shin-Etsu Chemical Co., Ltd.), KF-102 (Shin-Etsu Chemical Co., Ltd.), KF-1001 ( Shin-Etsu Chemical Co., Ltd.), carboxyl-modified products such as X-22-3701E (Shin-Etsu Chemical Co., Ltd.), carbinol-modified products such as X-22-4039 (Shin-Etsu Chemical Co., Ltd.) (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-4015 (manufactured by Shin-Etsu Chemical Co., Ltd.), and amine-modified products include, for example, KF-393 (manufactured by Shin-Etsu Chemical Co., Ltd.).
　本発明の機械物性付与剤組成物においては、シリコーンオイルの中でも、機械物性付与剤粉末が凝集することを防止し、保存安定性の向上と、合成樹脂への分散性向上の点から、メチルハイドロジェンシリコーンオイルが好ましい。 In the mechanical property-imparting agent composition of the present invention, among silicone oils, the mechanical property-imparting agent powder is prevented from agglomerating, the storage stability is improved, and the dispersibility in the synthetic resin is improved. Jen silicone oil is preferred.
　エポキシ系カップリング剤は、機械物性付与剤粉末の凝集を防止し、保存安定性の向上のためや、耐水性、耐熱性を付与するという機能を有する。エポキシ系カップリング剤としては、例えば、一般式Ａ－（ＣＨ２）ｋ－Ｓｉ（ＯＲ）３で表される化合物であってエポキシ基を有する化合物が挙げられる。Ａはエポキシ環を有する基であり、ｋは１～３の数を表し、Ｒはメチル基またはエチル基を表す。ここでいうエポキシ環を有する基としては、グリシドキシ基や３，４－エポキシシクロヘキシル基が挙げられる。 The epoxy-based coupling agent has the function of preventing aggregation of the mechanical property-imparting agent powder, improving storage stability, and imparting water resistance and heat resistance. Epoxy coupling agents include, for example, compounds represented by the general formula A—(CH 2 ) k —Si(OR) 3 and having an epoxy group. A is a group having an epoxy ring, k represents a number from 1 to 3, and R represents a methyl group or an ethyl group. The group having an epoxy ring as used herein includes a glycidoxy group and a 3,4-epoxycyclohexyl group.
　エポキシ系カップリング剤としては、例えば、エポキシ基を有するシランカップリング剤として、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルトリエトキシシラン、グリシドキシオクチルトリメトキシシラン等が挙げられる。 Examples of epoxy coupling agents include silane coupling agents having an epoxy group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxyoctyltrimethoxysilane and the like.
　ハイドロタルサイトは、天然物や合成物として知られるマグネシウム、アルミニウム、水酸基、炭酸基および任意の結晶水からなる複合塩化合物であり、マグネシウムまたはアルミニウムの一部をアルカリ金属や亜鉛など他の金属で置換したものや水酸基、炭酸基を他のアニオン基で置換したものが挙げられる。具体的には、例えば、下記式（３）で表されるハイドロタルサイトや、下記式（３）で表されるハイドロタルサイトの金属をアルカリ金属に置換したものが挙げられる。また、Ａｌ－Ｌｉ系のハイドロタルサイトとしては、式（４）で表される化合物も用いることができる。 Hydrotalcite is a complex salt compound consisting of magnesium, aluminum, hydroxyl group, carbonate group and optional water of crystallization, which are known as natural or synthetic products. Substituted ones and those in which hydroxyl groups and carbonate groups are substituted with other anionic groups can be mentioned. Specifically, for example, hydrotalcite represented by the following formula (3) and hydrotalcite represented by the following formula (3) in which the metal is replaced with an alkali metal can be mentioned. A compound represented by the formula (4) can also be used as the Al—Li-based hydrotalcite.
Figure JPOXMLDOC01-appb-C000001
 　式（３）中、ｘ１およびｘ２は、各々０≦ｘ２／ｘ１＜１０および２≦ｘ１＋ｘ２≦２０を満たす数を表し、ｐは０または正の数を表す。
Figure JPOXMLDOC01-appb-C000001
 In formula (3), x1 and x2 represent numbers satisfying 0≤x2/x1<10 and 2≤x1+x2≤20, respectively, and p represents 0 or a positive number.
Figure JPOXMLDOC01-appb-C000002
 　式（４）中、Ａｑ－は、ｑ価のアニオンを表し、ｐは０または正の数を表す。
Figure JPOXMLDOC01-appb-C000002
 In formula (4), A q- represents a q-valent anion, and p represents 0 or a positive number.
　また、前記ハイドロタルサイトにおける炭酸アニオンは、一部を他のアニオンで置換されていてもよい。 In addition, the carbonate anions in the hydrotalcite may be partly replaced with other anions.
　前記ハイドロタルサイトは、結晶水を脱水したものであってもよく、ステアリン酸等の高級脂肪酸、オレイン酸アルカリ金属塩等の高級脂肪酸金属塩、ドデシルベンゼンスルホン酸アルカリ金属塩等の有機スルホン酸金属塩、高級脂肪酸アミド、高級脂肪酸エステルまたはワックス等で被覆されている場合がある。 The hydrotalcite may be obtained by dehydrating the water of crystallization, and includes higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic metal sulfonates such as alkali metal dodecylbenzenesulfonate. It may be coated with salt, higher fatty acid amide, higher fatty acid ester, wax, or the like.
　滑剤としては、流動パラフィン、天然パラフィン、マイクロワックス、合成パラフィン、低分子量ポリエチレン、ポリエチレンワックス等の純炭化水素系滑剤；ハロゲン化炭化水素系滑剤；高級脂肪酸、オキシ脂肪酸等の脂肪酸系滑剤；脂肪酸アミド、ビス脂肪酸アミド等の脂肪酸アミド系滑剤；脂肪酸の低級アルコールエステル、グリセリド等の脂肪酸の多価アルコールエステル、脂肪酸のポリグリコールエステル、脂肪酸の脂肪アルコールエステル（エステルワックス）等のエステル系滑剤；金属石鹸、脂肪アルコール、多価アルコール、ポリグリコール、ポリグリセロール、脂肪酸と多価アルコールの部分エステル、脂肪酸とポリグリコール、ポリグリセロールの部分エステル系の滑剤や、シリコーンオイル、鉱油等が挙げられる。滑剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Lubricants include pure hydrocarbon lubricants such as liquid paraffin, natural paraffin, microwax, 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 lubricants such as bis fatty acid amides; lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids such as glycerides, polyglycol esters of fatty acids, ester lubricants such as fatty alcohol esters of fatty acids (ester wax); metal soaps , fatty alcohol, polyhydric alcohol, polyglycol, polyglycerol, partial ester of fatty acid and polyhydric alcohol, fatty acid and polyglycol, partial ester lubricant of polyglycerol, silicone oil, mineral oil, and the like. Lubricants may be used individually by 1 type, and may use 2 or more types together.
　難燃性の向上の点から、本発明の機械物性付与剤組成物に、シリコーンオイル、エポキシ系カップリング剤、ハイドロタルサイトおよび滑剤から選ばれる少なくとも１種（（Ｄ）成分）を含有させる場合、本発明の機械物性付与剤組成物中、（Ｄ）成分の含有量は、前記の（Ｄ）成分を含有する効果を効果的に発揮させる観点から、前記（Ａ）成分１００質量部に対して、０．０１～５質量部が好ましく、０．０１～３質量部がより好ましい。 When the mechanical property imparting agent composition of the present invention contains at least one selected from silicone oil, epoxy coupling agent, hydrotalcite and lubricant (component (D)) from the viewpoint of improving flame retardancy. In the mechanical property-imparting agent composition of the present invention, the content of component (D) is, from the viewpoint of effectively exhibiting the effect of containing component (D), relative to 100 parts by mass of component (A). 0.01 to 5 parts by mass is preferable, and 0.01 to 3 parts by mass is more preferable.
　特に、本発明の機械物性付与剤組成物にシリコーンオイルを含有させる場合のシリコーンオイルの含有量は、シリコーンオイルを含有することによる前記の効果を高める点から、前記（Ａ）成分１００質量部に対して、０．０１～３質量部が好ましく、０．１～１質量部がより好ましい。 In particular, when the mechanical property-imparting agent composition of the present invention contains a silicone oil, the content of the silicone oil is 100 parts by mass of the component (A) from the viewpoint of enhancing the above-mentioned effects due to the inclusion of the silicone oil. On the other hand, 0.01 to 3 parts by mass is preferable, and 0.1 to 1 part by mass is more preferable.
　特に、本発明の機械物性付与剤組成物にエポキシ系カップリング剤を含有させる場合のエポキシ系カップリング剤の含有量は、エポキシ系カップリング剤を含有することによる前記の効果を高める点から、前記（Ａ）成分１００質量部に対して、好ましくは０．０１～３質量部であり、より好ましくは０．１～１．５質量部である。 In particular, when the mechanical property-imparting agent composition of the present invention contains an epoxy coupling agent, the content of the epoxy coupling agent is It is preferably 0.01 to 3 parts by mass, more preferably 0.1 to 1.5 parts by mass, per 100 parts by mass of component (A).
　特に、本発明の機械物性付与剤組成物にハイドロタルサイトを含有させる場合のハイドロタルサイトの含有量は、ハイドロタルサイトを含有することによる前記の効果を高める点から、前記（Ａ）成分１００質量部に対して、好ましくは０．０１～５質量部であり、より好ましくは０．１～０．５質量部である。 In particular, when hydrotalcite is contained in the agent composition for imparting mechanical properties of the present invention, the content of hydrotalcite is 100% of component (A) from the viewpoint of enhancing the above-mentioned effects due to the inclusion of hydrotalcite. It is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 0.5 parts by mass.
　本発明の機械物性付与剤組成物に滑剤を含有させる場合の滑剤の含有量は、滑剤を含有することによる前記の効果を高める点から、前記（Ａ）成分１００質量部に対して、好ましくは０．０１～３質量部であり、より好ましくは０．１～０．５質量部である。 When the mechanical property-imparting agent composition of the present invention contains a lubricant, the content of the lubricant is preferably It is 0.01 to 3 parts by mass, more preferably 0.1 to 0.5 parts by mass.
