WO2009090710A1 - Non-expandable vinyl chloride resin composition - Google Patents
Non-expandable vinyl chloride resin composition Download PDFInfo
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- WO2009090710A1 WO2009090710A1 PCT/JP2008/003740 JP2008003740W WO2009090710A1 WO 2009090710 A1 WO2009090710 A1 WO 2009090710A1 JP 2008003740 W JP2008003740 W JP 2008003740W WO 2009090710 A1 WO2009090710 A1 WO 2009090710A1
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- vinyl chloride
- chloride resin
- resin composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
Definitions
- the present invention relates to a non-foaming vinyl chloride resin composition, and particularly to a non-foaming vinyl chloride resin composition having excellent heat resistance and color resistance.
- Chlorine-containing resins such as vinyl chloride resin are used in various fields because they are excellent in flame retardancy and chemical resistance. However, since chlorine-containing resins are thermally decomposed to generate hydrogen chloride, they have the disadvantage that the mechanical strength is reduced and coloring occurs and the commercial value is impaired.
- ultraviolet absorbers such as organic phosphite compounds, epoxy compounds, phenolic antioxidants, benzophenone or benzotriazoles, Various additives such as hindered amine light stabilizers are combined and used as a stabilizing aid for improving resistance to light, heat, oxidation and the like.
- Various additives such as hindered amine light stabilizers are combined and used as a stabilizing aid for improving resistance to light, heat, oxidation and the like.
- Patent Document 1 describes that a Ca-Zn stabilizer and a higher fatty acid potassium salt are used in combination.
- Patent Document 1 describes that a Ca-Zn stabilizer and a higher fatty acid potassium salt are used in combination.
- the system using the foaming agent as described above has a drawback that it is not possible to sufficiently obtain an improvement effect on heat resistance and color resistance.
- an object of the present invention is to provide a non-foamable vinyl chloride resin composition capable of providing a product excellent in heat resistance and color resistance without using a heavy metal stabilizer such as lead. There is.
- the present inventors have found that in the case of a non-foamable vinyl chloride resin composition that does not use a foaming agent, an organic acid calcium salt, an organic acid zinc salt, and It has been found that the heat resistance and coloration resistance of the vinyl chloride resin composition can be remarkably improved by using the organic acid potassium salt in combination, and the present invention has been achieved.
- the present invention provides a non-foamable vinyl chloride resin composition containing no foaming agent, comprising at least (a) an organic acid calcium salt, (b) an organic acid zinc salt, and (c) an organic acid potassium salt.
- a non-foamable vinyl chloride resin composition comprising 5 parts by mass, (b) 0.01 to 5 parts by mass, and (c) 0.001 to 1 part by mass.
- the component (a) and the component (b) are preferably used so that the molar ratio of calcium to zinc is 1/1 to 10/1.
- the component (c) includes the component (a) and It is preferable that potassium is used in an amount of 0.01 to 0.3 mol with respect to 1 mol of the total amount of component (b) calcium and zinc.
- non-foamable vinyl chloride resin composition of the present invention is excellent in thermal stability and color resistance, it is possible to provide a vinyl chloride resin molded product of higher quality than conventional products.
- the vinyl chloride resin used in the present invention can be obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like, and the polymerization method is not particularly limited.
- Specific resins include, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer.
- Examples of the organic acid calcium salt as the component (a) used in the present invention include calcium salts of organic carboxylic acids, phenols and organic phosphoric acids.
- organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, and tridecanoic acid.
- phenols for example, tert-butylphenol, nonylphenol, di-nonylphenol, cyclohexyl phenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n- butylphenol, isoamyl phenol, ethyl phenol, isopropyl phenol, isooctylphenol, Examples include 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, and methyltertiaryoctylphenol.
- organic phosphoric acids examples include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, Examples include phosphonic acid stearyl ester.
- the amount of the organic acid calcium salt added in the present invention is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- organic acid zinc salt (b) used in the present invention examples include zinc salts of organic carboxylic acids, phenols and organic phosphoric acids. What was mentioned above is mentioned as an example of organic carboxylic acid, phenols, and organic phosphoric acids.
- the zinc salts of the organic carboxylic acids, phenols and organic phosphoric acids described above may be any of acidic salts, neutral salts and basic salts, and some or all of the bases of the basic salts.
- An overbased complex neutralized with carbonic acid may be used.
- the amount of the organic acid zinc salt which is the component (b) is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
- Examples of the organic acid potassium salt as component (c) used in the present invention include zinc salts of organic carboxylic acids, phenols and organic phosphoric acids.
- Examples of organic carboxylic acids, phenols and organic phosphoric acids include those already exemplified.
- the zinc salts of the organic carboxylic acids, phenols and organic phosphoric acids may be any of acidic salts, neutral salts and basic salts, and these may be a part or all of the bases in the basic salts.
- An overbased complex obtained by neutralizing with carbonic acid may be used.
- the amount of the organic acid potassium salt added is 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the vinyl chloride resin.
- the ratio of the component (a) and the component (b) is 1 / molar ratio of calcium and zinc. It is preferably 1 to 10/1, and more preferably 2/1 to 8/1. Furthermore, the ratio of the component (c) is preferably 0.01 to 0.3 mol, more preferably 0.05 to 0.25 mol of potassium with respect to 1 mol of the total amount of calcium and zinc of the components (a) and (b). More preferred.
- composition of the present invention includes other additives usually used in vinyl chloride resin compositions, such as plasticizers, hydrotalcite compounds, zeolite compounds, ⁇ -diketone compounds, perchlorates, epoxy compounds.
- plasticizers such as plasticizers, hydrotalcite compounds, zeolite compounds, ⁇ -diketone compounds, perchlorates, epoxy compounds.
- Polyhydric alcohol, phosphorus-based, phenol-based and sulfur-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, fillers, lubricants, and the like can be added.
- plasticizer examples include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like; dioctyl adipate, diisononyl adipate , Diisodecyl adipate, di (butyl diglycol) adipate and the like adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri Phosphate such as (butoxyethyl) phosphate, oct
- polyester plasticizer using acid, terephthalic acid, etc., and monohydric alcohol or monocarboxylic acid as a stopper if necessary; tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearin Acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid Plasticizers, biphenyltetracarboxylic acid ester plasticizer, and chlorinated plasticizers and the like.
- the hydrotalcite compound is a carbonate double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (I).
- x1 and x2 in the formula (I) each represent a number satisfying the condition represented by the following formula, and m represents a real number. 0 ⁇ x2 / x1 ⁇ 10 and 2 ⁇ x1 + x2 ⁇ 20.
- the hydrotalcite compound may be a natural product or a synthetic product.
- a method for synthesizing the above synthetic product known methods such as those described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 61-174270, etc. Things can be used.
- the hydrotalcite compound can be used without being limited by the crystal structure, the crystal particle size, the presence or absence of crystal water, and the amount thereof.
- hydrotalcite treated with perchloric acid can also be used, and the surface thereof has higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, alkali dodecylbenzenesulfonate.
- An organic sulfonic acid metal salt such as a metal salt, a higher fatty acid amide, a higher fatty acid ester, or a wax coated with a wax can also be used.
- the zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and representative examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Site, sodalite group aluminosilicate, clinobutyrolite, erionite, chabazite and the like.
- These zeolitic compounds may be water-containing substances having crystal water (so-called zeolite water) or anhydrides from which crystal water has been removed.
- the particle diameter of these compounds is preferably from 0.1 to 50 ⁇ m, particularly preferably from 0.5 to 10 ⁇ m.
- ⁇ -diketone compound examples include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and the like. In the present invention, these metal salts are also useful as described above.
- perchlorates include perchloric acid metal salts, ammonium perchlorate, perchloric acid-treated hydrotalcite, and perchloric acid-treated silicates.
- metal constituting the metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum.
- the perchloric acid metal salt may be an anhydride or a hydrated salt.
- butyl diglycol even those dissolved in an alcohol-based solvent and ester type such as butyl diglycol adipate, may be the dehydrated product.
- epoxy compound examples include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil.
- polyhydric alcohol examples include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate,
- examples include glycerin, diglycerin, and tris (2-hydroxyethyl) isocyanurate.
- Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tride
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6- Ter
- sulfur-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and ⁇ -alkyl mercapto of polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl
- ⁇ -alkyl mercapto of polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate).
- propionic acid esters examples include propionic acid esters.
- Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone).
- 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis 2-
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Butyl-2- (3,5-ditert-butyl
- filler examples include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotlite, MOS, phosphate fiber, and glass fiber. , Carbonate fiber, aramid fiber and the like.
