CN102177203B - 透明制品用氯乙烯系树脂组合物以及将该组合物成形而成的透明成形品 - Google Patents
透明制品用氯乙烯系树脂组合物以及将该组合物成形而成的透明成形品 Download PDFInfo
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- CN102177203B CN102177203B CN200980139867.2A CN200980139867A CN102177203B CN 102177203 B CN102177203 B CN 102177203B CN 200980139867 A CN200980139867 A CN 200980139867A CN 102177203 B CN102177203 B CN 102177203B
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- acid
- vinyl chloride
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- resin composition
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000000465 moulding Methods 0.000 title abstract description 8
- -1 organic acid zinc salt Chemical class 0.000 claims abstract description 90
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000011701 zinc Substances 0.000 claims description 51
- 239000011777 magnesium Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 27
- 229960001545 hydrotalcite Drugs 0.000 claims description 27
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 23
- 239000000194 fatty acid Substances 0.000 claims description 23
- 229930195729 fatty acid Natural products 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 22
- 239000004902 Softening Agent Substances 0.000 claims description 21
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000314 lubricant Substances 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 17
- 230000004048 modification Effects 0.000 claims description 17
- 150000007524 organic acids Chemical class 0.000 claims description 16
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000004014 plasticizer Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052718 tin Inorganic materials 0.000 abstract description 9
- 229910052788 barium Inorganic materials 0.000 abstract description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 239000003381 stabilizer Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 20
