WO2022118751A1 - Agent conférant une résistance aux amines pour une résine de chlorure de vinyle - Google Patents

Agent conférant une résistance aux amines pour une résine de chlorure de vinyle Download PDF

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Publication number
WO2022118751A1
WO2022118751A1 PCT/JP2021/043389 JP2021043389W WO2022118751A1 WO 2022118751 A1 WO2022118751 A1 WO 2022118751A1 JP 2021043389 W JP2021043389 W JP 2021043389W WO 2022118751 A1 WO2022118751 A1 WO 2022118751A1
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Prior art keywords
vinyl chloride
acid
chloride resin
imparting agent
amine
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PCT/JP2021/043389
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English (en)
Japanese (ja)
Inventor
祐介 岩崎
祥晴 山本
忠士 仙石
一暢 田中
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株式会社Adeka
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Priority to JP2022566886A priority Critical patent/JPWO2022118751A1/ja
Publication of WO2022118751A1 publication Critical patent/WO2022118751A1/fr

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/02Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/36Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/39Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to an amine resistance imparting agent for vinyl chloride resin (hereinafter, also referred to as “amine resistance imparting agent”), and the present invention can suppress discoloration of the vinyl chloride resin due to amine.
  • Vinyl chloride resin has excellent properties such as flame retardancy, chemical resistance, mechanical stability, heat resistance, and weather resistance, and is inexpensive, so it is widely used as a general-purpose resin material with high utility value. It is widely used as a skin material for automobile interior materials.
  • an interior material for an automobile is composed of a skin layer for giving a feeling (texture) such as a soft feeling, a high-class feeling, and a design such as an aesthetic appearance, and a base material layer for holding a structure.
  • a feeling such as a soft feeling, a high-class feeling, and a design such as an aesthetic appearance
  • a base material layer for holding a structure.
  • the epidermis layer is often lined with a foam layer such as urethane to give a softer feeling.
  • vinyl chloride resin As this skin layer, vinyl chloride resin, thermoplastic elastomer, polyolefin foam such as polyethylene, etc. are used. Among them, vinyl chloride resin is widely used because it can give various tactile sensations from semi-hard to soft depending on the amount of plasticizer, and it is also excellent in molding processability and design. ..
  • Patent Documents 1 and 2 propose a vinyl chloride resin composition to which zinc dithiocarbamate is added.
  • Patent Document 3 is for improving the blackening promotion phenomenon (zinc burning phenomenon) of the vinyl chloride resin due to zinc and the weather resistance, and suppresses the discoloration of the vinyl chloride resin due to the amine. It is clearly different from what we do, and the current situation is that we cannot obtain any knowledge on this point.
  • an object of the present invention is an amine resistance imparting agent for vinyl chloride resin, a stabilizer composition for vinyl chloride resin, a vinyl chloride resin composition, which can suppress discoloration of vinyl chloride resin due to amine. It is an object of the present invention to provide a vinyl chloride resin molded body, a laminate, an automobile interior material, and a method for suppressing discoloration of a vinyl chloride resin.
  • a predetermined zinc dithiocarbamate compound can suppress discoloration of a vinyl chloride resin due to an amine, and have completed the present invention.
  • the amine resistance-imparting agent for vinyl chloride resin of the present invention is characterized by containing one or more of the zinc dithiocarbamate compounds represented by the following general formula (1).
  • R 1 and R 2 each independently have an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms. Represented, R 1 and R 2 may be linked to form a ring with the nitrogen atom to which they are bonded.
  • the vinyl chloride resin is preferably a vinyl chloride resin for automobile interior materials.
  • the vinyl chloride resin for the automobile interior material is a raw material resin for the vinyl chloride resin molded body used in the automobile interior material composed of a laminate of the vinyl chloride resin molded body and the polyurethane foam molded body. Is preferable.
  • the stabilizer composition for a vinyl chloride resin of the present invention is characterized by containing one or more of the stabilizers for a vinyl chloride resin and the amine resistance imparting agent for a vinyl chloride resin of the present invention. It is something to do.
  • the vinyl chloride-based resin composition of the present invention is characterized by containing a vinyl chloride-based resin and an amine resistance-imparting agent for a vinyl chloride-based resin of the present invention.
  • the content of the amine resistance imparting agent for vinyl chloride resin is 0.005 to 3.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Is preferable.
  • the vinyl chloride resin composition of the present invention is suitable for powder molding.
  • the vinyl chloride-based resin molded product of the present invention is characterized by being obtained from the vinyl chloride-based resin composition of the present invention.
  • the laminate of the present invention is a laminate of a vinyl chloride resin molded product and a polyurethane foam, and is characterized in that the vinyl chloride resin molded product is obtained from the vinyl chloride resin composition of the present invention. It is something to do.
  • the automobile interior material of the present invention is characterized by containing the vinyl chloride resin molded product of the present invention.
  • Other automobile interior materials of the present invention are characterized by containing the laminate of the present invention.
  • the method for suppressing discoloration of a vinyl chloride resin of the present invention is a method for suppressing discoloration of an automobile interior material including a laminate of a vinyl chloride resin molded body and a polyurethane foamed molded body, and is an amine resistance resistant method for a vinyl chloride resin of the present invention. It is characterized in that the sex-imparting agent is blended with a vinyl chloride-based resin, which is a raw material resin for a vinyl chloride-based resin molded body.