- the lubricant examples include hydrocarbons such as natural paraffin and low molecular weight polyethylene, fatty acids such as stearic acid, lauric acid and erucic acid, aliphatic alcohols such as cetyl alcohol and stearyl alcohol, stearic acid amide, and melenbis.
- fatty acid amides such as stearamide, lower alcohol esters of fatty acids such as butyl stearate, higher alcohol esters of higher fatty acids such as glycerol monostearate, and the like.
- additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatment agents, flame retardants , Fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, processing aids, antioxidants, light stabilizers, and the like.
- composition of the present invention can be used regardless of the processing method of the vinyl chloride resin.
- it can be suitably used for calendar processing, roll processing, extrusion molding processing, melt rolling, injection molding processing, pressure molding processing, paste processing, powder molding processing, foam molding processing, and the like.
- composition of the present invention comprises: wall materials, floor materials, window frames, wall materials, corrugated sheets, gutters, etc .; automotive interior and exterior materials; fish food packaging materials such as trays; packings, gaskets, hoses, pipes, It can be used for joints, sheets, toys, etc.
- non-foamable vinyl chloride resin composition of the present invention can provide a vinyl chloride resin molded product having better thermal stability and color resistance than conventional products, it can be used in various industrial fields. worth it.
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Abstract
Disclosed is a non-expandable vinyl chloride resin composition which contains at least (a) an organic acid calcium salt, (b) an organic acid zinc salt and (c) an organic acid potassium salt and which does not contain any foaming agent. The contents of the organic acid calcium salt (a), the organic acid zinc salt (b) and the organic acid potassium salt (c) are 0.01 to 5 parts by mass, 0.01 to 5 parts by mass and 0.001 to 1 part by mass, respectively, relative to 100 parts by mass of a vinyl chloride resin. It becomes possible to provide a non-expandable vinyl chloride resin composition having excellent heat resistance and coloring resistance without the need of using any heavy metal stabilizer such as lead.
Description
本発明は、非発泡性塩化ビニル系樹脂組成物に関し、特に、耐熱性及び耐着色性に優れた非発泡性塩化ビニル系樹脂組成物に関する。
The present invention relates to a non-foaming vinyl chloride resin composition, and particularly to a non-foaming vinyl chloride resin composition having excellent heat resistance and color resistance.
塩化ビニル樹脂等の塩素含有樹脂は、難燃性及び耐薬品性に優れていることから、種々の分野において用いられている。しかしながら、塩素含有樹脂は、熱的に分解して塩化水素を発生するために、機械的強度の低下や着色が生じて商品価値を損なうという欠点を有している。
Chlorine-containing resins such as vinyl chloride resin are used in various fields because they are excellent in flame retardancy and chemical resistance. However, since chlorine-containing resins are thermally decomposed to generate hydrogen chloride, they have the disadvantage that the mechanical strength is reduced and coloring occurs and the commercial value is impaired.
上記欠点を解決するために、従来から種々の安定剤が開発されており、特に鉛化合物やカドミウム化合物とバリウム化合物の混合物等が優れた安定化効果をもつことが知られている。しかしながら、近年、安全性の観点から鉛化合物やカドミウム化合物の使用が制限される傾向にあるため、安全性の高い亜鉛化合物と、アルカリ土類金属の有機酸塩やハイドロタルサイト、ゼオライト等の無機化合物を併用することによる安定化方法に変更されつつある。
In order to solve the above drawbacks, various stabilizers have been developed, and it is known that a lead compound, a mixture of a cadmium compound and a barium compound, etc. have an excellent stabilizing effect. However, in recent years, the use of lead compounds and cadmium compounds tends to be restricted from the viewpoint of safety. Therefore, highly safe zinc compounds and alkaline earth metal organic acid salts, hydrotalcite, zeolites and other inorganic materials It is being changed to the stabilization method by using a compound together.
ところが、これらの低毒性の安定剤は、それだけでは十分な安定化効果が得られないため、有機ホスファイト化合物、エポキシ化合物、フェノール系酸化防止剤、ベンゾフェノン系又はベンゾトリアゾール系等の紫外線吸収剤、ヒンダードアミン系光安定剤等の、種々の添加剤が組合わされ、光、熱、酸化等に対する耐性を向上させるための安定化助剤として使用されている。
しかしながら、これらの非金属系安定化助剤を組み合わせただけでは、耐熱性を十分に向上させることは困難であった。 However, since these low-toxic stabilizers do not provide a sufficient stabilizing effect by themselves, ultraviolet absorbers such as organic phosphite compounds, epoxy compounds, phenolic antioxidants, benzophenone or benzotriazoles, Various additives such as hindered amine light stabilizers are combined and used as a stabilizing aid for improving resistance to light, heat, oxidation and the like.
However, it has been difficult to sufficiently improve the heat resistance only by combining these nonmetallic stabilizing aids.
しかしながら、これらの非金属系安定化助剤を組み合わせただけでは、耐熱性を十分に向上させることは困難であった。 However, since these low-toxic stabilizers do not provide a sufficient stabilizing effect by themselves, ultraviolet absorbers such as organic phosphite compounds, epoxy compounds, phenolic antioxidants, benzophenone or benzotriazoles, Various additives such as hindered amine light stabilizers are combined and used as a stabilizing aid for improving resistance to light, heat, oxidation and the like.
However, it has been difficult to sufficiently improve the heat resistance only by combining these nonmetallic stabilizing aids.
一方、熱分解型発泡剤が使用されてなる発泡性塩化ビニル系樹脂に対しては、高級脂肪酸カリウム塩やアルカリ金属無機塩と共に、特定のリン酸エステルを含有させてなる組成物が提案されており（特許文献1）、Ca-Zn系安定剤と高級脂肪酸カリウム塩を組み合せて使用することも記載されている。しかしながら、このように発泡剤を使用した系では、耐熱性及び耐着色性に対する改善効果を十分に得ることができないという欠点があった。
特公平7-30197号公報
On the other hand, for a foamable vinyl chloride resin in which a pyrolytic foaming agent is used, a composition containing a specific phosphate ester together with a higher fatty acid potassium salt or an alkali metal inorganic salt has been proposed. (Patent Document 1) describes that a Ca-Zn stabilizer and a higher fatty acid potassium salt are used in combination. However, the system using the foaming agent as described above has a drawback that it is not possible to sufficiently obtain an improvement effect on heat resistance and color resistance.
Japanese Patent Publication No. 7-30197
従って、本発明の目的は、鉛等の重金属系安定剤を使用することなく、耐熱性及び耐着色性に優れた製品を提供することのできる、非発泡性塩化ビニル系樹脂組成物を提供することにある。
Accordingly, an object of the present invention is to provide a non-foamable vinyl chloride resin composition capable of providing a product excellent in heat resistance and color resistance without using a heavy metal stabilizer such as lead. There is.
本発明者等は、上記の目的を達成するために鋭意検討を重ねた結果、発泡剤を使用しない非発泡性塩化ビニル系樹脂組成物の場合には、有機酸カルシウム塩、有機酸亜鉛塩及び有機酸カリウム塩を組み合わせて使用することにより、塩化ビニル系樹脂組成物の耐熱性及び耐着色性を著しく改善することができることを見出し、本発明に到達した。
As a result of intensive studies to achieve the above object, the present inventors have found that in the case of a non-foamable vinyl chloride resin composition that does not use a foaming agent, an organic acid calcium salt, an organic acid zinc salt, and It has been found that the heat resistance and coloration resistance of the vinyl chloride resin composition can be remarkably improved by using the organic acid potassium salt in combination, and the present invention has been achieved.
即ち本発明は、少なくとも、(a)有機酸カルシウム塩、(b)有機酸亜鉛塩及び(c)有機酸カリウム塩を含有してなる、発泡剤を含有しない非発泡性塩化ビニル系樹脂組成物であって、前記(a)有機酸カルシウム塩、(b)有機酸亜鉛塩及び(c)有機酸カリウム塩の含有量が、それぞれ、塩化ビニル系樹脂100質量部に対し、(a)0.01～5質量部、(b)0.01～5質量部及び(c)0.001～1質量部であることを特徴とする、非発泡性塩化ビニル系樹脂組成物である。
That is, the present invention provides a non-foamable vinyl chloride resin composition containing no foaming agent, comprising at least (a) an organic acid calcium salt, (b) an organic acid zinc salt, and (c) an organic acid potassium salt. Wherein the contents of the (a) organic acid calcium salt, (b) organic acid zinc salt, and (c) organic acid potassium salt are (a) 0.01 to 0.01 parts per 100 parts by mass of the vinyl chloride resin, respectively. A non-foamable vinyl chloride resin composition, comprising 5 parts by mass, (b) 0.01 to 5 parts by mass, and (c) 0.001 to 1 part by mass.