　本発明で使用される機械物性付与剤組成物には、必要に応じて、フェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤、その他の酸化防止剤、核剤、紫外線吸収剤、光安定剤、可塑剤、充填剤、脂肪酸金属塩、帯電防止剤、顔料、染料等を配合することができる。
　これらの成分は本発明の機械物性付与剤組成物にあらかじめ配合することができ、該機械物性付与剤組成物を樹脂に配合することで、これらの成分を樹脂組成物に配合することができる。これらを配合することにより樹脂組成物を安定化することが好ましい。 The mechanical property-imparting agent composition used in the present invention may optionally contain a phenolic antioxidant, a phosphite antioxidant, a thioether antioxidant, other antioxidants, a nucleating agent, and an ultraviolet absorbing agent. agents, light stabilizers, plasticizers, fillers, fatty acid metal salts, antistatic agents, pigments, dyes and the like can be blended.
These components can be blended in advance in the mechanical property-imparting agent composition of the present invention, and by blending the mechanical property-imparting agent composition into the resin, these components can be blended into the resin composition. It is preferable to stabilize the resin composition by blending these.
　前記フェノール系酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、２－ｔｅｒｔ－ブチル－４，６－ジメチルフェノール、スチレン化フェノール、２，２’－メチレンビス（４－エチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－チオビス－（６－ｔｅｒｔ－ブチル－４－メチルフェノール）、２，２’－チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－メチル－４，６－ビス（オクチルスルファニルメチル）フェノール、２，２’－イソブチリデンビス（４，６－ジメチルフェノール）、イソオクチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、Ｎ，Ｎ’－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオンアミド］、２，２’－オキサミド－ビス［エチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、２－エチルヘキシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート、２，２’－エチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ－ベンゼンプロパン酸およびＣ１３－１５アルキルのエステル、２，５－ジ－ｔｅｒｔ－アミルヒドロキノン、ヒンダードフェノールの重合物（アデカパルマロール社製商品名ＡＯ．ＯＨ．９８）、２，２’－メチレンビス［６－（１－メチルシクロヘキシル）－ｐ－クレゾール］、２－ｔｅｒｔ－ブチル－６－（３－ｔｅｒｔ－ブチル－２－ヒドロキシ－５－メチルベンジル）－４－メチルフェニルアクリレート、２－［１－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ペンチルフェニル）エチル］－４，６－ジ－ｔｅｒｔ－ペンチルフェニルアクリレート、６－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチル）プロポキシ］－２，４，８，１０－テトラ－ｔｅｒｔ－ブチルベンズ［ｄ，ｆ］［１，３，２］－ジオキサホスフォビン、ヘキサメチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ビス［モノエチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート］カルシウム塩、５，７－ビス（１，１－ジメチルエチル）－３－ヒドロキシ－２（３Ｈ）－ベンゾフラノンとｏ－キシレンとの反応生成物、２，６－ジ－ｔｅｒｔ－ブチル－４－［４，６－ビス（オクチルチオ）－１，３，５－トリアジン－２－イルアミノ］フェノール、ＤＬ－ａ－トコフェノール（ビタミンＥ）、２，６－ビス（α－メチルベンジル）－４－メチルフェノール、ビス［３，３－ビス－（４’－ヒドロキシ－３’－ｔｅｒｔ－ブチルフェニル）ブタン酸］グリコールエステル、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、２，６－ジフェニル－４－オクタデシロキシフェノール、ステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート、ジステアリル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）ホスホネート、トリデシル－３，５－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルチオアセテート、チオジエチレンビス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、４，４’－チオビス（６－ｔｅｒｔ－ブチル－ｍ－クレゾール）、２－オクチルチオ－４，６－ジ（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェノキシ）－ｓ－トリアジン、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、ビス［３，３－ビス（４－ヒドロキシ－３－ｔｅｒｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’－ブチリデンビス（２，６－ジ－ｔｅｒｔ－ブチルフェノール）、４，４’－ブチリデンビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール）、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタン、ビス［２－ｔｅｒｔ－ブチル－４－メチル－６－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェニル］テレフタレート、１，３，５－トリス（２，６－ジメチル－３－ヒドロキシ－４－ｔｅｒｔ－ブチルベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－２，４，６－トリメチルベンゼン、１，３，５－トリス［（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、テトラキス［メチレン－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、２－ｔｅｒｔ－ブチル－４－メチル－６－（２－アクリロイルオキシ－３－ｔｅｒｔ－ブチル－５－メチルベンジル）フェノール、３，９－ビス［２－［３－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロパノイルオキシ］－１，１－ジメチルエチル］－２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、トリエチレングリコールビス－３－（３－ｔｅｒｔ－４－ヒドロキシ－５－メチルフェニル）プロピオネート、ステアリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、パルミチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ミリスチル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド、ラウリル－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオン酸アミド等の３－（３，５－ジアルキル－４－ヒドロキシフェニル）プロピオン酸誘導体等が挙げられる。これらフェノール系酸化防止剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6 -dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2' -thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidene Bis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,2′-oxamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2 -ethylhexyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate, 2,2′-ethylenebis(4,6-di-tert-butylphenol), 3,5-di -tert-butyl-4-hydroxy-benzenepropanoic acid and C 13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, hindered phenol polymer (manufactured by Adeka Palmarol Co., Ltd. under the trade name AO.OH. 98), 2,2′-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4 -methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert -butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylbenz[d,f][1,3,2]-dioxaphosphobin, hexamethylenebis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate]calcium salt, reaction product of 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-[4 ,6-bis(octylthio)-1,3,5-triazin-2-ylamino]phenol, DL-a-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, Bis[3,3-bis-(4′-hydroxy-3′-tert-butylphenyl)butanoic acid]glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4- Octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5- tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-tert-butyl-m-cresol ), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), Bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5- tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2 ,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5 -tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxy centre phenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy] -1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis-3-(3-tert-4-hydroxy-5-methylphenyl)propionate, stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, myristyl- 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic amide and the like 3-( 3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives and the like. One of these phenolic antioxidants may be used alone, or two or more thereof may be used in combination.
　これらのフェノール系酸化防止剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０１～１．０質量部となる量がより好ましい。 The amount of these phenolic antioxidants used is preferably 0.001 to 5 parts by mass in 100 parts by mass of the resin composition when blended in the resin, and 0.01 to 1.0 parts by mass. is more preferred.
　前記ホスファイト系酸化防止剤としては、例えば、トリフェニルホスファイト、ジイソオクチルホスファイト、ヘプタキス（ジプロピレングリコール）トリホスファイト、トリイソデシルホスファイト、ジフェニルイソオクチルホスファイト、ジイソオクチルフェニルホスファイト、ジフェニルトリデシルホスファイト、トリイソオクチルホスファイト、トリラウリルホスファイト、ジフェニルホスファイト、トリス（ジプロピレングリコール）ホスファイト、ジイソデシルペンタエリスリトールジホスファイト、ジオレイルヒドロゲンホスファイト、トリラウリルトリチオホスファイト、ビス（トリデシル）ホスファイト、トリス（イソデシル）ホスファイト、トリス（トリデシル）ホスファイト、ジフェニルデシルホスファイト、ジノニルフェニルビス（ノニルフェニル）ホスファイト、ポリ（ジプロピレングリコール）フェニルホスファイト、テトラフェニルジプロピレングリコールジホスファイト、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチル－５－メチルフェニル）ホスファイト、トリス［２－ｔｅｒｔ－ブチル－４－（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルチオ）－５－メチルフェニル］ホスファイト、トリ（デシル）ホスファイト、オクチルジフェニルホスファイト、ジ（デシル）モノフェニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールとステアリン酸カルシウム塩との混合物、アルキル（Ｃ１０）ビスフェノールＡホスファイト、ジ（トリデシル）ペンタエリスリトールジホスファイト、ジ（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４，６－トリ－ｔｅｒｔ－ブチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，４－ジクミルフェニル）ペンタエリスリトールジホスファイト、テトラフェニル－テトラ（トリデシル）ペンタエリスリトールテトラホスファイト、ビス（２，４－ジ－ｔｅｒｔ－ブチル－６－メチルフェニル）エチルホスファイト、テトラ（トリデシル）イソプロピリデンジフェノールジホスファイト、テトラ（トリデシル）－４，４’－ｎ－ブチリデンビス（２－ｔｅｒｔ－ブチル－５－メチルフェノール）ジホスファイト、ヘキサ（トリデシル）－１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔｅｒｔ－ブチルフェニル）ブタントリホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ビフェニレンジホスホナイト、９，１０－ジハイドロ－９－オキサ－１０－ホスファフェナンスレン－１０－オキサイド、（１－メチル－１－プロペニル－３－イリデン）トリス（１，１－ジメチルエチル）－５－メチル－４，１－フェニレン）ヘキサトリデシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－２－エチルヘキシルホスファイト、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－オクタデシルホスファイト、２，２’－エチリデンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）フルオロホスファイト、４，４’－ブチリデンビス（３－メチル－６－ｔｅｒｔ－ブチルフェニルジトリデシル）ホスファイト、トリス（２－［（２，４，８，１０－テトラキス－ｔｅｒｔ－ブチルジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン－６－イル）オキシ］エチル）アミン、３，９－ビス（４－ノニルフェノキシ）－２，４，８，１０－テトラオキサ－３，９－ジホスフェススピロ［５，５］ウンデカン、２，４，６－トリ－ｔｅｒｔ－ブチルフェニル－２－ブチル－２－エチル－１，３－プロパンジオールホスファイト、４，４’－イソプロピリデンジフェノールＣ１２－１５アルコールホスファイト、３，９－ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）－３，９－ビス－ジホスファ－２，４，８，１０－テトラオキサ－３，９－ジホスフェススピロ［５，５］ウンデカン、ジフェニル（イソデシル）ホスファイト、ビフェニルジフェニルホスファイト等が挙げられる。これらホスファイト系酸化防止剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the phosphite-based antioxidant include triphenylphosphite, diisooctylphosphite, heptakis (dipropylene glycol) triphosphite, triisodecylphosphite, diphenylisooctylphosphite, and diisooctylphenylphosphite. , diphenyltridecylphosphite, triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris(dipropyleneglycol)phosphite, diisodecylpentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryltrithiophosphite , bis(tridecyl)phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropyleneglycol)phenylphosphite, tetraphenyl Dipropylene glycol diphosphite, Trisnonylphenyl phosphite, Tris(2,4-di-tert-butylphenyl)phosphite, Tris(2,4-di-tert-butyl-5-methylphenyl)phosphite, Tris [2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tri(decyl)phosphite, octyldiphenylphosphite, di(decyl) ) monophenyl phosphite, distearyl pentaerythritol diphosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C 10 ) bisphenol A phosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl ) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tetra(tridecyl)isopropyl Redenediphenol 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-di-tert-butylphenyl)biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanth Lene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2'- methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylidenebis (4,6-di-tert-butylphenyl)fluorophosphite, 4,4′-butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2-[(2,4,8 , 10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2 ,4,8,10-tetraoxa-3,9-diphosphesspiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propane Diol phosphite, 4,4′-isopropylidenediphenol C 12-15 alcohol phosphite, 3,9-bis(2,6-di-tert-butyl-4-methylphenyl)-3,9-bis-diphospha -2,4,8,10-tetraoxa-3,9-diphosphesspiro[5,5]undecane, diphenyl(isodecyl)phosphite, biphenyldiphenylphosphite and the like. One of these phosphite-based antioxidants may be used alone, or two or more thereof may be used in combination.