  • an amine resistance imparting agent for vinyl chloride resin a stabilizer composition for vinyl chloride resin, a vinyl chloride resin composition, vinyl chloride, which can suppress discoloration of vinyl chloride resin due to amine. It is possible to provide a method for suppressing discoloration of a based resin molded body, a laminated body, an automobile interior material, and a vinyl chloride based resin.
  • the vinyl chloride resin molded product of the present invention suppresses discoloration due to an amine compound and is suitable as an automobile interior material.
  • the amine resistance imparting agent for vinyl chloride resin of the present invention has a function of imparting amine resistance to the vinyl chloride resin, which suppresses discoloration of the vinyl chloride resin due to the amine compound.
  • the amine resistance-imparting agent for vinyl chloride resin of the present invention contains one or more of zinc dithiocarbamate compounds represented by the following general formula (1).
  • R 1 and R 2 each independently have an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryl alkyl group having 7 to 20 carbon atoms. show.
  • Examples of the alkyl group having 1 to 20 carbon atoms of R 1 and R 2 of the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
  • n-pentyl isopentyl, neopentyl, tert-amyl, 1,2-dimethylpropyl, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, 1-isopropylpropyl, 1,2-dimethylbutyl, n-heptyl, 2- Heptyl, 1,4-dimethylpentyl, tert-heptyl, 2-methyl-1-isopropylpropyl, 1-ethyl-3-methylbutyl, n-octyl, tert-octyl, 2-ethylhexyl, 2-methylhexyl, 2-propyl Hexyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundesyl, n-dodecyl, isododecyl, n
  • Examples of the aryl group of R 1 and R 2 of the general formula (1) having 6 to 20 carbon atoms include phenyl, p-methylphenyl, o-methylphenyl, p-tert-butylphenyl and p-methoxyphenyl. o-biphenylyl, m-biphenylyl, p-biphenylyl, ⁇ -naphthyl, ⁇ -naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthril, 3-phenanthril, 4-phenanthryl, 9- Examples thereof include phenyl, benzyl and the like.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms of R 1 and R 2 of the general formula (1) include benzyl, phenethyl, 2-phenylpropane-2-yl, styryl, cinnamyl, diphenylmethyl and triphenylmethyl. And so on.
  • R 1 and R 2 of the general formula (1) may be linked to form a ring together with the nitrogen atom to which each is bonded.
  • Examples of such a ring include a pyrrolidine ring and a piperidine ring.
  • R 1 and R 2 are preferably an alkyl group, a phenyl group or a benzyl group having 1 to 4 carbon atoms, preferably a methyl group, an ethyl group or an n-propyl group, from the viewpoint of imparting amine resistance to the vinyl chloride resin.
  • An n-butyl group, a phenyl group or a benzyl group is more preferable, a methyl group or an ethyl group is even more preferable, and an ethyl group is particularly preferable.
  • zinc dithiocarbamate compound represented by the general formula (1) preferable from the viewpoint of imparting amine resistance include the following compound No. 1 to No. 7 is mentioned.
  • compound No. 1, No. 2. No. 4, No. 5, No. 6, No. 7 is more preferable, and compound No. 1, No. 2 is even more preferable, and compound No. 2 is particularly preferable.
  • the amine resistance imparting agent of the present invention is used in combination with one or more of the stabilizers for vinyl chloride resin and used as a stabilizer composition for vinyl chloride resin.
  • a zinc salt of an organic acid other than dithiocarbamic acid is preferable from the viewpoint of amine resistance and thermal stability.
  • the zinc salt of such an organic acid include zinc salts of organic carboxylic acids, phenols and organic phosphoric acids.
  • organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, benzoic acid, caproic acid, enant acid, capric acid, pelargonic acid, 2-ethylhexic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecic acid, and lauric acid.
  • Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as butane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, merophaneic acid and pyromellitic acid.
  • phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-.
  • Examples thereof include ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamilphenol, methylisohexylphenol, and methyl tertiary octylphenol.
  • 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, and phosphonic acid stearyl ester. Can be mentioned.
  • the zinc salt of the organic acid may be an acidic salt, a neutral salt, a basic salt, or a hyperbasic complex in which a part or all of the base of the basic salt is neutralized with carbonic acid.
  • the zinc salt of an organic acid may be composed of two or more kinds of organic acids.
  • a zinc salt made of a monovalent organic acid the same organic acid may form an anion moiety and form a salt with divalent zinc forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent zinc that forms an anionic moiety and forms a cation moiety.
  • Zinc salts include zinc benzoate, zinc tolurate, 4-tert-butyl zinc benzoate, zinc stearate, zinc laurate, zinc versaticate, zinc octylate, and oleic acid in terms of amine resistance and thermal stability. Zinc, palmitin zinc, and myristin zinc are preferred. Only one type of zinc salt of organic acid may be used, or two or more types may be used in combination.
  • the content of the zinc salt of the organic acid is the point of amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent. Therefore, 5 to 20000 parts by mass is preferable, 10 to 8000 parts by mass is more preferable, and 20 to 800 parts by mass is even more preferable.
  • the stabilizer to be used in combination with the amine resistance imparting agent is a group of barium salts of organic acids and barium carbonates of hyperbasic from the viewpoint of amine resistance and thermal stability.
  • the stabilizer to be used in combination with the amine resistance imparting agent is a group of barium salts of organic acids and barium carbonates of hyperbasic from the viewpoint of amine resistance and thermal stability.