- 150000002148 esters Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 15
- 239000003063 flame retardant Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- 238000006735 epoxidation reaction Methods 0.000 description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 7
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 6
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 229940059574 pentaerithrityl Drugs 0.000 description 5
- 150000003014 phosphoric acid esters Chemical class 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 4
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical class CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 4
- 229910020366 ClO 4 Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
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- 150000007513 acids Chemical class 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- 125000002947 alkylene group Chemical group 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 description 2
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- 239000010425 asbestos Substances 0.000 description 2
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Classifications
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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
- C08L27/02—Compositions 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
- C08L27/04—Compositions 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
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明是一种不含铅、锡、钡等的重金属系稳定剂的透明制品用氯乙烯系树脂组合物以及将该组合物成形而成的透明成形品。本发明的透明制品用氯乙烯系树脂组合物的特征在于：其是相对于氯乙烯系树脂100重量份而含有0.001重量份～10重量份的(A)有机酸锌盐的至少一种、以及0.001重量份～10重量份的(B)锌改性水滑石系化合物的至少一种而成。
Description
技术领域
本发明涉及一种透明制品用氯乙烯系树脂组合物，更详细来说，本发明涉及一种不使用重金属系稳定剂特别是锡系稳定剂的透明制品用氯乙烯系树脂组合物。
背景技术
氯乙烯系树脂可以通过添加增塑剂而容易地调整硬度，因此能用于各种用途。特别是完全不含增塑剂的硬质的氯乙烯系树脂组合物或者含有少量增塑剂的半硬质的氯乙烯系树脂组合物，由于刚性优异而被广泛用于建材等。因此，在完全不混合增塑剂的硬质氯乙烯系树脂组合物或仅少量混合增塑剂的半硬质氯乙烯系树脂组合物的情况下，当曝露在高温高压下加工时自不用说，即使是作为成形品的热稳定性及耐候性方面，也被要求有更高的性能。