　これらのホスファイト系酸化防止剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０１～１．０質量部となる量がより好ましい。 The amount of these phosphite-based antioxidants used is preferably 0.001 to 5 parts by mass, preferably 0.01 to 1.0 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. is more preferable.
　前記チオエーテル系酸化防止剤としては、例えば、３，３’－チオジプロピオン酸、アルキル（Ｃ１２－１４）チオプロピオン酸、ジ（ラウリル）－３，３’－チオジプロピオネート、３，３’－チオビスプロピオン酸ジトリデシル、ジ（ミリスチル）－３，３’－チオジプロピオネート、ジ（ステアリル）－３，３’－チオジプロピオネート、ジ（オクタデシル）－３，３’－チオジプロピオネート、ラウリルステアリルチオジプロピオネート、テトラキス［メチレン－３－（ドデシルチオ）プロピオネート］メタン、チオビス（２－ｔｅｒｔ－ブチル－５－メチル－４，１－フェニレン）ビス（３－（ドデシルチオ）プロピオナート）、２，２’－チオジエチレンビス（３－アミノブテノエート）、４，６－ビス（オクチルチオメチル）－ｏ－クレゾール、２，２’－チオジエチレンビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］、２，２’－チオビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－チオビス（６－ｔｅｒｔ－ブチル－ｐ－クレゾール）、２－エチルヘキシル－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）チオアセテート、４，４’－チオビス（６－ｔｅｒｔ－ブチル－３－メチルフェノール）、４，４’－チオビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、４，４’－［チオビス（メチレン）］ビス（２－ｔｅｒｔ－ブチル－６－メチル－１－ヒドロキシベンジル）、ビス（４，６－ジ－ｔｅｒｔ－ブチルフェノール－２－イル）スルファイド、トリデシル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルチオアセテート、１，４－ビス（オクチルチオメチル）－６－メチルフェノール、２，４－ビス（ドデシルチオメチル）－６－メチルフェノール、ジステアリル－ジサルファイド、ビス（メチル－４－［３－ｎ－アルキル（Ｃ１２／Ｃ１４）チオプロピオニルオキシ］５－ｔｅｒｔ－ブチルフェニル）スルファイド等が挙げられる。これらチオエーテル系酸化防止剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the thioether antioxidant include 3,3′-thiodipropionic acid, alkyl(C 12-14 )thiopropionic acid, di(lauryl)-3,3′-thiodipropionate, 3,3 '-ditridecyl thiobispropionate, di(myristyl)-3,3'-thiodipropionate, di(stearyl)-3,3'-thiodipropionate, di(octadecyl)-3,3'-thiodipropionate pionate, lauryl stearyl thiodipropionate, tetrakis[methylene-3-(dodecylthio)propionate]methane, thiobis(2-tert-butyl-5-methyl-4,1-phenylene)bis(3-(dodecylthio)propionate) , 2,2′-thiodiethylenebis(3-aminobutenoate), 4,6-bis(octylthiomethyl)-o-cresol, 2,2′-thiodiethylenebis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionate], 2,2′-thiobis(4-methyl-6-tert-butylphenol), 2,2′-thiobis(6-tert-butyl-p-cresol), 2 -ethylhexyl-(3,5-di-tert-butyl-4-hydroxybenzyl)thioacetate, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(4- methyl-6-tert-butylphenol), 4,4′-[thiobis(methylene)]bis(2-tert-butyl-6-methyl-1-hydroxybenzyl), bis(4,6-di-tert-butylphenol- 2-yl) sulfide, tridecyl-3,5-di-tert-butyl-4-hydroxybenzylthioacetate, 1,4-bis(octylthiomethyl)-6-methylphenol, 2,4-bis(dodecylthiomethyl )-6-methylphenol, distearyl-disulfide, bis(methyl-4-[3-n-alkyl(C 12 /C 14 )thiopropionyloxy]5-tert-butylphenyl)sulfide and the like. One of these thioether-based antioxidants may be used alone, or two or more thereof may be used in combination.
　これらのチオエーテル系酸化防止剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０１～１．０質量部となる量がより好ましい。 The amount of these thioether-based antioxidants used is preferably 0.001 to 5 parts by mass in 100 parts by mass of the resin composition when blended in the resin, and 0.01 to 1.0 parts by mass. is more preferred.
　前記その他の酸化防止剤としては、例えば、Ｎ－ベンジル－α－フェニルニトロン、Ｎ－エチル－α－メチルニトロン、Ｎ－オクチル－α－ヘプチルニトロン、Ｎ－ラウリル－α－ウンデシルニトロン、Ｎ－テトラデシル－α－トリデシルニトロン、Ｎ－ヘキサデシル－α－ペンタデシルニトロン、Ｎ－オクチル－α－ヘプタデシルニトロン、Ｎ－ヘキサデシル－α－ヘプタデシルニトロン、Ｎ－オクタデシル－α－ペンタデシルニトロン、Ｎ－ヘプタデシル－α－ヘプタデシルニトロン、Ｎ－オクタデシル－α－ヘプタデシルニトロン等のニトロン化合物、３－アリールベンゾフラン－２（３Ｈ）－オン、３－（アルコキシフェニル）ベンゾフラン－２－オン、３－（アシルオキシフェニル）ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－（３，４－ジメチルフェニル）－ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－（４－ヒドロキシフェニル）－ベンゾフラン－２（３Ｈ）－オン、５，７－ジ－ｔｅｒｔ－ブチル－３－［４－（２－ヒドロキシエトキシ）フェニル］－ベンゾフラン－２（３Ｈ）－オン、６－（２－［４－（５，７－ジ－ｔｅｒｔ－２－オキソ－２，３－ジヒドロベンゾフラン－３－イル）フェノキシ］エトキシ）－６－オキソヘキシル－６－［（６－ヒドロキシヘキサノイル）オキシ］ヘキサノエート、５－ジ－ｔｅｒｔ－ブチル－３－（４－［（１５－ヒドロキシ－３，６，９，１３－テトラオキサペンタデシル）オキシ］フェニル）ベンゾフラン－２（３Ｈ）オン等のベンゾフラン化合物等が挙げられる。これらその他の酸化防止剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of other antioxidants include N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-α-undecyl nitrone, N- Tetradecyl-α-tridecyl nitrone, N-hexadecyl-α-pentadecyl nitrone, N-octyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N- Nitrone compounds such as heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-heptadecyl nitrone, 3-arylbenzofuran-2(3H)-one, 3-(alkoxyphenyl)benzofuran-2-one, 3-(acyloxy Phenyl)benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl -3-(4-hydroxyphenyl)-benzofuran-2(3H)-one, 5,7-di-tert-butyl-3-[4-(2-hydroxyethoxy)phenyl]-benzofuran-2(3H)- on, 6-(2-[4-(5,7-di-tert-2-oxo-2,3-dihydrobenzofuran-3-yl)phenoxy]ethoxy)-6-oxohexyl-6-[(6- Hydroxyhexanoyl)oxy]hexanoate, 5-di-tert-butyl-3-(4-[(15-hydroxy-3,6,9,13-tetraoxapentadecyl)oxy]phenyl)benzofuran-2(3H) and benzofuran compounds such as on. These other antioxidants may be used alone or in combination of two or more.
　これらその他の酸化防止剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０１～１．０質量部となる量がより好ましい。 The amount of these other antioxidants used is preferably 0.001 to 5 parts by mass, and 0.01 to 1.0 parts by mass in 100 parts by mass of the resin composition when blended in the resin. quantity is more preferred.
　前記核剤としては、例えば、安息香酸ナトリウム、４－ｔｅｒｔ－ブチル安息香酸アルミニウム塩、アジピン酸ナトリウム、２ナトリウムビシクロ［２．２．１］ヘプタン－２，３－ジカルボキシレート等のカルボン酸金属塩、ナトリウムビス（４－ｔｅｒｔ－ブチルフェニル）ホスフェート、ナトリウム－２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート、リチウム－２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）ホスフェート等のリン酸エステル金属塩、ジベンジリデンソルビトール、ビス（メチルベンジリデン）ソルビトール、ビス（３，４－ジメチルベンジリデン）ソルビトール、ビス（ｐ－エチルベンジリデン）ソルビトール、ビス（ジメチルベンジリデン）ソルビトール、１，２，３－トリデオキシ－４，６：５，７－ビス－Ｏ－［（４－プロピルフェニル）メチレン］－ノニトール、１，３：２，４－ビス（ｐ－メチルベンジリデン）ソルビトール、１，３：２，４－ビス－Ｏ－ベンジリデン－Ｄ－グルシトール（ジベンジリデンソルビトール）等の多価アルコール誘導体、Ｎ，Ｎ’，Ｎ”－トリス［２－メチルシクロヘキシル］－１，２，３－プロパントリカルボキサミド、Ｎ，Ｎ’，Ｎ”－トリシクロヘキシルー１，３，５－ベンゼントリカルボキサミド、Ｎ，Ｎ’－ジシクロヘキシル－ナフタレンジカルボキサミド、１，３，５－トリ（ジメチルイソプロポイルアミノ）ベンゼン等のアミド化合物等を挙げることができる。これら核剤は１種を単独で用いることができ、２種以上を併用して用いることができる。 Examples of the nucleating agent include carboxylic acid metals such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate. salts, sodium bis(4-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, lithium-2,2′-methylenebis(4,6-di Phosphate metal salts such as -tert-butylphenyl)phosphate, dibenzylidene sorbitol, bis(methylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, bis(p-ethylbenzylidene) sorbitol, bis(dimethylbenzylidene) ) Sorbitol, 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonitol, 1,3:2,4-bis(p-methylbenzylidene) Sorbitol, polyhydric alcohol derivatives such as 1,3:2,4-bis-O-benzylidene-D-glucitol (dibenzylidene sorbitol), N,N',N''-tris[2-methylcyclohexyl]-1,2 ,3-propanetricarboxamide, N,N′,N″-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N′-dicyclohexyl-naphthalenedicarboxamide, 1,3,5-tri(dimethylisopropoxy) and amide compounds such as ylamino)benzene. One of these nucleating agents can be used alone, or two or more thereof can be used in combination.