前記(a)成分及び(b)成分は、カルシウムと亜鉛のモル比で1/1～10/1となるように使用されることが好ましく、更に、(c)成分は、(a)成分及び(b)成分のカルシウムと亜鉛の総量1モルに対し、カリウムが0.01～0.3モルとなるように使用されることが好ましい。
The component (a) and the component (b) are preferably used so that the molar ratio of calcium to zinc is 1/1 to 10/1. Furthermore, the component (c) includes the component (a) and It is preferable that potassium is used in an amount of 0.01 to 0.3 mol with respect to 1 mol of the total amount of component (b) calcium and zinc.
本発明の非発泡性塩化ビニル系樹脂組成物は、熱安定性及び耐着色性に優れるので、従来製品より高品質の、塩化ビニル系樹脂成型品を提供することができる。
Since the non-foamable vinyl chloride resin composition of the present invention is excellent in thermal stability and color resistance, it is possible to provide a vinyl chloride resin molded product of higher quality than conventional products.
以下、本発明の非発泡性塩化ビニル系樹脂組成物について詳細に説明する。
本発明に使用される塩化ビニル系樹脂は、塊状重合、溶液重合、懸濁重合、乳化重合等によって得ることができ、特にその重合方法が限定されることはない。具体的な樹脂としては、例えば、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-エチレン共重合体、塩化ビニル-プロピレン共重合体、塩化ビニル-スチレン共重合体、塩化ビニル-イソブチレン共重合体、塩化ビニル-塩化ビニリデン共重合体、塩化ビニル-スチレン-無水マレイン酸の三元共重合体、塩化ビニル-スチレン-アクリロニトリル共重合体、塩化ビニル-ブタジエン共重合体、塩化ビニル-イソプレン共重合体、塩化ビニル-塩素化プロピレン共重合体、塩化ビニル-塩化ビニリデン-酢酸ビニルの三元共重合体、塩化ビニル-マレイン酸エステル共重合体、塩化ビニル-メタクリル酸エステル共重合体、塩化ビニル-アクリロニトリル共重合体、塩化ビニル-各種ビニルエーテル共重合体等の塩化ビニル系樹脂、及びそれら相互のブレンド品、あるいは他の塩素を含まない合成樹脂、例えば、アクリロニトリル-スチレン共重合体、アクリロニトリル-ブタジエン-スチレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-エチル（メタ）アクリレート共重合体、ポリエステル等との混合物、ポリエステル等とのブロック共重合体及びグラフト共重合体等が挙げられる。 Hereinafter, the non-foamable vinyl chloride resin composition of the present invention will be described in detail.
The vinyl chloride resin used in the present invention can be obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like, and the polymerization method is not particularly limited. Specific resins include, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer. Polymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer Polymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer Polymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-each Vinyl chloride resins such as seed vinyl ether copolymers, and their blends , or other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene-acetic acid Examples thereof include vinyl copolymers, ethylene-ethyl (meth) acrylate copolymers, mixtures with polyesters, block copolymers with polyesters, graft copolymers, and the like.
本発明に使用される塩化ビニル系樹脂は、塊状重合、溶液重合、懸濁重合、乳化重合等によって得ることができ、特にその重合方法が限定されることはない。具体的な樹脂としては、例えば、ポリ塩化ビニル、塩素化ポリ塩化ビニル、ポリ塩化ビニリデン、塩素化ポリエチレン、塩化ビニル-酢酸ビニル共重合体、塩化ビニル-エチレン共重合体、塩化ビニル-プロピレン共重合体、塩化ビニル-スチレン共重合体、塩化ビニル-イソブチレン共重合体、塩化ビニル-塩化ビニリデン共重合体、塩化ビニル-スチレン-無水マレイン酸の三元共重合体、塩化ビニル-スチレン-アクリロニトリル共重合体、塩化ビニル-ブタジエン共重合体、塩化ビニル-イソプレン共重合体、塩化ビニル-塩素化プロピレン共重合体、塩化ビニル-塩化ビニリデン-酢酸ビニルの三元共重合体、塩化ビニル-マレイン酸エステル共重合体、塩化ビニル-メタクリル酸エステル共重合体、塩化ビニル-アクリロニトリル共重合体、塩化ビニル-各種ビニルエーテル共重合体等の塩化ビニル系樹脂、及びそれら相互のブレンド品、あるいは他の塩素を含まない合成樹脂、例えば、アクリロニトリル-スチレン共重合体、アクリロニトリル-ブタジエン-スチレン共重合体、エチレン-酢酸ビニル共重合体、エチレン-エチル（メタ）アクリレート共重合体、ポリエステル等との混合物、ポリエステル等とのブロック共重合体及びグラフト共重合体等が挙げられる。 Hereinafter, the non-foamable vinyl chloride resin composition of the present invention will be described in detail.
The vinyl chloride resin used in the present invention can be obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like, and the polymerization method is not particularly limited. Specific resins include, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer. Polymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer Polymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer Polymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-each Vinyl chloride resins such as seed vinyl ether copolymers, and their blends , or other chlorine-free synthetic resins, such as acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, ethylene-acetic acid Examples thereof include vinyl copolymers, ethylene-ethyl (meth) acrylate copolymers, mixtures with polyesters, block copolymers with polyesters, graft copolymers, and the like.
本発明に使用される(a)成分である有機酸カルシウム塩としては、有機カルボン酸、フェノール類及び有機リン酸類のカルシウム塩が挙げられる。
Examples of the organic acid calcium salt as the component (a) used in the present invention include calcium salts of organic carboxylic acids, phenols and organic phosphoric acids.
上記有機カルボン酸としては、例えば、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、2-エチルヘキシル酸、ネオデカン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、パルミチン酸、イソステアリン酸、ステアリン酸、12-ヒドロキシステアリン酸、ベヘニン酸、モンタン酸、安息香酸、モノクロル安息香酸、p-第三ブチル安息香酸、ジメチルヒドロキシ安息香酸、3，5-ジ第三ブチル-4-ヒドロキシ安息香酸、トルイル酸、ジメチル安息香酸、エチル安息香酸、クミン酸、n-プロピル安息香酸、アミノ安息香酸、N,N-ジメチルアミノ安息香酸、アセトキシ安息香酸、サリチル酸、p-第三オクチルサリチル酸、エライジン酸、オレイン酸、リノール酸、リノレイン酸、チオグリコール酸、メルカプトプロピオン酸、オクチルメルカプトプロピオン酸等の一価カルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、フタール酸、イソフタール酸、テレフタール酸、ヒドロキシフタール酸、クロルフタール酸、アミノフタール酸、マレイン酸、フマール酸、シトラコン酸、メタコン酸、イタコン酸、アコニット酸、チオジプロピオン酸等の二価カルボン酸あるいはこれらのモノエステル又はモノアマイド化合物；ブタントリカルボン酸、ブタンテトラカルボン酸、ヘミメリット酸、トリメリット酸、メロファン酸、ピロメリット酸等の、三価又は四価カルボン酸のジエステル化合物又はトリエステル化合物が挙げられる。
Examples of the organic carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, neodecanoic acid, capric acid, undecanoic acid, lauric acid, and tridecanoic acid. , Myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di Tertiary butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N, N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p -Tertiary octylsalicylic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thio Monovalent carboxylic acids such as richolic acid, mercaptopropionic acid, octyl mercaptopropionic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid , Terephthalic acid, hydroxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid and other divalent carboxylic acids or their monoesters or monoamides Compound: A diester compound or a triester compound of a trivalent or tetravalent carboxylic acid such as butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid, trimellitic acid, merophanic acid, or pyromellitic acid.
また、前記フェノール類としては、例えば、第三ブチルフェノール、ノニルフェノール、ジノニルフェノール、シクロヘキシルフェノール、フェニルフェノール、オクチルフェノール、フェノール、クレゾール、キシレノール、n-ブチルフェノール、イソアミルフェノール、エチルフェノール、イソプロピルフェノール、イソオクチルフェノール、2-エチルヘキシルフェノール、第三ノニルフェノール、デシルフェノール、第三オクチルフェノール、イソヘキシルフェノール、オクタデシルフェノール、ジイソブチルフェノール、メチルプロピルフェノール、ジアミルフェノール、メチルイソヘキシルフェノール、メチル第三オクチルフェノール等が挙げられる。
As the pre-Symbol phenols, for example, tert-butylphenol, nonylphenol, di-nonylphenol, cyclohexyl phenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n- butylphenol, isoamyl phenol, ethyl phenol, isopropyl phenol, isooctylphenol, Examples include 2-ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamylphenol, methylisohexylphenol, and methyltertiaryoctylphenol.