  • One or more selected from the above is preferable.
  • barium salt of organic acid examples include barium salts such as organic carboxylic acids, phenols and organic phosphoric acids.
  • organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, benzoic acid, caproic acid, enant acid, capric acid, pelargonic acid, 2-ethylhexic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecic acid, and lauric acid.
  • Examples thereof include di- or triester compounds of trivalent or tetravalent carboxylic acids such as butane tricarboxylic acid, butane tetracarboxylic acid, hemimellitic acid, trimellitic acid, merophaneic acid and pyromellitic acid.
  • phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, 2-.
  • Examples thereof include ethylhexylphenol, tertiary nonylphenol, decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamilphenol, methylisohexylphenol, and methyl tertiary octylphenol.
  • 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, and phosphonic acid stearyl ester. Can be mentioned.
  • the barium salt of an organic acid may be composed of two or more kinds of organic acids.
  • the same organic acid may form an anion moiety and form a salt with a divalent barium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with divalent barium that forms an anionic moiety and forms a cation moiety.
  • the barium salt of the organic acid may be used alone or in combination of two or more.
  • the barium salt of the organic acid may be an acid salt, a neutral salt, or a basic salt.
  • the superbasic barium carbonate salt is a liquid superbasic carboxylate / carbonate complex of barium.
  • This complex unlike a simple mixture of barium carboxylic acid positive salt and barium carbonate, is a complex formed by some interaction and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of a carboxylic acid positive salt of barium, barium carbonate, and a composite salt of barium carboxylic acid and carbonic acid as constituents, and is composed mainly of barium carbonate, barium carboxylic acid positive salt and barium carboxylic acid.
  • a complex salt of carbonic acid and carbonic acid exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • liquid perbasic carboxylate / carbonate complexes of barium can be produced, for example, by the production method shown in JP-A-2004-238364.
  • liquid perbasic carboxylate / carbonate complex of barium various commercially available complexes can be used as they are.
  • hyperbasic barium carbonate salts may be used alone or in combination of two or more.
  • the stabilizer composition of the present invention contains a barium salt or a perbasic carbonate barium salt of an organic acid
  • the content thereof is amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent. From the viewpoint of properties, 10 to 60,000 parts by mass is preferable, 30 to 10000 parts by mass is more preferable, and 50 to 2000 parts by mass is even more preferable.
  • the stabilizer to be used in combination with the amine resistance imparting agent is a group of calcium salts of organic acids and calcium carbonates of hyperbasic acid from the viewpoint of amine resistance and thermal stability.
  • the calcium salt of such an organic acid include calcium salts of organic carboxylic acids, phenols and organic phosphoric acids.
  • Examples of the organic carboxylic acid include those exemplified by barium salt.
  • Examples of the phenols include those exemplified by barium salts.
  • examples of the organic phosphoric acids include those exemplified by barium salts.
  • the calcium salt of an organic acid may be composed of two or more kinds of organic acids.
  • a calcium salt made of a monovalent organic acid the same organic acid may form an anion moiety and form a salt with a divalent calcium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent calcium that forms an anionic moiety and forms a cation moiety.
  • the calcium salt of the organic acid may be used alone or in combination of two or more.
  • the calcium salt of the organic acid may be an acid salt, a neutral salt, or a basic salt.
  • the hyperbasic calcium carbonate salt is a liquid perbasic carboxylate / carbonate complex of calcium.
  • This complex is different from a simple mixture of a positive carboxylic acid salt of calcium and calcium carbonate, which is a complex by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of calcium carboxylic acid positive salt, calcium carbonate, and a complex salt of calcium carboxylic acid and carbonic acid as constituents, and is composed mainly of calcium carbonate, calcium carboxylic acid positive salt and calcium carboxylic acid.
  • a complex salt of calcium and calcium exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • hyperbasic calcium carbonate salts may be used alone or in combination of two or more.
  • the stabilizer composition of the present invention contains a calcium salt of an organic acid or a perbasic calcium carbonate, the content thereof is amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent. From the viewpoint of properties, 10 to 60,000 parts by mass is preferable, 30 to 10000 parts by mass is more preferable, and 50 to 2000 parts by mass is even more preferable.
  • the ⁇ -diketone compound is preferable as the stabilizer used in combination with the amine resistance imparting agent from the viewpoint of amine resistance and thermal stability.
  • ⁇ -diketone compounds include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and distearoylmethane.
  • ⁇ -diketone compound Only one type of ⁇ -diketone compound may be used, or two or more types may be used in combination.
  • dibenzoylmethane, stearoylbenzoylmethane or acetylacetone zinc salt is preferable from the viewpoint of amine resistance and thermal stability.
  • the content thereof is 10 to 60,000 mass by mass with respect to 100 parts by mass of the amine resistance imparting agent from the viewpoint of amine resistance and thermal stability. Parts are preferable, 30 to 10000 parts by mass are more preferable, and 50 to 2000 parts by mass are even more preferable.
  • one or more phosphite ester compounds are preferable from the viewpoint of amine resistance and thermal stability.
  • phosphorous acid ester compounds include phosphorous acid trialkyl ester, phosphorous acid dialkyl ester, phosphorous acid dialkyl monoallyl ester, phosphorous acid alkylallyl ester, phosphorous acid monoalkyl diallyl ester, and phosphorous acid diallyl ester. , Phosphorous acid triallyl ester and the like.