以前，在由硬质的氯乙烯系树脂组合物所得的硬质透明成形品的情况下，被用于需要像玻璃那样的透明制品的容器类、工业板、装饰板、膜或片材(sheet)等广泛的制品。但另一方面，已知氯乙烯系树脂具有以下缺点：通常对于光或热的稳定性不足，在加热成形加工时或产品使用时，产生主要由脱卤化氢所引起的分解，容易产生着色或者物理特性下降。为了改善这种缺点，一直以来，人们尝试了混合有机酸的金属盐、有机锡化合物、有机亚磷酸酯化合物、环氧化合物、β-二酮化合物、抗氧化剂、紫外线吸收剂等各种稳定剂来改善氯乙烯系树脂的稳定性。
作为上述稳定剂，从成本方面的优势等观点来看，以前一直使用铅、镉等重金属系稳定剂，但是近年来环境问题日益受到关注，重金属等的毒性或者对环境的影响成为问题，而有使用钡-锌系的复合稳定剂的倾向。但是，最近人们也开始担心钡会影响环境，因此期望换成毒性更低的钙-锌系、镁-锌系或者钙-镁-锌系的复合稳定剂。
从这种观点来考虑，已提出了添加有机酸钙盐、有机酸锌盐、碱性亚磷酸盐及水滑石化合物的方法(专利文献1)，以及添加有机酸碱土金属盐、有机酸锌盐、碱性磷酸锌及水滑石化合物的方法(专利文献2)，但是即使将这些化合物组合使用，其耐热性等性能也是不足的。而且，这些文献中关于透明性完全没有记载，且没有任何与透明性的改善相关的启示。
进而，也提出了添加了无机填充剂、锌化合物、锌改性水滑石系化合物、热分解型有机发泡剂的发泡成形品用的氯乙烯系发泡性树脂组合物(专利文献3)，以及混合了己二酸酯系增塑剂、有机羧酸的钙盐、锌改性水滑石化合物的食品包装用聚氯乙烯系树脂组合物(专利文献4)。但是，这些文献中也都没有与透明性相关的任何记载，因此由这些文献无法获得与透明性改善相关的见解。
另外，作为可以提高透明性的稳定剂，提出了锡系稳定剂(专利文献5以及专利文献6)。但是，从对环境的影响或毒性的观点来看锡也不优选。另外，锡系稳定剂大多为液态，因此使用该液态的锡系稳定剂时，存在有不仅成形加工时的熔融树脂的润滑性下降，而且成形体的热变形温度(软化点)下降的问题。
先前技术文献
专利文献
专利文献1：日本专利特开平9-67489号公报
专利文献2：日本专利特开2003-160707号公报
专利文献3：日本专利特开平3-237140号公报
专利文献4：日本专利特开平6-100749号公报
专利文献5：日本专利特开昭62-4739号公报
专利文献6：日本专利特开2008-1840号公报
发明内容
因此，本发明的第一目的在于提供一种不使用铅、锡、钡等重金属系稳定剂的、透明性高而且加工性也优异的透明制品用氯乙烯系树脂组合物。
本发明的第二目的在于提供一种将不仅透明性高而且软化点等物理特性也优异的氯乙烯系树脂组合物成形而成的透明成形品。
即，本发明是一种透明制品用氯乙烯系树脂组合物以及将该组合物成形而成的透明成形品，所述透明制品用氯乙烯系树脂组合物的特征在于：其是相对于氯乙烯系树脂100重量份而含有0.001重量份～10重量份的(A)有机酸锌盐的至少一种、以及0.001重量份～10重量份的(B)锌改性水滑石系化合物的至少一种而成。
本发明中，优选使用下述通式(I)所示的化合物作为前述(B)成分的锌改性水滑石系化合物。
My1Zny2Alx(OH)2(CO3)x/2·mH2O (I)
其中，(I)式中的M表示镁、或者镁及钙，x、y1及y2分别表示满足下式所示条件的数，m表示0或者任意的正数；0＜x≤0.5，y1+y2＝1-x，y1≥y2，0.3≤y1＜1，0＜y2＜0.5。
本发明中，也可以进一步含有0.001重量份～10重量份的至少一种润滑剂作为(C)成分。进而，根据需要可以含有0重量份～50重量份、优选10重量份～50重量份、更优选20重量份～40重量份的增塑剂成分。通过像这样含有增塑剂，可以形成半硬质氯乙烯系树脂。另外，从毒性或环境问题角度，优选不含有机锡系化合物。
根据本发明，可以提供一种不仅透明性高而且加工性也优异的透明制品用氯乙烯系树脂组合物。本发明的透明制品用氯乙烯系树脂组合物特别适合于获得硬质或半硬质的、透明性高的、软化点等物理特性优异的成形品。
具体实施方式
以下，对本发明的透明制品用氯乙烯系树脂组合物加以详细说明。
本发明中使用的作为构成(A)成分有机酸锌盐的有机酸，可以列举：羧酸、有机磷酸或者酚类等。另外，该有机酸锌盐可以是酸性盐、碱性盐或者过碱性盐的任一种。