また、前記有機リン酸類としては、例えば、モノ-又はジオクチルリン酸、モノ-又はジドデシルリン酸、モノ-又はジオクタデシルリン酸、モノ-又はジ-（ノニルフェニル）リン酸、ホスホン酸ノニルフェニルエステル、ホスホン酸ステアリルエステル等が挙げられる。
Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, Examples include phosphonic acid stearyl ester.
また、前記した有機カルボン酸、フェノール類及び有機リン酸類のカルシウム塩は、酸性塩、中性塩、又は塩基性塩であっても、あるいは該塩基性塩の塩基の一部又は全部を炭酸で中和した過塩基性錯体であってもよい。
Also, the organic carboxylic acid, calcium salt of phenols and organic phosphorus acids, acid salts, neutral salts, or even basic salts, or some or all of the bases of the basic salt with carbon dioxide It may be a neutralized overbased complex.
前記した有機酸カルシウム塩の本発明における添加量は、塩化ビニル系樹脂100質量部に対して0.01～5質量部であり、好ましくは0.05～3質量部である。
The amount of the organic acid calcium salt added in the present invention is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
本発明に使用される(b)成分である有機酸亜鉛塩としては、有機カルボン酸、フェノール類及び有機リン酸類の亜鉛塩が挙げられる。有機カルボン酸、フェノール類及び有機リン酸類の例としては、前述したものが挙げられる。
Examples of the organic acid zinc salt (b) used in the present invention include zinc salts of organic carboxylic acids, phenols and organic phosphoric acids. What was mentioned above is mentioned as an example of organic carboxylic acid, phenols, and organic phosphoric acids.
また、上記した有機カルボン酸、フェノール類及び有機リン酸類の亜鉛塩は、酸性塩、中性塩、塩基性塩の何れであっても良く、又、前記塩基性塩の塩基の一部又は全部を炭酸で中和した、過塩基性錯体であってもよい。
The zinc salts of the organic carboxylic acids, phenols and organic phosphoric acids described above may be any of acidic salts, neutral salts and basic salts, and some or all of the bases of the basic salts. An overbased complex neutralized with carbonic acid may be used.
上記した(b)成分である有機酸亜鉛塩の添加量は、前記した塩化ビニル系樹脂100質量部に対して0.01～5質量部であり、好ましくは0.05～3質量部である。
The amount of the organic acid zinc salt which is the component (b) is 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
本発明に使用される(c)成分である有機酸カリウム塩としては、有機カルボン酸、フェノール類及び有機リン酸類の亜鉛塩が挙げられる。有機カルボン酸、フェノール類及び有機リン酸類の例としては、既に例示したものが挙げられる。
Examples of the organic acid potassium salt as component (c) used in the present invention include zinc salts of organic carboxylic acids, phenols and organic phosphoric acids. Examples of organic carboxylic acids, phenols and organic phosphoric acids include those already exemplified.
また、上記の有機カルボン酸、フェノール類及び有機リン酸類の亜鉛塩は、酸性塩、中性塩、塩基性塩の何れであっても良く、これらは、塩基性塩における塩基の一部又は全部を炭酸で中和してなる過塩基性錯体であってもよい。
The zinc salts of the organic carboxylic acids, phenols and organic phosphoric acids may be any of acidic salts, neutral salts and basic salts, and these may be a part or all of the bases in the basic salts. An overbased complex obtained by neutralizing with carbonic acid may be used.
上記の有機酸カリウム塩の添加量は、塩化ビニル系樹脂100質量部に対して0.001～1質量部であり、好ましくは0.01～0.5質量部である。
The amount of the organic acid potassium salt added is 0.001 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the vinyl chloride resin.
本発明において、耐着色性及び熱安定性に著しく優れた非発泡の成型品を製造するためには、(a)成分と(b)成分の使用比率が、カルシウムと亜鉛のモル比で1/1～10/1であることが好ましく、2/1～8/1であることが更に好ましい。更に、(c)成分の比率は、(a)成分及び(b)成分のカルシウムと亜鉛の総量1モルに対してカリウムが0.01～0.3モルであることが好ましく、0.05～0.25モルであることがより好ましい。
In the present invention, in order to produce a non-foamed molded product with excellent coloration resistance and thermal stability, the ratio of the component (a) and the component (b) is 1 / molar ratio of calcium and zinc. It is preferably 1 to 10/1, and more preferably 2/1 to 8/1. Furthermore, the ratio of the component (c) is preferably 0.01 to 0.3 mol, more preferably 0.05 to 0.25 mol of potassium with respect to 1 mol of the total amount of calcium and zinc of the components (a) and (b). More preferred.
また、本発明の組成物には、通常塩化ビニル系樹脂組成物に用いられる他の添加剤、例えば、可塑剤、ハイドロタルサイト化合物、ゼオライト化合物、β-ジケトン化合物、過塩素酸塩類、エポキシ化合物、多価アルコール、リン系、フェノール系及び硫黄系等の酸化防止剤、紫外線吸収剤、ヒンダードアミン系等の光安定剤、充填剤、滑剤等を添加することができる。
Further, the composition of the present invention includes other additives usually used in vinyl chloride resin compositions, such as plasticizers, hydrotalcite compounds, zeolite compounds, β-diketone compounds, perchlorates, epoxy compounds. Polyhydric alcohol, phosphorus-based, phenol-based and sulfur-based antioxidants, ultraviolet absorbers, hindered amine-based light stabilizers, fillers, lubricants, and the like can be added.
上記の可塑剤としては、例えば、ジブチルフタレート、ブチルヘキシルフタレート、ジヘプチルフタレート、ジオクチルフタレート、ジイソノニルフタレート、ジイソデシルフタレート、ジラウリルフタレート、ジシクロヘキシルフタレート、ジオクチルテレフタレート等のフタレート系可塑剤；ジオクチルアジペート、ジイソノニルアジペート、ジイソデシルアジペート、ジ(ブチルジグリコール)アジペート等のアジペート系可塑剤；トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリ(イソプロピルフェニル)ホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリ(ブトキシエチル)ホスフェート、オクチルジフェニルホスフェート等のホスフェート可塑剤系;多価アルコールとして、エチレングリコール、ジエチレングリコール、トリエチレングリコール、1,2-プロピレングリコール、1,3-プロピレングリコール、1,3-ブタンジオール、1,4-ブタンジオール、1,5-ヘキサンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール等と二塩基酸としてシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバチン酸、フタール酸、イソフタール酸、テレフタール酸等を用い、必要により一価アルコール、モノカルボン酸をストッパーに使用したポリエステル系可塑剤；その他、テトラヒドロフタール酸系可塑剤、アゼライン酸系可塑剤、セバチン酸系可塑剤、ステアリン酸系可塑剤、クエン酸系可塑剤、トリメリット酸系可塑剤、ピロメリット酸系可塑剤、ビフェニルテトラカルボン酸エステル系可塑剤、塩素系可塑剤等が挙げられる。
Examples of the plasticizer include dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, dioctyl terephthalate and the like; dioctyl adipate, diisononyl adipate , Diisodecyl adipate, di (butyl diglycol) adipate and the like adipate plasticizers; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri Phosphate such as (butoxyethyl) phosphate, octyl diphenyl phosphate Plasticizer system; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5- Hexanediol, 1,6-hexanediol, neopentyl glycol, etc. and dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid Polyester plasticizer using acid, terephthalic acid, etc., and monohydric alcohol or monocarboxylic acid as a stopper if necessary; tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearin Acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer, pyromellitic acid Plasticizers, biphenyltetracarboxylic acid ester plasticizer, and chlorinated plasticizers and the like.
前記ハイドロタルサイト化合物とは、マグネシウム及び/又は亜鉛とアルミニウムとの炭酸複塩化合物であり、好ましくは下記一般式(I)で表される化合物である。
Mgx1Znx2Al2(OH)2(X1+X2)+4・CO3・mH2O （I）
但し、（I）式中のx1及びx2は、各々下記の式で表される条件を満たす数を表し、mは実数を表す。0≦x2/x1＜10、且つ2≦x1＋x2＜20。 The hydrotalcite compound is a carbonate double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (I).
Mg x1 Zn x2 Al 2 (OH) 2 (X1 + X2) +4・ CO 3・ mH 2 O （I）
However, x1 and x2 in the formula (I) each represent a number satisfying the condition represented by the following formula, and m represents a real number. 0 ≦ x2 / x1 <10 and 2 ≦ x1 + x2 <20.
Mgx1Znx2Al2(OH)2(X1+X2)+4・CO3・mH2O （I）
但し、（I）式中のx1及びx2は、各々下記の式で表される条件を満たす数を表し、mは実数を表す。0≦x2/x1＜10、且つ2≦x1＋x2＜20。 The hydrotalcite compound is a carbonate double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (I).