  • a triester or a diester can be used, but from the viewpoint of thermal stability, it is preferable to use a triester.
  • Thioester can also be used.
  • phosphite compounds include triphenylphosphite, tricresylphosphite, tris (2,4-dithiary butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl).
  • Phenylphosphite Tris (mono- and di-mixed nonylphenyl) phosphite, Tris (2,4-di-tertiary butylphenyl) phosphite, diphenylphosphite, 2,2'-methylenebis (4,6-di) Tertiary Butylphenyl) Octylphosphite, 2,2'-Methylenebis (4,6-3rd Butylphenyl) -2-ethylhexylphosphite, 2,2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecyl Phenylphosphite, 2,2'-Ethyldenbis (4,6-dithiary butylphenyl) fluorophosphite, octyldiphenylphosphite, diphenyldecylphosphite, diphenyl (2-e
  • the phosphite ester compound may be used alone or in combination of two or more.
  • these subphosphate ester compounds from the viewpoint of thermal stability, it is preferable to use a subphosphate ester compound having 12 to 80 carbon atoms, and a subphosphate ester compound having 12 to 46 carbon atoms is used. It is more preferable to use a subphosphate ester compound having 12 to 36 carbon atoms, and it is more preferable to use a subphosphate ester compound having 18 to 30 carbon atoms.
  • the stabilizer composition of the present invention contains a phosphite ester compound
  • the content thereof is 10 to 60,000 from the viewpoint of amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent.
  • mass is preferable, 50 to 6000 parts by mass is more preferable, and 100 to 2000 parts by mass is even more preferable.
  • phenolic antioxidants are preferable from the viewpoint of amine resistance and thermal stability.
  • examples of such phenolic antioxidants include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditritiary butyl-4-4).
  • phenolic antioxidant only one type of phenolic antioxidant may be used, or two or more types may be used in combination.
  • these phenolic antioxidants pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or octadecyl 3- (3,5) from the viewpoint of thermal stability.
  • -Di-tert-butyl-4-hydroxyphenyl) propionate is preferred.
  • the stabilizer composition of the present invention contains a phenolic antioxidant, the content thereof is 1 to 2000 from the viewpoint of amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent. By mass is preferable, 2 to 200 parts by mass is more preferable, and 4 to 100 parts by mass is even more preferable.
  • hindered amine-based light stabilizers are preferable from the viewpoint of amine resistance and thermal stability.
  • hindered amine-based light stabilizers include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2.
  • the stabilizer composition of the present invention contains a hindered amine-based light stabilizer
  • the content thereof is 5 to 15,000 from the viewpoint of amine resistance and thermal stability with respect to 100 parts by mass of the amine resistance imparting agent.
  • mass is preferable, 10 to 2000 parts by mass is more preferable, and 20 to 700 parts by mass is even more preferable.
  • one or more inorganic auxiliary agents are preferable from the viewpoint of amine resistance and thermal stability.
  • examples of such an inorganic auxiliary agent include hydrotalcite compounds and zeolite compounds.
  • hydrotalcite compound examples include compounds represented by the following general formula (2).
  • x1, x2 and y1 represent numbers that satisfy the conditions represented by the following formulas, 0 ⁇ x2 / x1 ⁇ 10, 2 ⁇ x1 + x2 ⁇ 20, 0 ⁇ y1 ⁇ 2, respectively, and m is Indicates 0 or any integer.
  • hydrotalcite compound magnesium and aluminum, or a double salt compound composed of zinc, magnesium and aluminum are preferably used. Further, the water of crystallization may be dehydrated. Such hydrotalcite compounds may be natural products or synthetic products. There are no restrictions on the crystal structure, crystal particle size, etc. of the hydrotalcite compound.
  • the surface thereof is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as oleic acid alkali metal salt, an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt, a higher fatty acid amide, and a higher grade.
  • a higher fatty acid ester, wax, or the like can also be used.
  • the hydrotalcite compound containing a perchlorate anion or treated with perchlorate can be used, but in terms of safety and environment. Considering the above points, its use is not preferable.
  • hydrotalcite compound Only one type of hydrotalcite compound may be used, or two or more types may be used in combination.
  • Zeolites are alkali or alkaline earth metal aluminosilicates with a unique three-dimensional zeolite crystal structure, typically A-type, X-type, Y-type and P-type zeolites, monodenites, and analsites. , Sodalite aluminosilicate, clinobtyrolite, erionite, chavasite, etc., and water-containing substances having crystalline water (so-called zeolite water) of these zeolite compounds or anhydrous products from which crystalline water has been removed.
  • zeolite water water-containing substances having crystalline water
  • any of these may be used, and those having a particle size of 0.1 to 50 ⁇ m can be used, and those having a particle size of 0.5 to 10 ⁇ m are particularly preferable. Only one kind of zeolite compound may be used, or two or more kinds may be used in combination.
  • the inorganic auxiliary agent only one type may be used, two or more types may be used in combination, or a hydrotalcite compound and a zeolite compound may be used in combination.
  • the stabilizer composition of the present invention contains an inorganic auxiliary agent
  • the content thereof is 50 to 80,000 mass by mass with respect to 100 parts by mass of the amine resistance imparting agent from the viewpoint of amine resistance and thermal stability. Parts are preferable, 100 to 8000 parts by mass are more preferable, and 400 to 4000 parts by mass are even more preferable.
  • the vinyl chloride-based resin composition of the present invention is characterized in that the amine-resistant imparting agent of the present invention is blended with the vinyl chloride-based resin.