　これらの核剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０１～１．０質量部となる量がより好ましい。 The amount of these nucleating agents to be used is preferably 0.001 to 5 parts by mass, and preferably 0.01 to 1.0 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. more preferred.
　前記紫外線吸収剤としては、例えば、２，４－ジヒドロキシベンゾフェノン、５，５’－メチレンビス（２－ヒドロキシ－４－メトキシベンゾフェノン）、２－ヒドロキシ－４－ノルマルオクトキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－ドデシルオキシベンゾフェノン、２，２’－ジヒドロキシ―４－メトキシベンゾフェノン等のベンゾフェノン系や、２－（２－ヒドロキシ－５－メチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－５－ｔｅｒｔ－オクチルフェニル）ベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２－ヒドロキシ－３，５－ジクミルフェニル）ベンゾトリアゾール、２，２’－メチレンビス（４－ｔｅｒｔ－オクチル－６－ベンゾトリアゾリルフェノール）、２－（２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－カルボキシフェニル）ベンゾトリアゾールのポリエチレングリコールエステル、２－［２－ヒドロキシ－３－（２－アクリロイルオキシエチル）－５－メチルフェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－オクチルフェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－（２－メタクリロイルオキシエチル）－５－ｔｅｒｔ－ブチルフェニル］－５－クロロベンゾトリアゾール、２－［２－ヒドロキシ－５－（２－メタクリロイルオキシエチル）フェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（２－メタクリロイルオキシエチル）フェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－ｔｅｒｔ－アミル－５－（２－メタクリロイルオキシエチル）フェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－３－ｔｅｒｔ－ブチル－５－（３－メタクリロイルオキシプロピル）フェニル］－５－クロロベンゾトリアゾール、２－［２－ヒドロキシ－４－（２－メタクリロイルオキシメチル）フェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－４－（３－メタクリロイルオキシ－２－ヒドロキシプロピル）フェニル］ベンゾトリアゾール、２－［２－ヒドロキシ－４－（３－メタクリロイルオキシプロピル）フェニル］ベンゾトリアゾール等のベンゾトリアゾール系や、フェニルサリシレート、レゾルシノールモノベンゾエート、２，４－ジ－ｔｅｒｔ－ブチルフェニル－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンゾエート、オクチル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ドデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、テトラデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ヘキサデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、オクタデシル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート、ベヘニル（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシ）ベンゾエート等のベンゾエート系や、２－エチル－２’－エトキシオキザニリド、２－エトキシ－４’－ドデシルオキザニリド、２－エチル－２’－エトキシ－５’－ｔｅｒｔ－ブチル－オキザニリド等の置換オキザニリド系や、エチル－α－シアノ－β，β－ジフェニルアクリレート、メチル－２－シアノ－３－メチル－３－（ｐ－メトキシフェニル）アクリレート、テトラキス（α－シアノ－β，β－ジフェニルアクリルロイルオキシメチル）メタン等のシアノアクリレート系や、２－（２－ヒドロキシ－４－［２－（２－エチルヘキサノイルオキシ）エチルオキシ］）－４，６－ジフェニル－１，３，５－トリアジン、２，４，６－トリス（２－ヒドロキシ－４－ヘキシルオキシ－３－メチルフェニル）－１，３，５－トリアジン、２－（２－ヒドロキシ－４－オクチルフオキシフェニル）－４，６－ビス（２，４－ジメチルフェニル）－１，３，５－トリアジン、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－ヘキシルオキシフェノール、２－（［４，６－ジ（１，１’－ビフェニル）４－イル］－１，３，５－トリアジン－２－イル）－５－（２－エチルヘキシルオキシ）フェノール等のトリアジン系が挙げられる。これら紫外線吸収剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone), 2-hydroxy-4-normal octoxybenzophenone, 2-hydroxy-4- Benzophenones such as methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2- hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-tert-butyl- 5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)benzotriazole, 2,2′-methylenebis(4-tert-octyl-6-benzotriazolylphenol ), polyethylene glycol ester of 2-(2-hydroxy-3-tert-butyl-5-carboxyphenyl)benzotriazole, 2-[2-hydroxy-3-(2-acryloyloxyethyl)-5-methylphenyl]benzo triazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert- Octylphenyl]benzotriazole, 2-[2-hydroxy-3-(2-methacryloyloxyethyl)-5-tert-butylphenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyl oxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy- 4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxy-2-hydroxy benzotriazoles such as hydroxypropyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole, phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert -butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-tert-butyl-4 -hydroxy)benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl (3,5-di-tert-butyl-4-hydroxy)benzoate, octadecyl (3,5-di-tert -butyl-4-hydroxy)benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy)benzoate, 2-ethyl-2'-ethoxyoxanylide, 2-ethoxy-4' -dodecyl oxanilide, 2-ethyl-2'-ethoxy-5'-tert-butyl-oxanilide and substituted oxanilides such as ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3 -Methyl-3-(p-methoxyphenyl) acrylate, tetrakis (α-cyano-β, β-diphenylacrylloyloxymethyl) cyanoacrylates such as methane, 2-(2-hydroxy-4-[2-( 2-ethylhexanoyloxy)ethyloxy])-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1, 3,5-triazine, 2-(2-hydroxy-4-octylphoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(4,6- Diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-([4,6-di(1,1′-biphenyl)4-yl]-1,3,5-triazine triazines such as -2-yl)-5-(2-ethylhexyloxy)phenol. One of these ultraviolet absorbers may be used alone, or two or more thereof may be used in combination.
　これらの紫外線吸収剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０５～０．５質量部となる量がより好ましい。 The amount of these ultraviolet absorbers used is preferably an amount of 0.001 to 5 parts by mass, and an amount of 0.05 to 0.5 parts by mass in 100 parts by mass of the resin composition when blended in the resin. is more preferred.
　前記光安定剤としては、例えば、２，２，６，６－テトラメチル－４－ピペリジルステアレート、１，２，２，６，６－ペンタメチル－４－ピペリジルステアレート、２，２，６，６－テトラメチル－４－ピペリジルベンゾエート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、テトラキス（２，２，６，６－テトラメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（２，２，６，６－テトラメチル－４－ピペリジル）・ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－ジ（トリデシル）－１，２，３，４－ブタンテトラカルボキシレート、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）－２－ブチル－２－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）マロネート、１－（２－ヒドロキシエチル）－２，２，６，６－テトラメチル－４－ピペリジノ－ル／コハク酸ジエチル重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－モルホリノ－ｓ－トリアジン重縮合物、１，６－ビス（２，２，６，６－テトラメチル－４－ピペリジルアミノ）ヘキサン／２，４－ジクロロ－６－ｔｅｒｔ－オクチルアミノ－ｓ－トリアジン重縮合物、１，５，８，１２－テトラキス（２，４－ビス［Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジ）アミノ］－ｓ－トリアジン－６－イル）－１，５，８，１２－テトラアザドデカン、１，５，８，１２－テトラキス（２，４－ビス［Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ］－ｓ－トリアジン－６－イル）－１，５，８－１２－テトラアザドデカン、１，６，１１－トリス（２，４－ビス［Ｎ－ブチル－Ｎ－（２，２，６，６－テトラメチル－４－ピペリジル）アミノ］－ｓ－トリアジン－６－イル）アミノウンデカン、１，６，１１－トリス（２，４－ビス［Ｎ－ブチル－Ｎ－（１，２，２，６，６－ペンタメチル－４－ピペリジル）アミノ］－ｓ－トリアジン－６－イル）アミノウンデカン、ビス［４－（１－オクチルオキシ－２，２，６，６－テトラメチル）ピペリジル］デカンジオナート、ビス［４－（２，２，６，６－テトラメチル－１－ウンデシルオキシ）ピペリジル］カーボナート、チバ・スペシャルティ・ケミカルズ製ＴＩＮＵＶＩＮ　ＮＯＲ　３７１、２，２，６，６－テトラメチル－４－ピペリジルメタクリレート、１，２，３，４－ブタンテトラカルボン酸、２，２－ビス（ヒドロキシメチル）－１，３－プロパンジオールおよび３－ヒドロキシ－２，２－ジメチルプロパナールトノポリマー、１，２，２，６，６－ペンタメチル－４－ピペリジニルエステル、１，３－ビス（２，２，６，６－テトラメチルピペリジン－４－イル）－２，４－ジトリデシルベンゼン－１，２，３，４－テトラカルボキシレート、ビス（１－オクチルオキシ－２，２，６，６－テトラメチル－４－ピペリジル）セバケート、ポリ［［６－［（１，１，３，３－テトラメチルブチル）アミノ］－１，３，５－トリアジン－２，４－ジイル］［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］－１，６－ヘキサンジイル［（２，２，６，６－テトラメチル－４－ピペリジニル）イミノ］］）等が挙げられる。これら光安定剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the 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-piperidyl benzoate, bis(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(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-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)hexane/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-piperidi)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)amino Undecane, bis[4-(1-octyloxy-2,2,6,6-tetramethyl l) piperidyl]decandionate, bis[4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl]carbonate, Ciba Specialty Chemicals TINUVIN NOR 371, 2,2,6, 6-tetramethyl-4-piperidyl methacrylate, 1,2,3,4-butanetetracarboxylic acid, 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanediol Panart Nopolymer, 1,2,2,6,6-pentamethyl-4-piperidinyl ester, 1,3-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2,4-ditri Decylbenzene-1,2,3,4-tetracarboxylate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly[[6-[(1,1, 3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexane diyl [(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) and the like. One of these light stabilizers may be used alone, or two or more of them may be used in combination.
　これらの光安定剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．００５～０．５質量部となる量がより好ましい。 The amount of these light stabilizers to be used is preferably an amount of 0.001 to 5 parts by mass, and an amount of 0.005 to 0.5 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. is more preferred.