Mg x1 Zn x2 Al 2 (OH) 2 (X1 + X2) +4・ CO 3・ mH 2 O （I）
However, x1 and x2 in the formula (I) each represent a number satisfying the condition represented by the following formula, and m represents a real number. 0 ≦ x2 / x1 <10 and 2 ≦ x1 + x2 <20.
また、上記ハイドロタルサイト化合物は、天然物であっても合成品であってもよい。上記合成品の合成方法としては、特公昭46-2280号公報、特公昭50-30039号公報、特公昭51-29129号公報、特開昭61-174270号公報に記載された方法等、公知のものを使用することができる。また、本発明においては、上記ハイドロタルサイト化合物の結晶構造、結晶の粒子径、あるいは結晶水の有無及びその量等に制限されることなく使用することができる。
The hydrotalcite compound may be a natural product or a synthetic product. As a method for synthesizing the above synthetic product, known methods such as those described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 61-174270, etc. Things can be used. In the present invention, the hydrotalcite compound can be used without being limited by the crystal structure, the crystal particle size, the presence or absence of crystal water, and the amount thereof.
また本発明においては、過塩素酸処理したハイドロタルサイトを使用することもでき、その表面をステアリン酸のような高級脂肪酸、オレイン酸アルカリ金属塩のような高級脂肪酸金属塩、ドデシルベンゼンスルホン酸アルカリ金属塩のような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、又はワックス等で被覆したものも使用することができる。
In the present invention, hydrotalcite treated with perchloric acid can also be used, and the surface thereof has higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, alkali dodecylbenzenesulfonate. An organic sulfonic acid metal salt such as a metal salt, a higher fatty acid amide, a higher fatty acid ester, or a wax coated with a wax can also be used.
前記ゼオライト化合物は、独特の三次元のゼオライト結晶構造を有するアルカリ又はアルカリ土類金属のアルミノケイ酸塩であり、その代表例としては、A型、X型、Y型及びP型ゼオライト、モノデナイト、アナルサイト、ソーダライト族アルミノケイ酸塩、クリノブチロライト、エリオナイト及びチャバサイト等を挙げることができる。これらのゼオライト化合物は結晶水（いわゆるゼオライト水）を有する含水物であっても、結晶水を除去した無水物であっても良い。これらの化合物の粒径は、0.1～50μｍであることが好ましく、特に、0.5～10μｍであることが好ましい。
The zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and representative examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Site, sodalite group aluminosilicate, clinobutyrolite, erionite, chabazite and the like. These zeolitic compounds may be water-containing substances having crystal water (so-called zeolite water) or anhydrides from which crystal water has been removed. The particle diameter of these compounds is preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 10 μm.
前記β-ジケトン化合物としては、例えば、デヒドロ酢酸、ジベンゾイルメタン、パルミトイルベンゾイルメタン、ステアロイルベンゾイルメタン等が挙げられる。本発明においてはこれらの金属塩も上記のものと同様に有用である。
Examples of the β-diketone compound include dehydroacetic acid, dibenzoylmethane, palmitoylbenzoylmethane, stearoylbenzoylmethane, and the like. In the present invention, these metal salts are also useful as described above.
前記過塩素酸塩類としては、過塩素酸金属塩、過塩素酸アンモニウム、過塩素酸処理ハイドロタルサイト、過塩素酸処理珪酸塩等が挙げられる。ここで、金属塩を構成する金属としては、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム、ストロンチウム、バリウム、亜鉛、カドミウム、鉛、アルミニウム等を例示することができる。上記過塩素酸金属塩は、無水物であっても含水塩であってもよい。また、ブチルジグリコール、ブチルジグリコールアジペート等のアルコール系及びエステル系の溶剤に溶かしたものであっても、その脱水物であってもよい。
Examples of the perchlorates include perchloric acid metal salts, ammonium perchlorate, perchloric acid-treated hydrotalcite, and perchloric acid-treated silicates. Here, examples of the metal constituting the metal salt include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, and aluminum. The perchloric acid metal salt may be an anhydride or a hydrated salt. Moreover, butyl diglycol, even those dissolved in an alcohol-based solvent and ester type such as butyl diglycol adipate, may be the dehydrated product.
前記エポキシ化合物としては、例えば、ビスフェノール型及びノボラック型のエポキシ樹脂、エポキシ化大豆油、エポキシ化アマニ油、エポキシ化桐油、エポキシ化魚油、エポキシ化牛脂油、エポキシ化ヒマシ油、エポキシ化サフラワー油、エポキシ化トール油脂肪酸オクチル、エポキシ化アマニ油脂肪酸ブチル、エポキシステアリン酸メチル、エポキシステアリン酸ブチル、エポキシステアリン酸2-エチルヘキシル、エポキシステアリン酸ステアリル、トリス(エポキシプロピル)イソシアヌレート、3-(2-キセノキシ)-1,2-エポキシプロパン、エポキシ化ポリブタジエン、ビスフェノール-Aジグリシジルエーテル、ビニルシクロヘキセンジエポキサイド、ジシクロペンタジエンジエポキサイド、3,4-エポキシシクロヘキシル-6-メチルエポキシシクロヘキサンカルボキシレート、ビス(3,4-エポキシシクロヘキシル)アジペート等が挙げられる。
Examples of the epoxy compound include bisphenol type and novolak type epoxy resins, epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil. , Epoxidized tall oil fatty acid octyl, epoxidized linseed oil fatty acid butyl, epoxy methyl stearate, epoxy butyl stearate, 2-ethylhexyl epoxy stearate, stearyl epoxy stearate, tris (epoxypropyl) isocyanurate, 3- (2- Xenoxy) -1,2-epoxypropane, epoxidized polybutadiene, bisphenol-A diglycidyl ether, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, 3,4-epoxycyclohexyl-6-methylepoxy Hexane carboxylate, bis (3,4-epoxycyclohexyl) adipate, and the like.
前記多価アルコールとしては、例えば、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、マンニトール、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール又はジペンタエリスリトールのステアリン酸部分エステル、ビス(ジペンタエタスリトール)アジペート、グリセリン、ジグリセリン、トリス(2-ヒドロキシエチル)イソシアヌレート等が挙げられる。
Examples of the polyhydric alcohol include pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolpropane, ditrimethylolpropane, pentaerythritol or stearic acid partial ester of dipentaerythritol, bis (dipentaerythritol) adipate, Examples include glycerin, diglycerin, and tris (2-hydroxyethyl) isocyanurate.
前記リン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、トリス(2,4-ジ第三ブチルフェニル)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(ジノニルフェニル)ホスファイト、トリス(モノ、ジ混合ノニルフェニル)ホスファイト、ビス(2-第三ブチル-4,6-ジメチルフェニル)・エチルホスファイト、ジフェニルアシッドホスファイト、2,2'-メチレンビス(4,6-ジ第三ブチルフェニル)オクチルホスファイト、ジフェニルデシルホスファイト、フェニルジイソデシルホスファイト、トリブチルホスファイト、トリス(2-エチルヘキシル)ホスファイト、トリデシルホスファイト、トリラウリルホスファイト、ジブチルアシッドホスファイト、ジラウリルアシッドホスファイト、トリラウリルトリチオホスファイト、ビス(ネオペンチルグリコール)・1,4-シクロヘキサンジメチルジホスファイト、ビス(2,4-ジ第三ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ第三ブチル-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、ジステアリルペンタエリスリトールジホスファイト、テトラ(C12-15混合アルキル)-4,4'-イソプロピリデンジフェニルホスファイト、ビス[2,2'-メチレンビス(4,6-ジアミルフェニル)]・イソプロピリデンジフェニルホスファイト、水素化-4,4'-イソプロピリデンジフェノールポリホスファイト、テトラトリデシル・4,4'-ブチリデンビス(2-第三ブチル-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-5-第三ブチル-4-ヒドロキシフェニル)ブタン・トリホスホナイト、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、2-ブチル-2-エチルプロパンジオール・2,4,6-トリ第三ブチルフェノールモノホスファイト等が挙げられる。
Examples of the phosphorus antioxidant include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris ( Mono, di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butyl) Phenyl) octyl phosphite, diphenyl decyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite, dilauryl acid phosphite, Trilauryl trithiophosphite, bis (neopench Glycol) ・ 1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol Diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methylenebis (4,6-diamilphenyl)]・ Isopropylidene diphenyl phosphite, hydrogenated-4,4′-isopropylidene diphenol polyphosphite, tetratridecyl ・ 4,4′-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) ) ・ 1,1,3-Tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphonite, 9,10-dihydro-9-oxa-10-phosphafenance Down-10-oxide, 2-butyl-2-ethyl-propanediol-2,4,6-tri-tert-butylphenol monophosphite, and the like.