  • the vinyl chloride-based resin in the vinyl chloride-based resin composition of the present invention is not particularly limited to its polymerization method such as massive polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and is, for example, polyvinyl chloride and chlorinated poly.
  • Vinyl chloride polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer Combined, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonilittle copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene Polymers, vinyl chloride-chlorinated propylene copolymers, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride- Vinyl chloride resins such as acrylon
  • vinyl chloride resins examples thereof include copolymers, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, blended products with polyesters, block copolymers, graft copolymers and the like.
  • These vinyl chloride resins may be a mixture of two or more kinds, or may be a mixture with other synthetic resins.
  • the vinyl chloride resin used is preferably polyvinyl chloride from the viewpoint of amine resistance, and particularly preferably polyvinyl chloride used for powder molding.
  • the amine resistance imparting agent of the present invention is 0.005 to 100 parts by mass with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of imparting amine resistance to the vinyl chloride resin. 3.0 parts by mass is preferable, 0.01 to 2.0 parts by mass is more preferable, 0.02 to 1.0 parts by mass is even more preferable, and 0.05 to 0.5 parts by mass is even more preferable. preferable. If it is less than 0.005 parts by mass, the amine resistance may be insufficient, and if it exceeds 3.0 parts by mass, the improvement of the effect is small, and rather it may adversely affect other performance.
  • the amine resistance imparting agent may be blended in the vinyl chloride resin as a stabilizer composition, or may be blended in the vinyl chloride resin separately from the stabilizer and other components to be blended.
  • the vinyl chloride resin composition of the present invention contains a plasticizer.
  • plasticizers include dibutylphthalate, butylhexylphthalate, diheptylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, dilaurylphthalate, dicyclohexylphthalate, dioctylterephthalate and other phthalate plasticizers; dioctyl adipate, diisononyl adipate, etc.
  • Adipate-based plasticizers such as diisodecyl adipate and di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Butoxyethyl) phosphate, octyldiphenyl phosphate and other phosphate plasticizers; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butane Polyhydric alcohols such as diols, 1,5-hexanediols, 1,6-hexanediols and neopentylglycols, and oxalic acid, malonic acid, succin
  • At least one selected from the group consisting of the trimellitic acid-based plasticizer which is a trimellitic acid ester compound and the pyromellitic acid-based plasticizer which is a pyromellitic acid ester compound has an amine resistance. Is preferable.
  • trimellitic acid ester compound or pyromellitic acid ester compound a trimellitic acid or a trimellitic acid and a monovalent alcohol triester compound or a tetraester compound are used, respectively.
  • the monohydric alcohol used for producing the trimellitic acid trimester compound or the pyromellitic acid tetraester compound includes, for example, methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, secondary butyl alcohol, and the like.
  • Tertiary butyl alcohol pentyl alcohol, isopentyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, isononyl alcohol, decanol, isodecanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradeca Examples thereof include linear or branched alcohols such as Noor, Pentadecanol, Hexadecanol, Heptadecanol, Octadecanol, Nonadecanol, Icosanol, Henicosanol, Docosanol and mixtures thereof.
  • the content of the plasticizer is preferably 5 to 200 parts by mass, preferably 10 to 100 parts by mass, with respect to 100 parts by mass of the vinyl chloride resin from the viewpoint of amine resistance. More preferred.
  • the vinyl chloride resin composition of the present invention preferably contains one or more stabilizers.
  • the stabilizer may be blended as a stabilizer composition or may be blended individually.
  • the vinyl chloride resin composition of the present invention other additives usually used for the vinyl chloride resin composition, for example, an epoxy compound, a polyhydric alcohol compound, an ultraviolet absorber, a filler and the like are added. be able to.
  • 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 fat oil, epoxidized castor oil, and epoxidized safflower oil.
  • polyhydric alcohol examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentylglycol, trimethylolpropane, ditrimethylolpropane, and 1,3,5-tris (2-hydroxyethyl) isocyanurate.
  • ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone) and the like.
  • fillers calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium alumina silicate, hydrocarbimite.
  • the vinyl chloride resin composition of the present invention includes a cross-linking agent, a foaming agent, an antistatic agent, an antifogging agent, a plate-out inhibitor, a surface treatment agent, a lubricant, a flame retardant, a fluorescent agent, and the like.
  • Antistatic agents, bactericidal agents, metal deactivators, mold release agents, pigments, processing aids, solvents and the like can be blended.
  • lubricants examples include hydrocarbon-based lubricants such as low-molecular-weight wax, paraffin wax, polyethylene wax, chlorinated hydrocarbons, and fluorocarbon; natural wax-based lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, and behenin.
  • Higher fatty acids such as acids and fatty acid-based lubricants such as oxy fatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide and oleylamide, and alkylene bis such as methylenebisstearylamide and ethylenebisstearylamide.
  • An aliphatic amide-based lubricant such as an aliphatic amide; a fatty acid monovalent alcohol ester compound such as stearyl stearate, butyl stearate, and distearyl phthalate, and also glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, and dipenta.
  • Fatty acid polyvalent alcohol ester compounds such as erythritol hexastearate, polyglycerin polylysinolate, and hardened castor oil, monovalent fatty acids such as dipentaerythritol adipic acid / stearic acid ester, and polybasic organic acids.