　前記可塑剤としては、例えば、エポキシ化大豆油、エポキシ化亜麻仁油、エポキシ化脂肪酸オクチルエステル等のエポキシ系や、メタクリレート系や、ジカルボン酸と多価アルコールとの重縮合物、多価カルボン酸と多価アルコールとの重縮合物等のポリエステル系や、ジカルボン酸と多価アルコールとアルキレングリコールとの重縮合物、ジカルボン酸と多価アルコールとアリーレングリコールとの重縮合物、多価カルボン酸と多価アルコールとアルキレングリコールとの重縮合物、多価カルボン酸と多価アルコールとアリーレングリコールとの重縮合物等のポリエーテルエステル系や、アジピン酸エステル、コハク酸エステル等の脂肪族エステル系や、フタル酸エステル、テレフタル酸エステル、トリメリット酸エステル、ピロメリット酸エステル、安息香酸エステル等の芳香族エステル系などが挙げられる。これら可塑剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the plasticizer include epoxy-based soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl ester and the like; methacrylate-based; polycondensates of dicarboxylic acid and polyhydric alcohol; Polyesters such as polycondensates with polyhydric alcohols, polycondensates of dicarboxylic acids, polyhydric alcohols and alkylene glycol, polycondensates of dicarboxylic acids, polyhydric alcohols and arylene glycol, polyether esters such as polycondensates of a polyhydric alcohol and an alkylene glycol, polycondensates of a polyhydric carboxylic acid, a polyhydric alcohol and an arylene glycol; aliphatic esters such as adipic acid esters and succinic acid esters; Aromatic esters such as phthalate, terephthalate, trimellitate, pyromellitate, benzoate and the like are included. These plasticizers may be used individually by 1 type, and may use 2 or more types together.
　これらの可塑剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．１～５００質量部となる量が好ましく、１～１００質量部となる量がより好ましい。 The amount of these plasticizers used is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
　前記充填剤としては、例えば、タルク、マイカ、炭酸カルシウム、酸化カルシウム、水酸化カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、硫酸マグネシウム、水酸化アルミニウム、硫酸バリウム、ガラス粉末、ガラス繊維、クレー、ドロマイト、マイカ、シリカ、アルミナ、チタン酸カリウムウィスカー、ワラステナイト、繊維状マグネシウムオキシサルフェート、モンモリロナイト等を挙げることができ、粒子径（繊維状においては繊維径や繊維長およびアスペクト比）を適宜選択して用いることができる。これら充填剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, montmorillonite, etc. can be mentioned, and the particle size (in the fibrous form, the fiber diameter, fiber length and aspect ratio) can be selected appropriately. can be used These fillers may be used individually by 1 type, and may use 2 or more types together.
　これらの充填剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、１～１００質量部となる量が好ましく、３～８０質量部となる量がより好ましい。 The amount of these fillers used is preferably 1 to 100 parts by mass, more preferably 3 to 80 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
　前記脂肪酸金属塩の脂肪酸としては、例えば、カプリン酸、２－エチルヘキサン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルチミン酸、マルガリン酸、ステアリン酸、ノナデシル酸、アラキジン酸、ヘイコシル酸、ベヘン酸、トリコシル酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸等の飽和脂肪酸、４－デセン酸、４－ドデセン酸、パルミトレイン酸、α－リノレン酸、リノール酸、γ－リノレン酸、ステアリドン酸、ペトロセリン酸、オレイン酸、エライジン酸、バクセン酸、エイコサペンタエン酸、ドコサペンタエン酸、ドコサヘキサエン酸等の直鎖不飽和脂肪酸、トリメシン酸等の芳香族脂肪酸であるものが挙げられ、特に、ミリスチン酸、ステアリン酸、１２－ヒドロキシステアリン酸等の飽和脂肪酸が好ましい。脂肪酸金属塩の金属としては、例えば、アルカリ金属、マグネシウム、カルシウム、ストロンチウム、バリウム、チタニウム、マンガン、鉄、亜鉛、珪素、ジルコニウム、イットリウム、バリウムまたはハフニウム等が挙げられるが、特に、ナトリウム、リチウム、カリウム等のアルカリ金属が好ましい。これら脂肪酸金属塩は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the fatty acid of the fatty acid metal salt include capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, Heicosylic acid, behenic acid, tricosylic acid, lignoceric acid, cerotic acid, montanic acid, saturated fatty acids such as melissic acid, 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid , stearidonic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid and other linear unsaturated fatty acids, and trimesic acid and other aromatic fatty acids, particularly , myristic acid, stearic acid and 12-hydroxystearic acid are preferred. Examples of the metal of the fatty acid metal salt include alkali metals, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium or hafnium, and particularly sodium, lithium, Alkali metals such as potassium are preferred. One of these fatty acid metal salts may be used alone, or two or more thereof may be used in combination.
　これらの脂肪酸金属塩の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．００１～５質量部となる量が好ましく、０．０５～３質量部となる量がより好ましい。 The amount of these fatty acid metal salts used is preferably 0.001 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the resin composition when blended in the resin. preferable.
　前記帯電防止剤としては、例えば、脂肪酸第四級アンモニウムイオン塩、ポリアミン四級塩等のカチオン系帯電防止剤や、高級アルコールリン酸エステル塩、高級アルコールＥＯ付加物、ポリエチレングリコール脂肪酸エステル、アニオン型のアルキルスルホン酸塩、高級アルコール硫酸エステル塩、高級アルコールエチレンオキシド付加物硫酸エステル塩、高級アルコールエチレンオキシド付加物リン酸エステル塩等のアニオン系帯電防止剤や、多価アルコール脂肪酸エステル、ポリグリコールリン酸エステル、ポリオキシエチレンアルキルアリルエーテル等のノニオン系帯電防止剤や、アルキルジメチルアミノ酢酸ベタイン等の両性型アルキルベタイン、イミダゾリン型両性活性剤等の両性帯電防止剤が挙げられる。これら帯電防止剤は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts, higher alcohol phosphate salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, and anionic antistatic agents. Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates, polyhydric alcohol fatty acid esters, polyglycol phosphate esters , polyoxyethylene alkylallyl ether and other nonionic antistatic agents, amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric antistatic agents such as imidazoline type amphoteric surfactants. One of these antistatic agents may be used alone, or two or more thereof may be used in combination.
　これらの帯電防止剤の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．０１～２０質量部となる量が好ましく、３～１０質量部となる量がより好ましい。 The amount of these antistatic agents used is preferably 0.01 to 20 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the resin composition when mixed with the resin.
　前記顔料は、市販の顔料を用いることもでき、例えば、ピグメントレッド１、２、３、９、１０、１７、２２、２３、３１、３８、４１、４８、４９、８８、９０、９７、１１２、１１９、１２２、１２３、１４４、１４９、１６６、１６８、１６９、１７０、１７１、１７７、１７９、１８０、１８４、１８５、１９２、２００、２０２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４；ピグメントオレンジ１３、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、６５、７１や、ピグメントイエロー１、３、１２、１３、１４、１６、１７、２０、２４、５５、６０、７３、８１、８３、８６、９３、９５、９７、９８、１００、１０９、１１０、１１３、１１４、１１７、１２０、１２５、１２６、１２７、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１６６、１６８、１７５、１８０、１８５や、ピグメントグリーン７、１０、３６や、ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、２２、２４、５６、６０、６１、６２、６４や、ピグメントバイオレット１、１９、２３、２７、２９、３０、３２、３７、４０、５０等が挙げられる。これら顔料は１種を単独で用いてもよく、２種以上を併用してもよい。 Commercially available pigments can also be used as the pigment, for example Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112 , 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224 Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71 and pigment yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114,117,120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180,185 and pigment green 7,10 , 36, Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 56, 60, 61, 62, 64, Pigment Violet 1 , 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like. These pigments may be used individually by 1 type, and may use 2 or more types together.
　これらの顔料の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．０００１～１０質量部となる量が好ましい。 The amount of these pigments to be used is preferably 0.0001 to 10 parts by mass in 100 parts by mass of the resin composition when mixed with the resin.
　前記染料は、市販の染料を用いることもでき、例えば、アゾ染料、アントラキノン染料、インジゴイド染料、トリアリールメタン染料、キサンテン染料、アリザリン染料、アクリジン染料、スチルベン染料、チアゾール染料、ナフトール染料、キノリン染料、ニトロ染料、インダミン染料、オキサジン染料、フタロシアニン染料、シアニン染料等の染料等が挙げられる。これら染料は１種を単独で用いてもよく、２種以上を併用してもよい。 Commercially available dyes can also be used as the dyes. Examples include dyes such as nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These dyes may be used individually by 1 type, and may use 2 or more types together.
　これらの染料の使用量は、樹脂に配合したときに、樹脂組成物１００質量部中、０．０００１～１０質量部となる量が好ましい。 The amount of these dyes used is preferably 0.0001 to 10 parts by mass based on 100 parts by mass of the resin composition when mixed with the resin.
　本発明の機械物性付与剤組成物を得るためには、必須成分の（Ａ）成分、（Ｂ）成分、および必要に応じて（Ｃ）～（Ｄ）成分、並びに、さらに必要に応じて他の任意成分を混合すればよく、混合には各種混合機を用いることができる。混合時には加熱することができる。使用できる混合機の例を挙げると、ターブラーミキサー、ヘンシェルミキサー、リボンブレンダー、Ｖ型混合機、Ｗ型混合機、スーパーミキサー、ナウターミキサー等が挙げられる。 In order to obtain the mechanical property-imparting agent composition of the present invention, the essential components (A), (B), and optionally (C) to (D), and optionally other Any of the optional components may be mixed, and various mixers can be used for mixing. Heat can be applied during mixing. Examples of mixers that can be used include Turbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauta mixers, and the like.
　本発明の機械物性付与剤組成物は、樹脂に機械物性を付与する効果があり、樹脂用組成物（「樹脂用添加剤」と呼ばれることもある）、特に機械物性付与剤として有用である。本発明の機械物性付与剤組成物は、これを樹脂に配合することで、機械物性が付与された樹脂組成物（以下、本発明の樹脂組成物ともいう）として好ましく用いられる。 The mechanical property-imparting agent composition of the present invention has the effect of imparting mechanical properties to resins, and is useful as a resin composition (sometimes referred to as a "resin additive"), particularly as a mechanical property-imparting agent. The mechanical property-imparting agent composition of the present invention is preferably used as a resin composition imparted with mechanical properties (hereinafter also referred to as the resin composition of the present invention) by blending it with a resin.