前記フェノール系酸化防止剤としては、例えば、2,6-ジ第三ブチル-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-ジ第三ブチル-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-ジ第三ブチル-4-ヒドロキシベンジル)ホスホネート、チオジエチレングリコールビス〔(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオネート〕、1,6-ヘキサメチレンビス〔(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオネート〕、1,6-ヘキサメチレンビス〔(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオン酸アミド〕、4,4'-チオビス(6-第三ブチル-m-クレゾール)、2,2'-メチレンビス(4-メチル-6-第三ブチルフェノール)、2,2'-メチレンビス(4-エチル-6-第三ブチルフェノール)、ビス〔3,3-ビス(4-ヒドロキシ-3-第三ブチルフェニル)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(6-第三ブチル-m-クレゾール)、2,2'-エチリデンビス(4,6-ジ第三ブチルフェノール)、2,2'-エチリデンビス(4-第二ブチル-6-第三ブチルフェノール)、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-第三ブチルフェニル)ブタン、ビス〔2-第三ブチル-4-メチル-6-(2-ヒドロキシ-3-第三ブチル-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-第三ブチルベンジル)イソシアヌレート、1,3,5-トリス(3,5-ジ第三ブチル-4-ヒドルキシベンジル)イソシアヌレート、1,3,5-トリス(3,5-ジ第三ブチル-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-ジ第三ブチル-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-ジ第三ブチル-4-ヒドロキシフェニル)プロピオネート〕メタン、2-第三ブチル-4-メチル-6-(2-アクリロイルオキシ-3-第三ブチル-5-メチルベンジル)フェノール、3,9-ビス〔1,1-ジメチル-2-{(3-第三ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}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-第三ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート〕等が挙げられる。
Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6- Tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) buty Rick acid) glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis ( 4-sec-butyl-6-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-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl)- 2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5- The third -4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1 -Dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like.
前記硫黄系酸化防止剤としては、例えば、チオジプロピオン酸ジラウリル、ジミリスチル、ジステアリル等のジアルキルチオジプロピオネート類及びペンタエリスリトールテトラ(β-ドデシルメルカプトプロピオネート)等のポリオールのβ-アルキルメルカプトプロピオン酸エステル類が挙げられる。
Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include propionic acid esters.
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、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-オクト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)等の2-ヒドロキシベンゾフェノン類；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-3',5'-ジ第三ブチルフェニル)ベンゾトリアゾール、2-(2'-ヒドロキシ-3',5'-ジ第三ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2'-ヒドロキシ-3'-第三ブチル-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-5'-第三オクチルフェニル)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-第三オクチル-6-ベンゾトリアゾリル)フェノール等の2-(2'-ヒドロキシフェニル)ベンゾトリアゾール類；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-ジ第三ブチルフェニル-3',5'-ジ第三ブチル-4'-ヒドロキシベンゾエート、ヘキサデシル-3,5-ジ第三ブチル-4-ヒドロキシベンゾエート等のベンゾエート類；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等の置換オキザニリド類；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)アクリレート等のシアノアクリレート類が挙げられる。
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis 2- (2'-hydro, such as (4-tert-octyl-6-benzotriazolyl) phenol Cyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ', 5'-ditertiarybutyl-4'-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl Benzoates such as -4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl And cyanoacrylates such as acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.
前記ヒンダードアミン系光安定剤としては、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、N-(2,2,6,6-テトラメチル-4-ピペリジル)ドデシルコハク酸イミド、1-〔(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオニルオキシエチル〕-2,2,6,6-テトラメチル-4-ピペリジル-(3,5-ジ第三ブチル-4-ヒドロキシフェニル)プロピオネート、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート、ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)セバケート、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-ジ第三ブチル-4-ヒドロキシベンジル)マロネート、N,N'-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミン、テトラ(2,2,6,6-テトラメチル-4-ピペリジル)ブタンテトラカルボキシレート、テトラ(1,2,2,6,6-ペンタメチル-4-ピペリジル)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)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)ブタンテトラカルボキシレート、3,9-ビス〔1,1-ジメチル-2-{トリス(2,2,6,6-テトラメチル-4-ピペリジルオキシカルボニルオキシ)ブチルカルボニルオキシ}エチル〕-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン、3,9-ビス〔1,1-ジメチル-2-{トリス(1,2,2,6,6-ペンタメチル-4-ピペリジルオキシカルボニルオキシ)ブチルカルボニルオキシ}エチル〕-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン、1,5,8,12-テトラキス〔4,6-ビス{N-(2,2,6,6-テトラメチル-4-ピペリジル)ブチルアミノ}-1,3,5-トリアジン-2-イル〕-1,5,8,12-テトラアザドデカン、1-(2-ヒドロキシエチル)-2,2,6,6-テトラメチル-4-ピペリジノール/コハク酸ジメチル縮合物、2-第三オクチルアミノ-4,6-ジクロロ-s-トリアジン/N,N'-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミン縮合物、N,N'-ビス(2,2,6,6-テトラメチル-4-ピペリジル)ヘキサメチレンジアミン/ジブロモエタン縮合物等が挙げられる。
Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4- Hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6- Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- Butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2 , 2,6,6-Tetramethyl-4-pipe (Zyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) -di ( Tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- { Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1 , 1-Dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane, 1,5,8,12-tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazine-2- Il -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino- 4,6-dichloro-s-triazine / N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6 , 6-Tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.
前記充填剤としては、例えば、炭酸カルシウム、シリカ、クレー、ガラスビーズ、マイカ、セリサイト、ガラスフレーク、アスベスト、ウオラストナイト、チタン酸カリウム、PMF、石膏繊維、ゾノトライト、MOS、ホスフェートファイバー、ガラス繊維、炭酸繊維、アラミド繊維等が挙げられる。
Examples of the filler include calcium carbonate, silica, clay, glass beads, mica, sericite, glass flake, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonotlite, MOS, phosphate fiber, and glass fiber. , Carbonate fiber, aramid fiber and the like.
前記滑剤としては、例えば、天然パラフィン、低分子ポリエチレン等の炭化水素類、ステアリン酸、ラウリン酸、エルカ酸等の脂肪酸類、セチルアルコール、ステアリルアルコール等の脂肪族アルコール類、ステアリン酸アミド、メレンビスステアロアミド等の脂肪酸アミド類、ブチルステアレート等の脂肪酸の低級アルコールエステル類、グリセリンモノステアレート等の高級脂肪酸の高級アルコールエステル等が挙げられる。
Examples of the lubricant include hydrocarbons such as natural paraffin and low molecular weight polyethylene, fatty acids such as stearic acid, lauric acid and erucic acid, aliphatic alcohols such as cetyl alcohol and stearyl alcohol, stearic acid amide, and melenbis. Examples include fatty acid amides such as stearamide, lower alcohol esters of fatty acids such as butyl stearate, higher alcohol esters of higher fatty acids such as glycerol monostearate, and the like.
その他、本発明の組成物には、必要に応じて通常塩化ビニル系樹脂に使用される添加剤、例えば、架橋剤、帯電防止剤、防曇剤、プレートアウト防止剤、表面処理剤、難燃剤、蛍光剤、防黴剤、殺菌剤、金属不活性剤、離型剤、加工助剤、酸化防止剤、光安定剤等を配合することができる。
In addition, in the composition of the present invention, additives that are usually used in vinyl chloride resins as necessary, for example, crosslinking agents, antistatic agents, antifogging agents, plate-out preventing agents, surface treatment agents, flame retardants , Fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, processing aids, antioxidants, light stabilizers, and the like.
本発明の組成物は、塩化ビニル系樹脂の加工方法とは無関係に使用することが可能である。例えば、カレンダー加工、ロール加工、押し出し成形加工、溶融圧延法、射出成形加工、加圧成形加工、ペースト加工、粉体成形加工、発泡成形加工等に好適に使用することができる。
The composition of the present invention can be used regardless of the processing method of the vinyl chloride resin. For example, it can be suitably used for calendar processing, roll processing, extrusion molding processing, melt rolling, injection molding processing, pressure molding processing, paste processing, powder molding processing, foam molding processing, and the like.
本発明の組成物は、壁材、床材、窓枠、壁材、波板、雨樋等の建材；自動車用内外装材；トレイ等の魚食品包装材；パッキン、ガスケット、ホース、パイプ、継ぎ手、シート、玩具等に使用することができる。
The composition of the present invention comprises: wall materials, floor materials, window frames, wall materials, corrugated sheets, gutters, etc .; automotive interior and exterior materials; fish food packaging materials such as trays; packings, gaskets, hoses, pipes, It can be used for joints, sheets, toys, etc.