  • Fatty acid alcohol ester-based lubricants such as composite ester compounds of alcohol; fatty alcohol-based lubricants such as steearic acid, lauryl alcohol, and palmityl alcohol; metal soaps; montanic acid-based lubricants such as partially saponified montanic acid esters; acrylic lubricants ; Silicone oil and the like can be mentioned. Only one kind of these lubricants may be used, or two or more kinds thereof may be used in combination.
  • processing aids are homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; co-polymers of the above alkyl methacrylate and alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate.
  • pigments examples include white pigments such as titanium dioxide and blue pigments such as ultramarine blue and phthalocyanine blue.
  • the vinyl chloride-based resin composition of the present invention further includes other additives usually used for vinyl chloride-based resins, such as sulfur-based antioxidants, impact resistance improvers, reinforcing materials, perchlorates, and organic substances.
  • additives usually used for vinyl chloride-based resins such as sulfur-based antioxidants, impact resistance improvers, reinforcing materials, perchlorates, and organic substances.
  • Magnesium salts of acids, perbasic magnesium carbonates, flame retardants, flame retardant aids and the like can also be blended within a range that does not impair the effects of the present invention.
  • sulfur-based antioxidants examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). ⁇ -Alkyl mercaptopropionic acid esters and the like. Only one kind of these sulfur-based antioxidants may be used, or two or more kinds thereof may be used in combination.
  • impact resistance improvers examples include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene.
  • System-based graft copolymer acrylonitrile-styrene-butadiene-based copolymer rubber, acrylonitrile-styrene-butadiene-based graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene -Ethethylene-butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silicone Examples include rubber-based rubber.
  • EPDM diene examples include 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene and the like. Only one kind of these impact resistance improving agents may be used, or two or more kinds thereof may be used in combination.
  • fibrous, plate-shaped, granular, or powder-like ones that are usually used for strengthening synthetic resins can be used.
  • These fortifiers may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated with a coupling agent such as aminosilane or epoxysilane. It may have been processed. Only one kind of these fortifiers may be used, or two or more kinds thereof may be used in combination.
  • perchlorate salts include perchloric acid metal salts, ammonium perchlorate, perchloric acid-treated silicates, and the like.
  • metal constituting these metal salts include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, aluminum and the like.
  • the perchloric acid metal salt may be an anhydride or a hydrous salt, or may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof. Only one kind of these perchlorates may be used, or two or more kinds may be used in combination. However, in the resin composition of the present invention, the use of perchlorates is not preferable in consideration of safety and environmental aspects.
  • the magnesium salt of organic acid will be explained.
  • Examples of the magnesium salt of an organic acid include magnesium salts of organic carboxylic acids, phenols and organic phosphoric acids.
  • Examples of the organic carboxylic acid include those exemplified by the barium salt of the organic acid.
  • examples of the phenols include those exemplified by the barium salt of an organic acid.
  • examples of organic phosphoric acids include those exemplified by barium salts of organic acids.
  • the magnesium salt of an organic acid may be composed of two or more kinds of organic acids.
  • a magnesium salt made of a monovalent organic acid the same organic acid may form an anion moiety and form a salt with a divalent magnesium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent magnesium that forms an anionic moiety and forms a cation moiety. Only one type of magnesium salt of organic acid may be used, or two or more types may be used in combination.
  • the magnesium salt of the organic acid may be an acid salt, a neutral salt, or a basic salt.
  • the hyperbasic magnesium carbonate salt is a liquid perbasic carboxylate / carbonate complex of magnesium.
  • This complex unlike a simple mixture of magnesium, a positive carboxylic acid salt, and magnesium carbonate, is a complex formed by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of magnesium carboxylic acid positive salt, magnesium carbonate, and a composite salt of magnesium carboxylic acid and carbonic acid as constituents, and is composed mainly of magnesium carbonate, magnesium carboxylic acid positive salt, and magnesium carboxylic acid.
  • a complex salt of magnesium and carbon dioxide exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • the liquid perbasic carboxylate / carbonate complex of magnesium can be produced by the same method as the liquid superbasic liquid carboxylate / carbonate complex of barium. Further, a commercially available complex can be used as it is.
  • hyperbasic magnesium carbonate salts may be used alone or in combination of two or more.
  • flame retardants and flame retardants include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen-based flame retardants, silicone-based flame retardants, phosphoric acid ester-based flame retardants, condensed phosphoric acid ester-based flame retardants. , Intomescent flame retardants, antioxidants such as antimon trioxide, other inorganic flame retardants, organic flame retardants and the like.
  • triazine ring-containing compound examples include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butyreneguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, and trimethylenedi.
  • examples thereof include melamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene melamine and the like.
  • metal hydroxide examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.
  • Examples of phosphoric acid ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyldiphenyl phosphate.
  • Trixylenyl phosphate Trixylenyl phosphate, Octyldiphenyl phosphate, Xylenyldiphenyl phosphate, Trisisopropylphenyl phosphate, 2-Ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, Bis- (t-butylphenyl) phenyl phosphate, Tris- (t-) Examples thereof include butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like.
  • Examples of the condensed phosphoric acid ester flame retardant include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like.
  • Examples of the flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.
  • inorganic flame-retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.
  • inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc
  • surface-treated products thereof include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.
  • TIPAQUE R-680 titanium oxide: Ishihara Sangyo (Titanium oxide: Ishihara Sangyo)
  • Kyowamag 150 magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.