　本発明の機械物性付与剤組成物によって機械物性が付与される樹脂としては、熱可塑性樹脂および熱硬化性樹脂等の合成樹脂が挙げられる。具体的には、熱可塑性樹脂としては、ポリオレフィン系樹脂、バイオマス含有ポリオレフィン系樹脂、含ハロゲン樹脂、芳香族ポリエステル樹脂、直鎖ポリエステル樹脂、分解性脂肪族、ポリアミド樹脂、セルロースエステル系樹脂；ポリカーボネート樹脂、ポリウレタン樹脂、ポリフェニレンオキシド系樹脂、ポリフェニレンスルフィド系樹脂、アクリル系樹脂等の熱可塑性樹脂およびこれらのブレンド物を挙げることができる。一方、熱硬化性樹脂としては、フェノール樹脂、ユリア樹脂、メラミン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等を挙げることができる。 Synthetic resins such as thermoplastic resins and thermosetting resins are examples of resins to which mechanical properties are imparted by the agent composition for imparting mechanical properties of the present invention. Specifically, thermoplastic resins include polyolefin resins, biomass-containing polyolefin resins, halogen-containing resins, aromatic polyester resins, linear polyester resins, degradable aliphatics, polyamide resins, cellulose ester resins; polycarbonate resins. , thermoplastic resins such as polyurethane resins, polyphenylene oxide resins, polyphenylene sulfide resins, acrylic resins, and blends thereof. On the other hand, thermosetting resins include phenol resins, urea resins, melamine resins, epoxy resins, unsaturated polyester resins, and the like.
　本発明の機械物性付与剤組成物によって機械物性が付与される別の合成樹脂として、オレフィン系熱可塑性エラストマー、スチレン系熱可塑性エラストマー、ポリエステル系熱可塑性エラストマー、ニトリル系熱可塑性エラストマー、ナイロン系熱可塑性エラストマー、塩化ビニル系熱可塑性エラストマー、ポリアミド系熱可塑性エラストマー、ポリウレタン系熱可塑性エラストマー等も挙げることができる。 Other synthetic resins to which mechanical properties are imparted by the agent composition for imparting mechanical properties of the present invention include olefinic thermoplastic elastomers, styrene thermoplastic elastomers, polyester thermoplastic elastomers, nitrile thermoplastic elastomers, and nylon thermoplastic elastomers. Elastomers, vinyl chloride-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and the like can also be used.
　これら樹脂は、１種を単独で用いてもよく、２種以上を併用してもよい。また樹脂はアロイ化されている場合がある。 These resins may be used singly or in combination of two or more. Also, the resin may be alloyed.
　本発明で使用する樹脂は、分子量、重合度、密度、軟化点、溶媒への不溶分の割合、立体規則性の程度、触媒残渣の有無、原料となるモノマーの種類や配合比率、重合触媒の種類（例えば、チーグラー触媒、メタロセン触媒等）等に関わらず、使用することができる。 The resin used in the present invention has molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of raw material monomer, polymerization catalyst. It can be used regardless of the type (for example, Ziegler catalyst, metallocene catalyst, etc.).
　以上の各種樹脂の中でも、優れた機械物性を付与できる点から、ポリオレフィン系樹脂またはポリウレタン系熱可塑性エラストマーが好ましい。ポリオレフィン系樹脂としては、例えば、ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ホモポリプロピレン、ランダムコポリマーポリプロピレン、ブロックコポリマーポリプロピレン、インパクトコポリマーポリプロピレン、ハイインパクトコポリマーポリプロピレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、ヘミアイソタクチックポリプロピレン、無水マレイン酸変性ポリプロピレン、ポリブテン、シクロオレフィンポリマー、ステレオブロックポリプロピレン、ポリ－３－メチル－１－ブテン、ポリ－３－メチル－１－ペンテン、ポリ－４－メチル－１－ペンテン等のα－オレフィン重合体、エチレン／プロピレンブロックまたはランダム共重合体、エチレン－メチルメタクリレート共重合体、エチレン－酢酸ビニル共重合体等のα－オレフィン共重合体等が挙げられる。 Among the various resins described above, polyolefin-based resins or polyurethane-based thermoplastic elastomers are preferable because they can impart excellent mechanical properties. Examples of polyolefin resins include 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, and isotactic. Polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, maleic anhydride-modified polypropylene, polybutene, cycloolefin polymer, stereoblock polypropylene, poly-3-methyl-1-butene, poly-3-methyl-1-pentene, poly - α-olefin polymers such as 4-methyl-1-pentene, ethylene/propylene block or random copolymers, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate copolymers, etc. is mentioned.
　またポリウレタン系熱可塑性エラストマーとしては、熱可塑性ポリウレタン樹脂（ＴＰＵ）が挙げられる。熱可塑性ポリウレタン樹脂（ＴＰＵ）は分子構造中に、ウレタン基（－ＮＨＣＯＯ－）を有するゴム状弾性体であり、ソフトセグメントと称される動きやすい長鎖部分と、ハードセグメントと称される極めて結晶性の強い部分とからなり、一般に、ポリオール、ジイソシアネート、および鎖延長剤を用いて調製される。 Thermoplastic polyurethane resins (TPU) can also be mentioned as thermoplastic polyurethane elastomers. Thermoplastic polyurethane resin (TPU) is a rubber-like elastic body having a urethane group (-NHCOO-) in its molecular structure. It consists of strong moieties and is generally prepared using polyols, diisocyanates, and chain extenders.
　また、熱可塑性ポリウレタン樹脂は、その成形方法により、液状で型に注入・硬化反応させる注型タイプ、従来のゴムと同じくロール混練後プレス成形するタイプおよび一般熱可塑性樹脂と同様に加工できるタイプに大別できるが、本発明では、それらを区別するものではない。 Depending on the molding method, thermoplastic polyurethane resin can be divided into a casting type in which liquid is poured into a mold and cured, a type in which roll-kneading and press molding is performed as with conventional rubber, and a type that can be processed in the same manner as general thermoplastic resins. Although they can be broadly classified, the present invention does not distinguish between them.
　前記熱可塑性ポリウレタン樹脂の具体例としては、エステル（ラクトン）系ポリウレタン共重合体、エステル（アジペート）系ポリウレタン共重合体、エーテル系ポリウレタン共重合体、カーボネート系ポリウレタン共重合体、エーテル・エステル系ポリウレタン共重合体が挙げられ、これらの熱可塑性ポリウレタン樹脂（ＴＰＵ）は、単独で用いることができ、組み合わせて用いることができる。 Specific examples of the thermoplastic polyurethane resin include ester (lactone)-based polyurethane copolymers, ester (adipate)-based polyurethane copolymers, ether-based polyurethane copolymers, carbonate-based polyurethane copolymers, and ether/ester-based polyurethanes. Copolymers are included, and these thermoplastic polyurethane resins (TPU) can be used alone or in combination.
　本発明の樹脂組成物において、樹脂の含有量は、好ましくは５０～９９．９質量％であり、より好ましくは６０～９０質量％である。また本発明の樹脂組成物は、樹脂１００質量部に対し、機械物性付与剤組成物を１０質量部～４００質量部含有することが好ましく、２０～８０質量部含有することがより好ましい。本発明の機械物性付与剤組成物の含有量を１０質量部以上に設定することで十分な難燃性および機械物性が発揮され、４００質量部以下に設定することで樹脂本来の物性が損なわれにくくなる。
　本発明の樹脂組成物はこれを成形することにより、難燃性および機械物性に優れた成形品を得ることができる。成形方法は、特に限定されるものではなく、押し出し加工、カレンダー加工、射出成形、ロール、圧縮成形、ブロー成形等が挙げられ、樹脂板、シート、フィルム、異形品等の種々の形状の成形品が製造できる。 In the resin composition of the present invention, the resin content is preferably 50 to 99.9% by mass, more preferably 60 to 90% by mass. The resin composition of the present invention preferably contains 10 to 400 parts by mass, more preferably 20 to 80 parts by mass, of the mechanical property imparting agent composition per 100 parts by mass of the resin. By setting the content of the mechanical property-imparting agent composition of the present invention to 10 parts by mass or more, sufficient flame retardancy and mechanical properties are exhibited, and by setting the content to 400 parts by mass or less, the original physical properties of the resin are impaired. becomes difficult.
By molding the resin composition of the present invention, a molded article having excellent flame retardancy and mechanical properties can be obtained. The molding method is not particularly limited, and includes extrusion, calendering, injection molding, roll molding, compression molding, blow molding, etc., and molded products of various shapes such as resin plates, sheets, films, irregular shaped products, etc. can be manufactured.
　本発明の樹脂組成物およびその成形体は、電気・電子・通信、エレクトロニック＆エンジニアリング、農林水産、鉱業、建設、食品、繊維、衣類、医療、石炭、石油、ゴム、皮革、自動車、精密機器、木材、建材、土木、家具、印刷、楽器等の幅広い産業分野に使用することができる。より具体的には、プリンター、パソコン、ワープロ、キーボード、ＰＤＡ（小型情報端末機）、電話機、複写機、ファクシミリ、ＥＣＲ（電子式金銭登録機）、電卓、電子手帳、カード、ホルダー、文具等の事務、ＯＡ機器、洗濯機、冷蔵庫、掃除機、電子レンジ、照明器具、ゲーム機、アイロン、コタツ等の家電機器、ＴＶ、ＶＴＲ、ビデオカメラ、ラジカセ、テープレコーダー、ミニディスク、ＣＤプレーヤー、スピーカー、液晶ディスプレー等のＡＶ機器、コネクター、リレー、コンデンサー、スイッチ、プリント基板、コイルボビン、半導体封止材料、ＬＥＤ封止材料、電線、ケーブル、トランス、偏向ヨーク、分電盤、時計等の電気・電子部品および通信機器、ＯＡ機器等のハウジング（枠、筐体、カバー、外装）や部品、自動車内外装材の用途に用いられる。この中でも特に、電線等の電子部品や自動車内外装部材等の自動車部品に好適に用いられる。 The resin composition of the present invention and its molded product are used in electrical/electronic/communication, electronic & engineering, 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 equipment, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, household appliances such as kotatsu, TVs, VTRs, video cameras, radio cassette players, tape recorders, mini discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, electrical and electronic parts such as clocks It is also used for housings (frames, cases, covers, exteriors) and parts of communication equipment, OA equipment, etc., and interior and exterior materials for automobiles. Among these, in particular, it is suitably used for electronic parts such as electric wires and automobile parts such as automobile interior and exterior members.