作为上述羧酸，例如可以列举：己酸、辛酸、壬酸、2-乙基己酸、癸酸、新癸酸、十一碳烯酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、12-羟基硬脂酸、氯硬脂酸、12-酮硬脂酸(12-ketostearic acid)、苯基硬脂酸、蓖麻油酸、亚油酸(linoleic acid)、亚麻酸(linolenic acid)、油酸、花生酸、山嵛酸、芥酸、巴西烯酸(brassidic acid)及类似酸，以及动物脂肪酸、椰子油 脂肪酸、桐油脂肪酸、大豆油脂肪酸及棉籽油脂肪酸等的、天然产出的上述酸的混合物，苯甲酸、对叔丁基苯甲酸、乙基苯甲酸、异丙基苯甲酸、甲基苯甲酸、二甲基苯甲酸、水杨酸、5-叔辛基水杨酸、环烷酸、环己甲酸等。
作为前述有机磷酸，可以列举：单或二辛基磷酸、单或二(十二烷基)磷酸、单或二(十八烷基)磷酸、单或二-(壬基苯基)磷酸、膦酸壬基苯基酯、膦酸硬脂酯等。
作为前述酚类，可以列举：苯酚、甲酚、乙酚、环己酚、壬酚、十二烷基苯酚等。
本发明中用作(A)成分的有机酸锌盐可以仅使用一种，也可以两种以上合用。无论是哪种情况，从本发明的组合物的热稳定性和透明性的观点来看，特别优选使用有机羧酸的锌盐。
相对于氯乙烯系树脂100重量份，用作(A)成分的上述有机酸锌盐的含量为0.001重量份～10重量份，优选0.01重量份～5重量份。若该含量少于0.001重量份，则着色性及耐候性不足，若超过10重量份则热稳定性下降。
所谓本发明中用作(B)成分的锌改性水滑石系化合物，是指以镁、锌及铝作为金属成分的复盐化合物，或者以镁、钙、锌及铝作为金属成分的复盐化合物。从透明性的观点来看，本发明特别优选使用以镁、锌及铝作为金属成分的复盐化合物。
这些复盐化合物能够以通常的方法，通过使用锌化合物对水滑石系化合物进行处理而获得。这些复盐化合物也可以是通过在上述水滑石系化合物合成时，利用锌化合物进行处理或者后处理而获得的锌改性水滑石系化合物。这些锌改性水滑石系化合物在例如日本专利特公昭46-2280号公报、日本专利特公昭47-32198号公报、日本专利特公昭50-30039号公报、日本专利特公昭48-29477号公报以及日本专利特公昭51-29129号公报等中有所记载。当然，本发明中也可以使用市售品。
本发明中，从加工性、热稳定性及透明性的观点来看，作为(B)成分的锌改性水滑石系化合物，优选使用下述通式(I)所示的化合物。
My1Zny2Alx(OH)2(CO3)x/2·mH2O (I)
其中，(I)式中的M表示镁、或者镁及钙，从透明性的观点来看，特别优选的是镁。x、y1以及y2分别表示满足下述关系式所示的条件的数，m表 示0或任意的正数。0＜x≤0.5，y1+y2＝1-x，y1≥y2，0.3≤y1＜1，0＜y2＜0.5。
作为本发明中使用的锌改性水滑石系化合物的具体例，可以列举以下所示的化合物。
Mg0.38Zn0.3Al0.32(OH)2(CO3)0.16·0.2H2O
Mg0.45Zn0.23Al0.32(OH)2(CO3)0.16
Mg0.48Zn0.18Al0.34(OH)2(CO3)0.17
Mg0.48Zn0.2Al0.32(OH)2(CO3)0.16
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.165·0.45H2O
Mg0.5Zn0.18Al0.32(OH)2(CO3)0.16
Mg0.5Zn0.2Al0.3(OH)2(CO3)0.16
Mg0.5Zn0.2Al0.3(OH)2(CO3)0.15·0.52H2O
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.125
Mg0.51Zn0.17Al0.32(OH)2(CO3)0.16
Mg0.52Zn0.16Al0.32(OH)2(CO3)0.16·0.5H2O
Mg0.55Zn0.15Al0.32(OH)2(CO3)0.15
Mg0.6Zn0.14Al0.26(OH)2(CO3)0.13
Mg0.6Zn0.16Al0.24(OH)2(CO3)0.12
Mg0.6Zn0.2Al0.2(OH)2(CO3)0.1
Mg0.4Ca0.1Zn0.18Al0.32(OH)2(CO3)0.16
Mg0.3Ca0.2Zn0.2Al0.3(OH)2(CO3)0.15
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17·0.5H2O
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17·0.42H2O
Mg0.6Zn0.16Al0.24(OH)2(CO3)0.12·0.45H2O