  • a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer can be used in the vinyl chloride-based resin composition of the present invention, it is preferable not to contain them from the viewpoint of toxicity and adverse effects on the environment. ..
  • a stabilizing aid usually used for vinyl chloride resin can be added within a range that does not impair the effect of the present invention.
  • a stabilizing aid for example, diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, silicate, p-tertiary butyl benzoic acid and the like are used.
  • additives usually used for vinyl chloride resins such as cross-linking agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, fungicides, fungicides, etc.
  • a metal deactivator, a mold release agent, etc. can be blended within a range that does not impair the effects of the present invention. Only one kind of these optional components may be used, or two or more kinds thereof may be used in combination.
  • the vinyl chloride resin composition of the present invention contains the amine resistance imparting agent of the present invention, the vinyl chloride resin and, if necessary, stabilizers, plasticizers and various additives, for example, a mortar mixer, a henschel mixer, a Banbury mixer, and the like. It can be mixed by stirring with a stirrer such as a ribbon blender to obtain a mixed powder of a vinyl chloride resin composition.
  • the amine resistance imparting agent, the vinyl chloride resin and, if necessary, a stabilizer, a plasticizer, and various additives of the present invention can be used, for example, a conical twin-screw extruder, a parallel twin-screw extruder, a single-screw extruder, or a conider.
  • a pellet-shaped vinyl chloride resin composition can also be obtained by melt-molding with a kneader such as a mold kneader or a roll kneader.
  • the vinyl chloride paste resin and, if necessary, stabilizers, plasticizers and various additives can be used, for example, a pony mixer, a butterfly mixer, a planetary mixer, a ribbon blender, a kneader, a dissolver, and the like. It is also possible to obtain a paste-like vinyl chloride resin composition by uniformly mixing with a mixer such as a shaft mixer, a Henshell mixer, or a three-roll mill and, if necessary, defoaming under reduced pressure.
  • the vinyl chloride resin molded product of the present invention is a vinyl chloride resin composition (blended powder or pellet) according to the present invention, which is vacuum-molded, compression-molded, extrusion-molded, injection-molded, calendar-molded, press-molded, or blow-molded. , By melt molding using a conventionally known method such as powder molding, it can be molded into a desired shape.
  • the paste-like vinyl chloride resin composition can be molded into a desired shape by molding using conventionally known methods such as spread molding, dipping molding, gravure molding, slash molding, and screen processing. can.
  • a molded product obtained by powder molding such as powder slush molding, fluid immersion molding, powder rotary molding is preferable, and molding obtained by powder slush molding is particularly preferable.
  • the body is particularly preferred.
  • the shape of the molded body is not particularly limited, and examples thereof include a rod shape, a sheet shape, a film shape, a plate shape, a cylindrical shape, a circular shape, an elliptical shape, for example, a star shape and a polygonal shape.
  • the vinyl chloride resin molded product of the present invention is preferably a laminate with polyurethane, particularly a polyurethane foam molded product, from the viewpoint of amine resistance.
  • the polyurethane particularly the polyurethane foam molded product, may be any conventionally known one, and can be obtained, for example, as follows. That is, it is obtained by reacting, foaming and curing a raw material of a polyurethane foam containing polyols, polyisocyanates, a foaming agent and a catalyst.
  • polyether polyol a polyether polyol or a polyester polyol is used.
  • polypropylene glycol polytetramethylene glycol
  • the polyhydric alcohol include glycerin and dipropylene glycol.
  • polyester polyol in addition to a condensed polyester polyol obtained by reacting a polycarboxylic acid such as adipic acid and phthalic acid with a polyol such as ethylene glycol, diethylene glycol, propylene glycol and glycerin, a lactone-based polyester polyol and a polycarbonate-based polyol. Polyols are used.
  • Polyisocyanates are compounds having a plurality of isocyanate groups, specifically, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalenediocyanate (NDI), and triphenylmethane tri.
  • TDI tolylene diisocyanate
  • MDI 4,4-diphenylmethane diisocyanate
  • NDI 1,5-naphthalenediocyanate
  • triphenylmethane tri triphenylmethane tri.
  • Isocyanate, xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), modified products thereof and the like are used.
  • the foaming agent is for foaming a polyurethane resin to form a polyurethane foam molded product.
  • a polyurethane resin for example, in addition to water, pentane, cyclopentane, hexane, cyclohexane, dichloromethane, carbon dioxide, etc. are used.
  • the catalyst is for accelerating the urethanization reaction between polyols and polyisocyanates, such as triethylenediamine, dimethylethanolamine, N, N', N'-trimethylaminoethylpiperazine, triphenylamine, triethylamine, N, N, N',, N'-tetramethyl-1,3-butanediamine, N-methylmorpholin, N-ethylmorpholin, N-acetylmorpholin, N-octylmorpholin, N-phenylmorpholin, N-hydroxylethylmorpholin, N-hydroxylmethylmorpholin, 4,4'-dithiodimorpholin, dimethylpiperazine, N, N, N', N'-tetramethylpropanediamine, trimethylaminoethylpiperazine, N, N-dimethylethanolamine, dimethylhexadecyl Amine, 1- (2-ethylhexenyl) piperazine, tri-n-octyl
  • the present invention is excellent and preferable because it is excellent in imparting the effect of suppressing discoloration of the vinyl chloride resin by the amine catalyst that promotes the urethanization reaction.
  • the vinyl chloride-based resin molded product of the present invention is useful and preferable as an automobile interior material from the viewpoint of amine resistance.