次に、実施例によって本発明を更に詳細に説明するが、本発明は下記の実施例によって制限を受けるものではない。
Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.
１．［表１］及び［表２］に示した物質を配合して得られた樹脂組成物を、170℃で5分間カレンダー加工して厚さが0.7mmのシートを得た。得られたシートを、190℃のギヤーオーブン中に入れて分解時間（分）を測定し、熱安定性を評価した。
２．上記１で得られたシートを貼り合わせて、180℃で5分間、及び180℃で30分間プレス加工を行い、厚さ1mmのシートを作製した。得られたシートそれぞれについて、色差計（TC-8600A：（有）東京電色製の商品名）を用いて黄色度を測定し、耐着色性を評価した。
３．［表１］及び［表２］に示した物質を配合して得られた樹脂組成物を、170℃でカレンダー加工して、カレンダーロールから剥離しなくなるまでの時間（ミル粘着時間、分）を測定し、耐熱性を評価した。
上記の評価結果を［表２］に示す。 1. The resin composition obtained by blending the substances shown in [Table 1] and [Table 2] was calendered at 170 ° C. for 5 minutes to obtain a sheet having a thickness of 0.7 mm. The obtained sheet was placed in a gear oven at 190 ° C. and the decomposition time (minutes) was measured to evaluate the thermal stability.
2. By bonding sheets obtained in the above 1, 5 min at 180 ° C., and for 30 minutes pressing at 180 ° C., it was created made of 1mm thick sheet. About each obtained sheet | seat, the yellowness was measured using the color difference meter (TC-8600A: The product name made from Tokyo Denshoku), and coloring resistance was evaluated.
3. The resin composition obtained by blending the substances shown in [Table 1] and [Table 2] was calendered at 170 ° C., and the time until peeling from the calender roll (mill adhesion time, minutes) Measured and evaluated heat resistance.
The above evaluation results are shown in [Table 2].
２．上記１で得られたシートを貼り合わせて、180℃で5分間、及び180℃で30分間プレス加工を行い、厚さ1mmのシートを作製した。得られたシートそれぞれについて、色差計（TC-8600A：（有）東京電色製の商品名）を用いて黄色度を測定し、耐着色性を評価した。
３．［表１］及び［表２］に示した物質を配合して得られた樹脂組成物を、170℃でカレンダー加工して、カレンダーロールから剥離しなくなるまでの時間（ミル粘着時間、分）を測定し、耐熱性を評価した。
上記の評価結果を［表２］に示す。 1. The resin composition obtained by blending the substances shown in [Table 1] and [Table 2] was calendered at 170 ° C. for 5 minutes to obtain a sheet having a thickness of 0.7 mm. The obtained sheet was placed in a gear oven at 190 ° C. and the decomposition time (minutes) was measured to evaluate the thermal stability.
2. By bonding sheets obtained in the above 1, 5 min at 180 ° C., and for 30 minutes pressing at 180 ° C., it was created made of 1mm thick sheet. About each obtained sheet | seat, the yellowness was measured using the color difference meter (TC-8600A: The product name made from Tokyo Denshoku), and coloring resistance was evaluated.
3. The resin composition obtained by blending the substances shown in [Table 1] and [Table 2] was calendered at 170 ° C., and the time until peeling from the calender roll (mill adhesion time, minutes) Measured and evaluated heat resistance.
The above evaluation results are shown in [Table 2].
＊2：オクチル酸カルシウム
＊3：ステアリン酸亜鉛
＊4：オクチル酸亜鉛
＊5：オクチル酸カリウム
［表２］から明らかなように、有機酸カルシウムと有機酸亜鉛のみを組み合わせて使用した場合(比較例1-1、2)には、得られた塩化ビニル樹脂の分解時間及びミル粘着時間が短く、熱安定性と耐熱性が不十分であることが確認された。また、ステアリン酸カルシウムとステアリン酸亜鉛との組合せに、更にオクチル酸カルシウムを少量添加しても(比較例1-3)、物性が改善されないことも確認された。
また、有機酸亜鉛のみに有機酸カリウムを組み合わせた場合(比較例1-4)には、耐熱性、耐着色性ともに著しく劣ることが確認された。 As is apparent from [Table 2], when only organic acid calcium and organic acid zinc are used in combination (Comparative Examples 1-1 and 2), the decomposition time and mill adhesion time of the obtained vinyl chloride resin It was confirmed to be short and insufficient in heat stability and heat resistance. It was also confirmed that even when a small amount of calcium octylate was added to the combination of calcium stearate and zinc stearate (Comparative Example 1-3), the physical properties were not improved.
In addition, when organic acid potassium was combined with only organic acid zinc (Comparative Example 1-4), it was confirmed that both heat resistance and coloring resistance were remarkably inferior.
また、有機酸亜鉛のみに有機酸カリウムを組み合わせた場合(比較例1-4)には、耐熱性、耐着色性ともに著しく劣ることが確認された。 As is apparent from [Table 2], when only organic acid calcium and organic acid zinc are used in combination (Comparative Examples 1-1 and 2), the decomposition time and mill adhesion time of the obtained vinyl chloride resin It was confirmed to be short and insufficient in heat stability and heat resistance. It was also confirmed that even when a small amount of calcium octylate was added to the combination of calcium stearate and zinc stearate (Comparative Example 1-3), the physical properties were not improved.
In addition, when organic acid potassium was combined with only organic acid zinc (Comparative Example 1-4), it was confirmed that both heat resistance and coloring resistance were remarkably inferior.
これに対して、有機酸カルシウムと有機酸亜鉛の総量に対し、少量の有機酸カリウムを添加した本発明の場合(実施例1-1、2)には、得られた塩化ビニル樹脂の熱安定性と耐熱性が著しく改善されると共に、耐着色性も改善されることが確認された。
In contrast, in the case of the present invention in which a small amount of potassium organic acid was added to the total amount of organic acid calcium and organic acid zinc (Examples 1-1 and 2), the thermal stability of the obtained vinyl chloride resin It was confirmed that the coloring property and the heat resistance were remarkably improved and the coloring resistance was also improved.
本発明の非発泡性塩化ビニル系樹脂組成物は、従来の製品より熱安定性及び耐着色性に優れた塩化ビニル系樹脂成型品を提供することができるので、種々の産業の分野に利用する価値がある。
Since the non-foamable vinyl chloride resin composition of the present invention can provide a vinyl chloride resin molded product having better thermal stability and color resistance than conventional products, it can be used in various industrial fields. worth it.
Since the non-foamable vinyl chloride resin composition of the present invention can provide a vinyl chloride resin molded product having better thermal stability and color resistance than conventional products, it can be used in various industrial fields. worth it.
Claims (10)
- 少なくとも、(a)有機酸カルシウム塩、(b)有機酸亜鉛塩及び(c)有機酸カリウム塩を含有してなる、発泡剤を含有しない非発泡性塩化ビニル系樹脂組成物であって、前記(a)有機酸カルシウム塩、(b)有機酸亜鉛塩及び(c)有機酸カリウム塩の含有量が、それぞれ、塩化ビニル系樹脂100質量部に対し、(a)0.01～5質量部、(b)0.01～5質量部及び(c)0.001～1質量部であることを特徴とする、非発泡性塩化ビニル系樹脂組成物。 A non-foamable vinyl chloride resin composition containing no foaming agent, comprising at least (a) an organic acid calcium salt, (b) an organic acid zinc salt and (c) an organic acid potassium salt, The content of (a) organic acid calcium salt, (b) organic acid zinc salt and (c) organic acid potassium salt is (a) 0.01-5 parts by mass, A non-foamable vinyl chloride resin composition, characterized in that it is b) 0.01-5 parts by mass and (c) 0.001-1 parts by mass.
- 前記(a)成分及び(b)成分が、カルシウムと亜鉛のモル比で1/1～10/1となるように使用されている、請求項1に記載された非発泡性塩化ビニル系樹脂組成物。 2. The non-foamable vinyl chloride resin composition according to claim 1, wherein the component (a) and the component (b) are used so that a molar ratio of calcium to zinc is 1/1 to 10/1. object.
- 前記(c)成分が、(a)成分及び(b)成分のカルシウムと亜鉛の総量1モルに対し、カリウムが0.01～0.3モルとなるように使用されている、請求項1又は2に記載された非発泡性塩化ビニル系樹脂組成物。 The component (c) is used according to claim 1 or 2, wherein potassium is used in an amount of 0.01 to 0.3 mol with respect to 1 mol of the total amount of calcium and zinc in the components (a) and (b). Non-foaming vinyl chloride resin composition.