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.13·0.39H2O
Mg0.5Zn0.17Al0.33(OH)2(CO3)0.17
Mg0.5Zn0.25Al0.25(OH)2(CO3)0.13
作为市售品，可以列举：Alcamizer 4(Alcamizer P-93)、Alcamizer-7等(均为协和化学工业制造的商品名)。从透明性的观点来看，特别优选使用Alcamizer 4(Alcamizer P-93)。本发明中，这些锌改性水滑石系化合物可以仅 使用一种，也可以两种以上合用。
本发明中，也可以使用以硬脂酸等高级脂肪酸类、油酸碱金属盐等高级脂肪酸金属盐类、十二烷基苯磺酸碱金属盐等有机磺酸金属盐类、高级脂肪酸酰胺类、高级脂肪酸酯类或者蜡等将上述锌改性水滑石系化合物的表面包覆而成的物质。
相对于聚氯乙烯系树脂100重量份，本发明中的作为(B)成分的锌改性水滑石系化合物的使用量为0.001重量份～10重量份，优选0.05重量份～5重量份。若使用量少于0.001重量份则树脂组合物的热稳定性不足，若超过10重量份，则树脂组合物的耐着色性产生问题。
本发明的透明制品用氯乙烯系树脂组合物中，从加工性的观点来看，优选进一步含有润滑剂作为(C)成分。
本发明中使用的润滑剂可以从公知的润滑剂中适当选择。作为公知的润滑剂，例如可以列举：低分子蜡、石蜡、聚乙烯蜡、氯化烃、氟碳等烃系润滑剂；巴西棕榈蜡、小烛树蜡(candelilla wax)等天然蜡系润滑剂；月桂酸、硬脂酸、山嵛酸等高级脂肪酸，或者羟基硬脂酸之类的羟基脂肪酸等脂肪酸系润滑剂；硬脂酰胺、月桂酰胺、油酰胺等脂肪族酰胺化合物或者亚甲基双硬脂酰胺、乙撑基双硬脂酰胺(ethylene bis-stearamide)之类的烷撑基(alkylene)双脂肪族酰胺等脂肪族酰胺系润滑剂；硬脂酸硬脂酯、硬脂酸丁酯等脂肪酸一元醇酯化合物，或者甘油三硬脂酸酯、山梨醇三硬脂酸酯、季戊四醇四硬脂酸酯、二季戊四醇六硬脂酸酯、聚甘油聚蓖麻油酸酯、氢化蓖麻油等脂肪酸多元醇酯化合物，或者二季戊四醇的己二酸/硬脂酸酯那样的一元脂肪酸及多元有机酸与多元醇的复合酯化合物等脂肪酸醇酯系润滑剂；硬脂醇、月桂醇、棕榈醇等脂肪族醇系润滑剂；金属皂类；部分皂化褐煤酸酯等褐煤酸系润滑剂；丙烯酸系润滑剂；硅油等。这些润滑剂可以仅使用一种，也可以两种以上合用。
本发明中，从透明性的观点来看，特别优选使用一元脂肪酸及多元有机酸与多元醇的复合酯化合物等脂肪酸醇酯系润滑剂。本发明的组合物中，相对于聚氯乙烯系树脂100重量份，作为(C)成分的润滑剂的含量优选0.001重量份～10重量份，特别优选0.05重量份～5重量份。若润滑剂的含量少于0.001重量份，则存在加工性变得不充分的情形，若超过10重量份则发生透明性下降等性能下降。
制造本发明的透明制品用氯乙烯系树脂组合物时，将(A)成分～(C)成分混合到氯乙烯系树脂中的时机并无特别限制。例如，可以预先将从(A)成分～(C)成分中选择的两种以上混合成一组分(one-pack)后混合到氯乙烯系树脂中，也可以对氯乙烯系树脂混合各成分。另外，混合成一组分(one-pack)时，可以将各成分各自粉碎后混合，也可以混合后进行粉碎。
作为本发明中使用的氯乙烯系树脂，例如可以列举：聚氯乙烯、氯化聚氯乙烯(CPVC)、聚偏二氯乙烯、氯化聚乙烯、氯化聚丙烯、氯化橡胶、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-丙烯共聚物、氯乙烯-苯乙烯共聚物、氯乙烯-异丁烯共聚物、氯乙烯-偏二氯乙烯共聚物、氯乙烯-苯乙烯-马来酸酐三元共聚物、氯乙烯-烷基、环烷基或者芳基马来酰亚胺共聚物、氯乙烯-苯乙烯-丙烯腈三元共聚物、氯乙烯-丁二烯共聚物、氯乙烯-异戊二烯共聚物、氯乙烯-氯化丙烯共聚物、氯乙烯-偏二氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-马来酸酯共聚物、氯乙烯-甲基丙烯酸酯共聚物、氯乙烯-丙烯腈共聚物、氯乙烯-氨基甲酸酯共聚物等氯乙烯系树脂，以及上述氯乙烯系树脂与聚乙烯、聚丙烯、聚丁烯、聚-3-甲基丁烯等α-烯烃聚合物、或者乙烯-乙酸乙烯酯共聚物、乙烯-丙烯共聚物等聚烯烃及它们的共聚物、聚苯乙烯、丙烯酸树脂、苯乙烯与其他单体(例如马来酸酐、丁二烯、丙烯腈等)的共聚物、丙烯腈-丁二烯-苯乙烯共聚物、甲基丙烯酸酯-丁二烯-苯乙烯共聚物、聚氨基甲酸酯的掺合物等。