  • the laminated body composed of the vinyl chloride resin molded body and the polyurethane foam molded body is the skin layer, and further is composed of the base material layer for maintaining the structure.
  • the base material layer a known material such as a polypropylene resin molded body or an ABS resin molded body is used.
  • Examples of automobile interior materials include instrument panels, door trims, console boxes, glove boxes, pillar trims, dashboards, trunk trims, seats, ceiling materials, AT shifts, armrests, headrests, floor carpets, wire harnesses, various malls, etc.
  • Examples thereof include sashes, sealing materials, weather strips, gaskets, undercoat materials, etc., and in particular, as the above-mentioned automobile interior materials laminated with a polyurethane foam molded body, for example, instrument panels, door trims, seat seats, ceiling materials, etc. It is useful and preferable.
  • Examples 1 to 8 Comparative Examples 1 to 3
  • Vinyl chloride resin manufactured by Shin-Etsu Chemical Industry Co., Ltd., TK-1300 (average polymerization degree 1300) 100 parts by mass, diisononyl phthalate (plasticizer) 50 parts by mass, calcium carbonate (filler) 10 parts by mass, large epoxidation 3 parts by mass of soybean oil (epoxy compound), 2 parts by mass of Ba—Zn-based stabilizer (manufactured by ADEKA Co., Ltd., AC-255), and the following compound No. 1 as an amine resistance imparting agent. 1, No. 2. No. 4. No. 5, No. 6, No. 7 was mixed in the blending amounts (parts by mass) shown in Tables 1 and 2 to obtain a vinyl chloride resin composition.
  • a sheet was prepared by powder slash molding. That is, the obtained vinyl chloride resin composition was heated in a gear oven at 130 ° C. for 90 minutes and dried up. The dry-up compound was sprinkled on a textured mold heated to a surface temperature of 250 ° C. and allowed to stand for 15 seconds to melt. After shaking off the excess compound, the mold was placed in an oven set at 250 ° C. and allowed to stand for 45 seconds. The mold was taken out from the oven and cooled with water to obtain a vinyl chloride resin sheet having a thickness of 1 mm.
  • the obtained vinyl chloride resin sheet was backed with polyurethane foam to a thickness of 10 mm to prepare a laminated body.
  • the following ⁇ amine resistance test> was performed using the obtained laminate.
  • the one containing no amine resistance-imparting agent was evaluated as Comparative Example 1 in the same manner as in Examples.
  • an amine resistance-imparting agent as a zinc compound, 0.1 parts by mass of zinc stearate was blended as Comparative Example 2, and 0.1 parts by mass of zinc benzoate was blended as Comparative Example 3. It was evaluated in the same manner as in the examples.
  • ⁇ Amine resistance test> First, the yellowness of the obtained vinyl chloride resin sheet was measured. Next, the obtained laminate was placed in an oven at 80 ° C. for 8 weeks, the vinyl chloride resin sheet and the polyurethane foam were separated, and the yellowness of the vinyl chloride resin sheet was measured to determine the color difference ( ⁇ E). It can be said that the smaller the value, the better the amine resistance. The degree of yellowness was measured according to JIS K7373.

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Abstract

La présente invention concerne un agent conférant une résistance aux amines pour une résine de chlorure de vinyle capable d'inhiber la décoloration de résine de chlorure de vinyle par une amine, une composition de stabilisant pour résine de chlorure de vinyle, une composition de résine de chlorure de vinyle, un article moulé en résine de chlorure de vinyle, un stratifié, un matériau d'intérieur d'automobile, et un procédé d'inhibition de la décoloration de résine de chlorure de vinyle. La présente invention concerne un agent conférant une résistance aux amines pour une résine de chlorure de vinyle comprenant un ou plusieurs types de composés de dithiocarbamate de zinc représentés par la formule générale (1). Dans la formule générale (1), R1 et R2 représentent chacun indépendamment un groupe alkyle en C1-C20, un groupe aryle en C6-C20, ou un groupe arylalkyle en C7-C20, et R1 et R2 peuvent être liés et former un cycle conjointement avec l'atome d'azote auquel chacun se lie.
PCT/JP2021/043389 2020-12-04 2021-11-26 Agent conférant une résistance aux amines pour une résine de chlorure de vinyle WO2022118751A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5468853A (en) * 1977-11-11 1979-06-02 Katsuta Kako Kk Composition for stabilizing halogenncontaining resin
JPS5740540A (en) * 1980-08-25 1982-03-06 Dainippon Ink & Chem Inc Vinyl chloride resin composition
JPS6268839A (ja) * 1985-09-19 1987-03-28 Katsuta Kako Kk ポリ塩化ビニル系樹脂組成物
JPS6327546A (ja) * 1986-07-18 1988-02-05 Dainippon Ink & Chem Inc 塩化ビニル樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5468853A (en) * 1977-11-11 1979-06-02 Katsuta Kako Kk Composition for stabilizing halogenncontaining resin
JPS5740540A (en) * 1980-08-25 1982-03-06 Dainippon Ink & Chem Inc Vinyl chloride resin composition
JPS6268839A (ja) * 1985-09-19 1987-03-28 Katsuta Kako Kk ポリ塩化ビニル系樹脂組成物
JPS6327546A (ja) * 1986-07-18 1988-02-05 Dainippon Ink & Chem Inc 塩化ビニル樹脂組成物

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