　さらに、本発明の樹脂組成物およびその成形体は、座席（詰物、表地等）、ベルト、天井張り、コンパーチブルトップ、アームレスト、ドアトリム、リアパッケージトレイ、カーペット、マット、サンバイザー、ホイルカバー、マットレスカバー、エアバック、絶縁材、吊り手、吊り手帯、電線被覆材、電気絶縁材、塗料、コーティング材、上張り材、床材、隅壁、カーペット、壁紙、壁装材、外装材、内装材、屋根材、デッキ材、壁材、柱材、敷板、塀の材料、骨組および繰形、窓およびドア形材、こけら板、羽目、テラス、バルコニー、防音板、断熱板、窓材等の、自動車、ハイブリッドカー、電気自動車、車両、船舶、航空機、建物、住宅および建築用材料や、土木材料、衣料、カーテン、シーツ、合板、合繊板、絨毯、玄関マット、シート、バケツ、ホース、容器、眼鏡、鞄、ケース、ゴーグル、スキー板、ラケット、テント、楽器等の生活用品、スポーツ用品、等の各種用途に使用される。 Furthermore, the resin composition of the present invention and its molded product can be used for seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers. , airbags, insulating materials, straps, straps, wire coating materials, electrical insulating materials, paints, coating materials, covering materials, floor materials, corner walls, carpets, wallpaper, wall covering materials, exterior materials, interior materials , roofing materials, decking materials, wall materials, pillar materials, decking boards, fence materials, frames and moldings, window and door profiles, shingles, siding, terraces, balconies, soundproofing boards, heat insulating boards, window materials, etc. , automobiles, hybrid cars, electric vehicles, vehicles, ships, aircraft, buildings, housing and construction materials, civil engineering materials, clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, entrance mats, sheets, buckets, hoses, containers , eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments and other daily necessities, and sports goods.
　以下、実施例により本発明をさらに詳細に説明する。しかし、本発明は以下の実施例より何ら制限されるものではない。なお、以下の表１～２中の各成分量の単位は質量部である。 The present invention will be described in more detail below with reference to examples. However, the present invention is in no way limited by the following examples. The unit of each component amount in Tables 1 and 2 below is parts by mass.
＜製造例１：（Ａ－１）メラミン塩の製造＞
　オルトリン酸メラミンを２２０℃で６時間、固相状態で加熱縮合反応させて、ピロリン酸メラミンを主成分とするメラミン塩を製造した。メラミン塩は精製せずにそのまま用いた。メラミン塩中のピロリン酸メラミンの純度は、９８．５％であった。 <Production Example 1: (A-1) Production of melamine salt>
Melamine orthophosphate was heat-condensed at 220° C. for 6 hours in a solid state to produce a melamine salt containing melamine pyrophosphate as a main component. The melamine salt was used as is without purification. The purity of melamine pyrophosphate in the melamine salt was 98.5%.
＜製造例２：（Ａ－２）ピペラジン塩の製造＞
　二リン酸ピペラジンを２５０℃で１時間、固相状態で加熱縮合反応させて、ピロリン酸ピペラジンを主成分とするピペラジン塩を製造した。ピペラジン塩は精製せずにそのまま用いた。ピペラジン塩中のピロリン酸ピペラジンの純度は、９９．０％であった。 <Production Example 2: (A-2) Production of piperazine salt>
Piperazine diphosphate was heated and condensed at 250° C. for 1 hour in a solid state to produce a piperazine salt containing piperazine pyrophosphate as a main component. The piperazine salt was used as is without purification. The purity of piperazine pyrophosphate in the piperazine salt was 99.0%.
　上記メラミン塩およびピペラジン塩の純度は、イオンクロマトグラフ測定装置ＩＣＳ－２１００（サーモフィッシャーサイエンティフィック株式会社）、Ｄｉｏｎｅｘ　ＩｏｎＰａｃ　ＡＳ－１９カラム（サーモフィッシャーサイエンティフィック株式会社）、電気伝導度検出器を用いて測定した。 The purities of the above melamine salts and piperazine salts were measured using an ion chromatograph ICS-2100 (Thermo Fisher Scientific Co., Ltd.), a Dionex IonPac AS-19 column (Thermo Fisher Scientific Co., Ltd.), and an electrical conductivity detector. was measured using
＜機械物性付与剤組成物の調製＞
　下記表１および２に記載の成分のうち、樹脂以外の成分を当該成分表に記載の割合で配合し、ヘンシェルミキサーを用いて混合した。但し、（Ｄ）成分を添加する場合には、その他の成分を予備混合した後に、（Ｄ）成分を添加してヘンシェルミキサーを用いて混合し、機械物性付与剤組成物を得た。
　メラミン塩およびピペラジン塩として上記製造例１～２で製造したものを用いた。 <Preparation of mechanical property imparting agent composition>
Of the components shown in Tables 1 and 2 below, the components other than the resin were blended at the ratios shown in the component tables and mixed using a Henschel mixer. However, when component (D) was added, after premixing the other components, component (D) was added and mixed using a Henschel mixer to obtain a composition for imparting mechanical properties.
As the melamine salt and piperazine salt, those produced in Production Examples 1 and 2 above were used.
＜樹脂組成物の調製１＞
・実施例１～１５および比較例１～５
　熱可塑性ポリウレタン樹脂（ＢＡＳＦ製　Ｅｌａｓｔｏｌｌａｎ　１１８５Ａ）１００質量部にステアリン酸カルシウム０．１質量部、グリセリンモノステアレート０．３質量部、テトラキス［３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオン酸メチル］メタン０．１質量部、２，２’－メチレンビス（４，６－ジ－ｔｅｒｔ－ブチルフェニル）－２－エチルヘキシルホスファイト０．１質量部を配合し、ヘンシェルミキサーにて予備混合して熱可塑性ポリウレタン樹脂組成物Ｘを得た。得られた熱可塑性ポリウレタン樹脂組成物Ｘに対して、表１または２に示す成分を表に記載の質量部配合し、ヘンシェルミキサーで混合し樹脂組成物を得た。 <Preparation 1 of resin composition>
・Examples 1 to 15 and Comparative Examples 1 to 5
Thermoplastic polyurethane resin (BASF Elastollan 1185A) 100 parts by weight calcium stearate 0.1 parts by weight, glycerin monostearate 0.3 parts by weight, tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl ) 0.1 part by mass of methyl propionate]methane and 0.1 part by mass of 2,2′-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite were blended, and preliminarily mixed with a Henschel mixer. A thermoplastic polyurethane resin composition X was obtained by mixing. The components shown in Table 1 or 2 were added to the obtained thermoplastic polyurethane resin composition X in parts by weight shown in the table, and mixed with a Henschel mixer to obtain a resin composition.
＜樹脂組成物の調製２＞
・実施例１６～２０および比較例６～１０
　ポリプロピレン（ＪＩＳ　Ｋ７２１０に準拠して測定された、荷重２．１６ｋｇ、２３０℃におけるメルトフローレート＝８ｇ／１０ｍｉｎ）１００質量部に、ステアリン酸カルシウム０．１質量部、テトラキス［３－（３，５－ジ第三ブチル－４－ヒドロキシフェニル）プロピオン酸メチル］メタン０．１質量部、トリス（２，４－ジ－第三ブチルフェニル）ホスファイト０．１質量部を配合し、ヘンシェルミキサーにて予備混合してポリプロピレン樹脂組成物Ｙを得た。得られたポリプロピレン樹脂組成物Ｙに対して、表１または表２に示す成分を表に記載の質量部配合し、ヘンシェルミキサーで混合し樹脂組成物を得た。 <Preparation of resin composition 2>
・Examples 16 to 20 and Comparative Examples 6 to 10
Polypropylene (measured in accordance with JIS K7210, load 2.16 kg, melt flow rate at 230 ° C. = 8 g / 10 min) 100 parts by mass, calcium stearate 0.1 parts by mass, tetrakis [3-(3,5- 0.1 part by mass of di-tert-butyl-4-hydroxyphenyl)methyl propionate]methane and 0.1 part by mass of tris(2,4-di-tert-butylphenyl) phosphite were blended, and a preliminary mixture was used in a Henschel mixer. A polypropylene resin composition Y was obtained by mixing. The components shown in Table 1 or Table 2 were added to the obtained polypropylene resin composition Y in the parts by weight shown in the table, and mixed with a Henschel mixer to obtain a resin composition.
＜評価用試験片の作製＞
　前記で得られた各樹脂組成物から以下の方法にてペレットを作製した。
　熱可塑性ポリウレタン樹脂を含有する実施例１～１５の樹脂組成物および比較例１～４の樹脂組成物を、二軸押出成形機（株式会社日本製鋼所製；ＴＥＸ－３０α）を用いて、シリンダー温度を１７０～２００℃、およびスクリュー速度１５０ｒｐｍの条件で溶融混練した。ダイスから吐出されたストランドを冷却バスにより冷却し、ペレタイザーにて切断することにより、樹脂組成物のペレットを作製した。
　ポリプロピレン樹脂を含有する実施例１６～２０の樹脂組成物および比較例５～８の樹脂組成物を、二軸押出成形機（株式会社日本製鋼所製；ＴＥＸ－３０α）を用いて、シリンダー温度２２０～２３０℃、およびスクリュー速度１５０ｒｐｍの条件で溶融混練した。ダイスから吐出されたストランドを冷却バスにより冷却し、ペレタイザーにて切断することにより、樹脂組成物のペレットを作製した。 <Preparation of test piece for evaluation>
Pellets were produced from each resin composition obtained above by the following method.
The resin compositions of Examples 1 to 15 containing a thermoplastic polyurethane resin and the resin compositions of Comparative Examples 1 to 4 were extruded into cylinders using a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.; TEX-30α). Melt-kneading was performed at a temperature of 170 to 200° C. and a screw speed of 150 rpm. The strand discharged from the die was cooled in a cooling bath and cut with a pelletizer to prepare pellets of the resin composition.
The resin compositions of Examples 16 to 20 and the resin compositions of Comparative Examples 5 to 8 containing polypropylene resin were extruded at a cylinder temperature of 220 using a twin-screw extruder (manufactured by Japan Steel Works, Ltd.; TEX-30α). Melt-kneading was carried out under conditions of ~230°C and a screw speed of 150 rpm. The strand discharged from the die was cooled in a cooling bath and cut with a pelletizer to prepare pellets of the resin composition.
　前記で得られた樹脂組成物のペレットを、射出成形機（日精樹脂工業社製；ＮＥＸ－８０）を用いて射出成形を行い、引張特性評価用のＩＳＯ　Ｔｙｐｅ－Ａダンベル片および長さ１２７ｍｍ、幅１２．７ｍｍ、厚さ１．６ｍｍの難燃性評価用試験片を得た。実施例１～１３および比較例については、スクリュー設定温度を１９０℃とし、金型温度を５０℃とした。実施例１４～１６および比較例７～１２については、スクリュー設定温度２３０℃とし、金型温度を４０℃とした。 The pellets of the resin composition obtained above were injection molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd.; NEX-80), and an ISO Type-A dumbbell piece for tensile property evaluation and a length of 127 mm, A test piece for flame retardancy evaluation having a width of 12.7 mm and a thickness of 1.6 mm was obtained. For Examples 1 to 13 and Comparative Example, the set screw temperature was 190°C and the mold temperature was 50°C. For Examples 14-16 and Comparative Examples 7-12, the set screw temperature was 230°C and the mold temperature was 40°C.