本发明的透明制品用氯乙烯系树脂组合物中，可以添加氯乙烯系树脂中通常使用的金属系稳定剂。但是，本发明中，添加铅系稳定剂、(有机)锡系稳定剂、镉系稳定剂、钡系稳定剂从对环境的影响或毒性的观点来看不优选。
作为本发明中可以使用的金属系稳定剂，例如可以列举：铅、锡、镉、钡以外的有机酸金属盐以及它们的复合稳定剂等。这些有机酸金属盐可以在无损本发明效果的范围内任意使用。但是，添加这些有机酸金属盐时，有透明性下降的倾向。
作为本发明中可以使用的作为上述金属系稳定剂的有机酸金属盐，可以列举：羧酸、有机磷酸类或者酚类的金属(Li、Na、K、Ca、Mg、Sr、Zn、Cs、Al)盐等。作为上述羧酸，例如可以列举：己酸、辛酸、壬酸、2-乙基己酸、癸酸、新癸酸、十一碳烯酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、异硬脂酸、 12-羟基硬脂酸、氯硬脂酸、12-酮硬脂酸、苯基硬脂酸、蓖麻油酸、亚油酸、亚麻酸、油酸、花生酸、山嵛酸、芥酸、巴西烯酸及类似酸以及动物脂肪酸、椰子油脂肪酸、桐油脂肪酸、大豆油脂肪酸及棉籽油脂肪酸等的天然产出的上述酸的混合物、苯甲酸、对叔丁基苯甲酸、乙基苯甲酸、异丙基苯甲酸、甲基苯甲酸、二甲基苯甲酸、水杨酸、5-叔辛基水杨酸、环烷酸、环己甲酸等。
另外，作为前述有机磷酸类，例如可以列举：单或二辛基磷酸、单或二(十二烷基)磷酸、单或二(十八烷基)磷酸、单或二-(壬基苯基)磷酸、膦酸壬基苯酯、膦酸硬脂酯等。
另外，作为前述酚类，可以列举：苯酚、甲酚、乙酚、环己酚、壬酚、十二烷基苯酚等。这些可以是正盐、酸性盐、碱性盐或过碱性络合物。
本发明的透明制品用氯乙烯系树脂组合物可以获得透明性高、软化点也高等物理性能优异的成形品，因此优选的是不混合增塑剂而用于硬质用途。但是，也可以相对于氯乙烯系树脂100重量份而含有0重量份～50重量份、优选10重量份～50重量份、更优选20～40重量份的增塑剂，用于半硬质用途。当使用增塑剂时，可以在无损本发明效果的范围内适当使用通常氯乙烯系树脂中所用的增塑剂。
作为上述增塑剂，例如可以列举：邻苯二甲酸二丁酯、邻苯二甲酸丁基己基酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯、邻苯二甲酸二月桂酯、邻苯二甲酸二环己酯、对苯二甲酸二辛酯等苯二甲酸酯系增塑剂；己二酸二辛酯、己二酸二异壬酯、己二酸二异癸酯、二(二乙二醇丁醚)己二酸酯等己二酸酯系增塑剂；磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯)酯、磷酸三(异丙基苯基)酯、磷酸三乙酯、磷酸三丁酯、磷酸三辛酯、磷酸三(丁氧基乙基)酯、磷酸辛基二苯基酯等磷酸酯系增塑剂；使用了乙二醇、二乙二醇、三乙二醇、1，2-丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、1，5-己二醇、1，6-己二醇、新戊二醇等多元醇与草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸等二元酸，根据需要使用一元醇、单羧酸作为终止剂(stopper)而成的聚酯系增塑剂；此外，还可以列举：四氢邻苯二甲酸系增塑剂、壬二酸系增塑剂、癸二酸系增塑剂、硬脂酸系增塑剂、柠檬酸系增塑剂、偏苯三甲酸系增塑剂、均苯四甲酸系增塑剂、联苯聚羧酸系增塑剂等。
另外，本发明的透明制品用氯乙烯系树脂组合物中，可以进一步在无损本发明效果的范围内混合通常用作氯乙烯系树脂用添加剂的各种添加剂，例如：有机亚磷酸酯化合物、酚系或者硫系抗氧化剂、(B)成分锌改性水滑石系化合物以外的水滑石化合物、环氧化合物、多元醇类、β-二酮化合物、紫外线吸收剂、受阻胺系光稳定剂、填充剂、阻燃剂、阻燃助剂等。
作为上述有机亚磷酸酯化合物，例如可以列举：亚磷酸三苯酯、亚磷酸三(2，4-二叔丁基苯基)酯、亚磷酸三(壬基苯基)酯、亚磷酸三(二壬基苯基)酯、亚磷酸三(混合单-和二壬基苯基)酯、酸式亚磷酸二苯酯(phenyl acid phosphite)、亚磷酸-2，2′-亚甲基双(4，6-二叔丁基苯基)辛基酯、亚磷酸二苯基癸基酯、亚磷酸苯基二异癸基酯、亚磷酸三丁酯、亚磷酸三(2-乙基己基)酯、亚磷酸十三烷基酯(tridecyl