- 前記(c)成分が、塩化ビニル系樹脂１００質量部に対して0.001～1質量部となるように使用されている、請求項1又は2に記載された非発泡性塩化ビニル系樹脂組成物。 3. The non-foamable vinyl chloride resin composition according to claim 1, wherein the component (c) is used in an amount of 0.001 to 1 part by mass with respect to 100 parts by mass of the vinyl chloride resin.
- 前記(a)成分が、有機カルボン酸、フェノール類及び有機リン酸類のカルシウム塩の中から選択された少なくとも１種の塩である、請求項１に記載された非発泡性塩化ビニル系樹脂組成物。 The non-foamable vinyl chloride resin composition according to claim 1, wherein the component (a) is at least one salt selected from organic carboxylic acids, phenols, and calcium salts of organic phosphoric acids. .
- 前記(b)成分が、有機カルボン酸、フェノール類及び有機リン酸類の亜鉛塩の中から選択された少なくとも１種の塩である、請求項１に記載された非発泡性塩化ビニル系樹脂組成物。 The non-foamable vinyl chloride resin composition according to claim 1, wherein the component (b) is at least one salt selected from organic carboxylic acids, phenols, and zinc salts of organic phosphoric acids. .
- 前記(c)成分が、有機カルボン酸、フェノール類及び有機リン酸類のカリウム塩の中から選択された少なくとも１種の塩である、請求項１に記載された非発泡性塩化ビニル系樹脂組成物。 The non-foamable vinyl chloride resin composition according to claim 1, wherein the component (c) is at least one salt selected from organic carboxylic acids, phenols, and potassium salts of organic phosphoric acids. .
- 前記(a)成分及び(b)成分が、カルシウムと亜鉛のモル比で2/1～8/1となるように使用されている、請求項2に記載された非発泡性塩化ビニル系樹脂組成物。 3. The non-foamable vinyl chloride resin composition according to claim 2, wherein the component (a) and the component (b) are used so that a molar ratio of calcium to zinc is 2/1 to 8/1. object.
- 前記(c)成分が、(a)成分及び(b)成分のカルシウムと亜鉛の総量1モルに対し、カリウムが0.05～0.25モルとなるように使用されている、請求項3に記載された非発泡性塩化ビニル系樹脂組成物。 The non-component according to claim 3, wherein the component (c) is used so that potassium is 0.05 to 0.25 mol with respect to 1 mol of the total amount of calcium and zinc of the components (a) and (b). Foamable vinyl chloride resin composition.
- 他の添加剤として、可塑剤、ハイドロタルサイト化合物、ゼオライト化合物、β-ジケトン化合物、過塩素酸塩類、エポキシ化合物、多価アルコール、リン系、フェノール系及び硫黄系等の酸化防止剤、紫外線吸収剤、ヒンダードアミン系等の光安定剤、充填剤、滑剤からなる群の中から選択された少なくとも１種を含有する、請求項1に記載された非発泡性塩化ビニル系樹脂組成物。
Other additives include plasticizers, hydrotalcite compounds, zeolite compounds, β-diketone compounds, perchlorates, epoxy compounds, polyhydric alcohols, phosphorus-based, phenol-based and sulfur-based antioxidants, UV absorption 2. The non-foamable vinyl chloride resin composition according to claim 1, comprising at least one selected from the group consisting of an agent, a light stabilizer such as a hindered amine, a filler, and a lubricant.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008006558A JP5424440B2 (en) | 2008-01-16 | 2008-01-16 | Non-foaming vinyl chloride resin composition |
| JP2008-006558 | 2008-01-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2009090710A1 true WO2009090710A1 (en) | 2009-07-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2008/003740 WO2009090710A1 (en) | 2008-01-16 | 2008-12-12 | Non-expandable vinyl chloride resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5424440B2 (en) |
| WO (1) | WO2009090710A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010087093A1 (en) * | 2009-01-29 | 2010-08-05 | 株式会社Adeka | Vinyl chloride resin composition |
| CN114174407A (en) * | 2019-08-15 | 2022-03-11 | Sika技术股份公司 | Thermally expandable composition comprising endothermic blowing agent |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358214B (en) * | 2019-07-10 | 2021-12-28 | 深圳市邻友通科技发展有限公司 | Peripheral belt material and inner pull belt material of inflatable mattress, preparation method of peripheral belt material and inner pull belt material and inflatable mattress |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5313659A (en) * | 1976-07-23 | 1978-02-07 | Adeka Argus Chem Co Ltd | Stabilized halogen-containing resin compositions |
| JPS54114556A (en) * | 1978-02-28 | 1979-09-06 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
| JPS60130629A (en) * | 1983-12-16 | 1985-07-12 | Dainippon Ink & Chem Inc | Vinyl chloride resin composition for foam |
| JPS63268755A (en) * | 1987-04-27 | 1988-11-07 | Mitsubishi Kasei Vinyl Co | Vinyl chloride-based polymer composition |
| JPH01292053A (en) * | 1988-05-18 | 1989-11-24 | Kiyoueishiya Yushi Kagaku Kogyo Kk | Plastisol composition curable at low temperature |
| JPH02232239A (en) * | 1989-03-03 | 1990-09-14 | Sakai Chem Ind Co Ltd | Expandable vinyl chloride resin composition |
| JPH0468044A (en) * | 1990-07-09 | 1992-03-03 | Sumitomo Chem Co Ltd | Vinyl chloride resin composition and matte finished article prepared therefrom |
| JPH10219004A (en) * | 1997-02-12 | 1998-08-18 | Asahi Denka Kogyo Kk | Agricultural thermoplastic resin film |
| JP2004189777A (en) * | 2002-12-06 | 2004-07-08 | Asahi Denka Kogyo Kk | Wire-coating chlorine-containing resin composition |
| JP2004189776A (en) * | 2002-12-06 | 2004-07-08 | Asahi Denka Kogyo Kk | Chlorine-containing resin composition for hose |
| JP2008214480A (en) * | 2007-03-02 | 2008-09-18 | Adeka Corp | Vinyl chloride resin composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04202452A (en) * | 1990-11-30 | 1992-07-23 | Katsuta Kako Kk | Polyvinyl chloride resin composition |
-
2008
- 2008-01-16 JP JP2008006558A patent/JP5424440B2/en not_active Expired - Fee Related
- 2008-12-12 WO PCT/JP2008/003740 patent/WO2009090710A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5313659A (en) * | 1976-07-23 | 1978-02-07 | Adeka Argus Chem Co Ltd | Stabilized halogen-containing resin compositions |
| JPS54114556A (en) * | 1978-02-28 | 1979-09-06 | Sakai Chem Ind Co Ltd | Chlorine-containing resin composition |
| JPS60130629A (en) * | 1983-12-16 | 1985-07-12 | Dainippon Ink & Chem Inc | Vinyl chloride resin composition for foam |
| JPS63268755A (en) * | 1987-04-27 | 1988-11-07 | Mitsubishi Kasei Vinyl Co | Vinyl chloride-based polymer composition |
| JPH01292053A (en) * | 1988-05-18 | 1989-11-24 | Kiyoueishiya Yushi Kagaku Kogyo Kk | Plastisol composition curable at low temperature |
| JPH02232239A (en) * | 1989-03-03 | 1990-09-14 | Sakai Chem Ind Co Ltd | Expandable vinyl chloride resin composition |
| JPH0468044A (en) * | 1990-07-09 | 1992-03-03 | Sumitomo Chem Co Ltd | Vinyl chloride resin composition and matte finished article prepared therefrom |
| JPH10219004A (en) * | 1997-02-12 | 1998-08-18 | Asahi Denka Kogyo Kk | Agricultural thermoplastic resin film |
| JP2004189777A (en) * | 2002-12-06 | 2004-07-08 | Asahi Denka Kogyo Kk | Wire-coating chlorine-containing resin composition |
| JP2004189776A (en) * | 2002-12-06 | 2004-07-08 | Asahi Denka Kogyo Kk | Chlorine-containing resin composition for hose |
| JP2008214480A (en) * | 2007-03-02 | 2008-09-18 | Adeka Corp | Vinyl chloride resin composition |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010087093A1 (en) * | 2009-01-29 | 2010-08-05 | 株式会社Adeka | Vinyl chloride resin composition |
| US8841371B2 (en) | 2009-01-29 | 2014-09-23 | Adeka Corporation | Vinyl chloride resin composition |
| CN114174407A (en) * | 2019-08-15 | 2022-03-11 | Sika技术股份公司 | Thermally expandable composition comprising endothermic blowing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2009167289A (en) | 2009-07-30 |
| JP5424440B2 (en) | 2014-02-26 |
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