［評価］
＜引張特性評価＞
　上記で得られたダンベル片を用い、ＩＳＯ　５２７に準拠した測定方法で、引張伸び（％）および引張強度（ＭＰａ）を測定した。評価結果を表１および表２に示す。
＜難燃性評価＞
　上記で得られた試験片を用い、ＩＳＯ　１２１０に準拠し２０ｍｍ垂直燃焼試験（ＵＬ９４　Ｖ試験）を行った。具体的には試験片を垂直に保ち、下端にバーナーの火を１０秒間接炎させた後で炎を取り除き、試験片に着火した火が消える時間を測定した。次に、火が消えると同時に２回目の接炎を１０秒間行い、１回目と同様にして着火した火が消える時間を測定した。また、落下する火種により試験片の下の綿が着火するか否かについても同時に評価した。１回目と２回目の燃焼時間、綿着火の有無等からＵＬ９４　Ｖ規格に従って燃焼ランクをつけた。燃焼ランクはＶ－０が最高のものであり、Ｖ－１、Ｖ－２となるに従って難燃性は低下する。Ｖ－０～Ｖ－２のランクの何れにも該当しないものはＮＲと判定した。評価結果を表１および表２に示す。 [evaluation]
<Tensile property evaluation>
Tensile elongation (%) and tensile strength (MPa) were measured by the measurement method based on ISO 527 using the dumbbell piece obtained above. Evaluation results are shown in Tables 1 and 2.
<Flame retardant evaluation>
Using the test piece obtained above, a 20 mm vertical burning test (UL94 V test) was conducted in accordance with ISO 1210. Specifically, the test piece was held vertically, a burner flame was applied to the lower end of the test piece for 10 seconds, the flame was removed, and the time for the test piece to extinguish was measured. Next, as soon as the fire was extinguished, the flame was applied for a second time for 10 seconds, and the time for the ignited fire to extinguish was measured in the same manner as the first time. At the same time, it was also evaluated whether or not the falling spark would ignite the cotton under the test piece. Combustion ranks were given according to the UL94 V standard from the first and second burning times, the presence or absence of cotton ignition, and the like. V-0 is the highest flammability rank, and flame retardance decreases as V-1 and V-2 are reached. Those that did not correspond to any of the ranks of V-0 to V-2 were judged as NR. Evaluation results are shown in Tables 1 and 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000004
  
Figure JPOXMLDOC01-appb-T000004
　表１～２に示す結果から明らかなとおり、（Ａ）成分および（Ｂ）成分を含有する機械物性付与剤組成物を樹脂に配合した各実施例において、ＵＬ－９４Ｖ試験における樹脂の難燃性評価および引張特性評価が向上することが判る。 As is clear from the results shown in Tables 1 and 2, in each example in which the resin was blended with the mechanical property-imparting agent composition containing the components (A) and (B), the flame retardance of the resin in the UL-94V test was It can be seen that the evaluation and tensile property evaluation are improved.
　これに対し、（Ａ－１）成分および（Ａ－２）成分の合計含有量１００質量部に対する（Ｂ）成分の含有量が１０質量部未満の場合（比較例１、３、５）は引張伸びおよび引張強度が不十分であり、４０質量部を超える場合（比較例２、４、６）は、難燃性評価ランクが下がる。 On the other hand, when the content of component (B) with respect to the total content of 100 parts by mass of components (A-1) and (A-2) is less than 10 parts by mass (Comparative Examples 1, 3, 5), tensile When the elongation and tensile strength are insufficient and the amount exceeds 40 parts by mass (Comparative Examples 2, 4 and 6), the flame retardancy evaluation rank is lowered.
　従って、本発明の機械物性付与剤組成物が、高い難燃性および良好な機械物性を樹脂に付与でき、機械物性付与剤として優れていることが判る。 Therefore, it can be seen that the mechanical property-imparting agent composition of the present invention can impart high flame retardancy and good mechanical properties to resins, and is excellent as a mechanical property-imparting agent.

Claims (7)

  1. 　（Ａ）成分：リン酸アミン塩および（Ｂ）成分：メラミンシアヌレートを含有する機械物性付与剤組成物であって、
    　（Ａ）成分が、下記（Ａ－１）成分および（Ａ－２）成分を含有し、
    　（Ａ－１）成分および（Ａ－２）成分の合計１００質量部に対して（Ｂ）成分を１０質量部以上４０質量部以下含有する、機械物性付与剤組成物。
    　（Ａ－１）成分：オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含むメラミン塩。
    　（Ａ－２）成分：オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含むピペラジン塩。     (A) component: amine phosphate salt and (B) component: a mechanical property-imparting agent composition containing melamine cyanurate,
    (A) component contains the following (A-1) component and (A-2) component,
    A mechanical property-imparting agent composition containing 10 parts by mass or more and 40 parts by mass or less of component (B) with respect to a total of 100 parts by mass of components (A-1) and (A-2).
    (A-1) Component: A melamine salt containing at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
    (A-2) Component: a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
  2. 　さらに（Ｃ）成分：酸化亜鉛を、（Ａ）成分１００質量部に対して０．０１～１０質量部含有する、請求項１に記載の機械物性付与剤組成物。 The composition for imparting mechanical properties according to claim 1, further comprising 0.01 to 10 parts by mass of component (C): zinc oxide per 100 parts by mass of component (A).
  3. 　さらに（Ｄ）成分：シリコーンオイル、エポキシ系カップリング剤、ハイドロタルサイトおよび滑剤からなる群から選ばれる少なくとも１種を、（Ａ）成分１００質量部に対して０．０１～５質量部含有する、請求項１または２に記載の機械物性付与剤組成物。 Furthermore, component (D): 0.01 to 5 parts by mass of at least one selected from the group consisting of silicone oil, epoxy coupling agent, hydrotalcite and lubricant per 100 parts by mass of component (A). 3. The composition for imparting mechanical properties according to claim 1 or 2.
  4. 　樹脂１００質量部に対して請求項１～３のいずれか１項に記載の機械物性付与剤組成物を１０～４００質量部含有する樹脂組成物。 A resin composition containing 10 to 400 parts by mass of the mechanical property imparting agent composition according to any one of claims 1 to 3 with respect to 100 parts by mass of the resin.
  5. 　請求項４に記載の樹脂組成物を用いてなる成形品。 A molded article using the resin composition according to claim 4.
  6. 　下記（Ａ－１）成分および（Ａ－２）成分を含有する（Ａ）成分：リン酸アミン塩と、（Ｂ）成分：メラミンシアヌレートとを、（Ａ－１）成分および（Ａ－２）成分の合計１００質量部に対して（Ｂ）成分１０～４０質量部の比率で含有する組成物を、樹脂と混合する、樹脂の機械物性付与方法。
    　（Ａ－１）成分：オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含むメラミン塩。
    　（Ａ－２）成分：オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含むピペラジン塩。     (A) component containing the following (A-1) component and (A-2) component: phosphoric acid amine salt, (B) component: melamine cyanurate, (A-1) component and (A-2) A method for imparting mechanical properties to a resin, comprising mixing a composition containing 10 to 40 parts by mass of component (B) with respect to a total of 100 parts by mass of components ).
    (A-1) Component: A melamine salt containing at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
    (A-2) Component: a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
  7. 　下記（Ａ－１）成分および（Ａ－２）成分を含有する（Ａ）成分：リン酸アミン塩と、（Ｂ）成分：メラミンシアヌレートとを、（Ａ－１）成分および（Ａ－２）成分の合計１００質量部に対して（Ｂ）成分１０～４０質量部の比率で含有する組成物の、機械物性付与剤としての使用。
    　（Ａ－１）成分：オルトリン酸メラミン、ピロリン酸メラミンおよびポリリン酸メラミンよりなる群から選択される少なくとも１種を含むメラミン塩。
    　（Ａ－２）成分：オルトリン酸ピペラジン、ピロリン酸ピペラジンおよびポリリン酸ピペラジンよりなる群から選択される少なくとも１種を含むピペラジン塩。
     
     
          (A) component containing the following (A-1) component and (A-2) component: phosphoric acid amine salt, (B) component: melamine cyanurate, (A-1) component and (A-2) ) as a mechanical property-imparting agent of a composition containing 10 to 40 parts by mass of component (B) per 100 parts by mass of components in total.
    (A-1) Component: A melamine salt containing at least one selected from the group consisting of melamine orthophosphate, melamine pyrophosphate and melamine polyphosphate.
    (A-2) Component: a piperazine salt containing at least one selected from the group consisting of piperazine orthophosphate, piperazine pyrophosphate and piperazine polyphosphate.
PCT/JP2022/016821 2021-04-08 2022-03-31 Mechanical property-imparting agent composition, resin composition and molded article WO2022215660A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09221567A (en) * 1996-02-13 1997-08-26 Chisso Corp Flame-retardant polyolefin resin composition
WO2012161070A1 (en) * 2011-05-25 2012-11-29 堺化学工業株式会社 Flame-retardant agent and flame-retardant resin composition
WO2014080821A1 (en) * 2012-11-21 2014-05-30 堺化学工業株式会社 Flame retardant and flame-retardant resin composition
WO2019021671A1 (en) * 2017-07-24 2019-01-31 株式会社Adeka Composition and flame-retardant resin composition
WO2019054155A1 (en) * 2017-09-12 2019-03-21 株式会社Adeka Composition and flame retardant resin composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09221567A (en) * 1996-02-13 1997-08-26 Chisso Corp Flame-retardant polyolefin resin composition
WO2012161070A1 (en) * 2011-05-25 2012-11-29 堺化学工業株式会社 Flame-retardant agent and flame-retardant resin composition
WO2014080821A1 (en) * 2012-11-21 2014-05-30 堺化学工業株式会社 Flame retardant and flame-retardant resin composition
WO2019021671A1 (en) * 2017-07-24 2019-01-31 株式会社Adeka Composition and flame-retardant resin composition
WO2019054155A1 (en) * 2017-09-12 2019-03-21 株式会社Adeka Composition and flame retardant resin composition

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