phosphite)、亚磷酸三月桂酯、酸式亚磷酸二丁酯、酸式亚磷酸二月桂酯、三硫代亚磷酸三月桂酯、双(新戊二醇)-1，4-环己烷二甲基二亚磷酸酯、双(2，4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2，6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、苯基-4，4′-异亚丙基二苯酚-季戊四醇二亚磷酸酯、四(C12～15混合烷基)-4，4′-异亚丙基二苯基二亚磷酸酯、氢化-4，4′-异亚丙基二苯酚聚亚磷酸酯、双(辛基苯基)-双[4，4′-正-亚丁基双(2-叔丁基-5-甲基苯酚)]-1，6-己二醇-二亚磷酸酯、四(十三烷基)-4，4′-亚丁基双(2-叔丁基-5-甲基苯酚)二亚磷酸酯、六(十三烷基)-1，1，3-三(2-甲基-5-叔丁基-4-羟基苯基)丁烷-三亚磷酸酯、9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物、2-丁基-2-乙基丙二醇-2，4，6-三叔丁基苯酚单亚磷酸酯等。
作为前述酚系抗氧化剂，例如可以列举：2，6-二叔丁基-对甲酚、2，6-二苯基-4-十八烷氧基苯酚、硬脂基(3，5-二叔丁基-4-羟基苯基)-丙酸酯、二硬脂基(3，5-二叔丁基-4-羟基苄基)膦酸酯、硫代二乙二醇双[(3，5-二叔丁基-4-羟基苯基)丙酸酯]、1，6-六亚甲基双[(3，5-二叔丁基-4-羟基苯基)丙酸酯]、1，6-六亚甲基双[(3，5-二叔丁基-4-羟基苯基)丙酰胺]、4，4′-硫代双(6-叔丁基-间甲酚)、2，2′-亚甲基双(4-甲基-6-叔丁基苯酚)、2，2′-亚甲基双(4-乙基-6-叔丁基苯酚)、双[3，3-双(4-羟基-3-叔丁基苯基)丁酸]甘醇酯、4，4’-亚丁基双(6-叔丁基-间甲酚)、2，2′-亚乙基双(4，6-二叔丁基苯酚)、2，2′-亚乙基双(4-仲丁基-6-叔丁基苯酚)、1，1，3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、双[2-叔丁基-4-甲基-6-(2-羟基-3-叔丁基-5-甲基苄基)苯基]对苯二甲酸酯、1，3，5-三(2，6-二甲基-3-羟基-4-叔丁基苄基)异氰 尿酸酯、1，3，5-三(3，5-二叔丁基-4-羟基苄基)异氰尿酸酯、1，3，5-三(3，5-二叔丁基-4-羟基苄基)-2，4，6-三甲基苯、1，3，5-三[(3，5-二叔丁基-4-羟基苯基)丙酰氧基乙基]异氰尿酸酯、四[亚甲基-3-(3′，5′-二叔丁基-4′-羟基苯基)丙酸酯]甲烷、2-叔丁基-4-甲基-6-(2-丙烯酰氧基-3-叔丁基-5-甲基苄基)苯酚、3，9-双[1，1-二甲基-2-{(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}乙基]-2，4，8，10-四氧杂螺[5.5]十一烷、三乙二醇-双[(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]等。
作为前述硫系抗氧化剂，例如可以列举：硫代二丙酸的二月桂酯、二肉豆蔻酯、肉豆蔻基硬脂基酯、二硬脂酯等硫代二丙酸二烷基酯类以及季戊四醇四(β-十二烷基巯基丙酸酯)等多元醇的β-烷基巯基丙酸酯类等。
作为前述(B)成分锌改性水滑石系化合物以外的水滑石化合物，例如可以列举下式所示的化合物。
Mg1-xAlx(OH)2(Aq-)x/q·aH2O
其中，式中的q为1或2，Aq-为q价的阴离子、即(CO3)2-或者(ClO4)-，X表示0＜X≤0.5，a表示0或者正数。
作为锌改性水滑石系化合物以外的水滑石的代表例，可以列举下述化合物。
Mg0.750Al0.250(OH)2(CO3)0.125·0.5H2O
Mg0.692Al0.308(OH)2(CO3)0.154·0.1H2O
Mg0.683Al0.317(OH)2(CO3)0.159·0.5H2O
Mg0.667Al0.333(OH)2(CO3)0.167·0.1H2O
Mg0.750Al0.250(OH)2(ClO4)0.250·0.5H2O
Mg0.692Al0.308(OH)2(ClO4)0.308·0.1H2O
Mg0.667Al0.333(OH)2(ClO4)0.333·0.1H2O
作为市售品，可以列举：DHT-4A(协和化学工业(株)制造)、Magceler1(协和化学工业(株)制造)等。
作为前述环氧化合物，例如可以列举：环氧化大豆油、环氧化亚麻籽油、环氧化桐油、环氧化鱼油、环氧化牛油、环氧化蓖麻油、环氧化红花油等环氧化动植物油，环氧化硬脂酸甲酯、环氧化硬脂酸丁酯、环氧化硬脂酸-2-乙基己酯、环氧化硬脂酸硬脂酯、环氧化聚丁二烯、三(环氧丙基)异氰尿酸酯、环氧化松油脂肪酸酯、环氧化亚麻籽油脂肪酸酯、双酚A二缩水甘油醚、乙烯基环己烯二环氧化物、二环己烯二环氧化物、3,4-环氧环己基甲基、环氧环己甲酸酯等环氧化合物。
作为前述多元醇化合物，例如可以列举：三羟甲基丙烷、二-三羟甲基丙烷、季戊四醇、二季戊四醇、聚季戊四醇、季戊四醇或二季戊四醇的硬脂酸半酯、双(二季戊四醇)己二酸酯、甘油、三(2-羟基乙基)异氰尿酸酯等。
作为前述β-二酮化合物，例如可以列举：乙酰丙酮、三乙酰基甲烷、2,4,6-庚三酮、丁酰基乙酰基甲烷、月桂酰基乙酰基甲烷、棕榈酰基乙酰基甲烷、硬脂酰基乙酰基甲烷、苯基乙酰基乙酰基甲烷、二环己基羰基甲烷、苯甲酰基甲酰基甲烷、苯甲酰基乙酰基甲烷、二苯甲酰基甲烷、辛基苯甲酰基甲烷、硬脂酰基苯甲酰基甲烷、双(4-辛基苯甲酰基)甲烷、苯甲酰基二乙酰基甲烷、4-甲氧基苯甲酰基苯甲酰基甲烷、双(4-羧甲基苯甲酰基)甲烷、2-羧甲基苯甲酰基乙酰基辛基甲烷、脱氢乙酸、环己烷-1,3-二酮、3,6-二甲基-2,4-二氧基环己烷-1-甲酸甲酯、2-乙酰基环己酮、5,5-二甲基-1,3-环己二酮（dimedone）、2-苯甲酰基环己烷等。
作为前述紫外线吸收剂，例如可以列举：2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、5,5'-亚甲基双(2-羟基-4-甲氧基二苯甲酮)等2-羟基二苯甲酮类；2-(2-羟基-5-甲基苯基)苯并三唑、2-(2-羟基-5-叔辛基苯基)苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羟基-3,5-二异丙苯基苯基)苯并三唑、2,2'-亚甲基双(4-叔辛基-6-苯并三唑基)苯酚、2-(2-羟基-3-叔丁基-5-羧基苯基)苯并三唑的聚乙二醇酯等2-(2-羟基苯基)苯并三唑类；水杨酸苯酯、间苯二酚单苯甲酸酯、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、十六烷基-3,5-二叔丁基-4-羟基苯甲酸酯等苯甲酸酯类；2-乙基-2'-乙氧基草酰替苯胺、2-乙氧基-4'-十二烷基草酰替苯胺等取代草酰替苯胺类；乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(对甲氧基苯基)丙烯酸酯等氰基丙烯酸酯类等。
作为前述受阻胺系光稳定剂，例如可列举：硬脂酸-2,2,6,6-四甲基-4-哌啶酯、硬脂酸-1,2,2,6,6-五甲基-4-哌啶酯、苯甲酸-2,2,6,6-四甲基-4-哌啶酯、癸二 酸双(2，2，6，6-四甲基-4-哌啶基)酯、癸二酸双(1，2，2，6，6-五甲基-4-哌啶基)酯、丁烷四甲酸四(2，2，6，6-四甲基-4-哌啶基)酯、丁烷四甲酸四(1，2，2，6，6-五甲基-4-哌啶基)酯、双(1，2，2，6，6-五甲基-4-哌啶基)-二(十三烷基)-1，2，3，4-丁烷四甲酸酯、双(1，2，2，6，6-五甲基-4-哌啶基)-2-丁基-2-(3，5-二叔丁基-4-羟基苄基)丙二酸酯、1-(2-羟基乙基)-2，2，6，6-四甲基-4-哌啶醇/琥珀酸二乙酯缩聚物、1，6-双(2，2，6，6-四乙基-4-哌啶基氨基)己烷/二溴乙烷缩聚物、1，6-双(2，2，6，6-四甲基-4-哌啶基氨基)己烷/2，4-二氯-6-吗啉基-均三嗪缩聚物、1，6-双(2，2，6，6-四甲基-4-哌啶基氨基)己烷/2，4-二氯-6-叔辛基氨基-均三嗪缩聚物、1，5，8，12-四[2，4-双(N-丁基-N-(2，2，6，6-四甲基-4-哌啶基)氨基)-均三嗪-6-基]-1，5，8，12-四氮杂十二烷、1，5，8，12-四[2，4-双(N-丁基-N-(1，2，2，6，6-五甲基-4-哌啶基)氨基)-均三嗪-6-基]-1，5，8，12-四氮杂十二烷、1，6，11-三[2，4-双(N-丁基-N-(2，2，6，6-四甲基-4-哌啶基)氨基)-均三嗪-6-基氨基]十一烷、1，6，11-三[2，4-双(N-丁基-N-(1，2，2，6，6-五甲基-4-哌啶基)氨基)-均三嗪-6-基氨基]十一烷等受阻胺化合物。
作为前述填充剂的具体例，可以列举：碳酸钙、氧化钙、氢氧化钙、氢氧化锌、碳酸锌、硫化锌、氧化镁、氢氧化镁、碳酸镁、氧化铝、氢氧化铝、硅铝酸钠、水滑石、水铝钙石(hydrocalumite)，硅酸铝、硅酸镁、硅酸钙、沸石等硅酸金属盐，活性白土、滑石、粘土、铁丹(bengala)、石棉、三氧化二锑、二氧化硅、玻璃珠粒、云母、绢云母、玻璃薄片(glass flake)、石棉、硅灰石(wollastonite)、钛酸钾、多晶莫来石纤维(PMF)、石膏纤维、烧蛭石(zonolite)、镁盐晶须(MOS)、磷酸盐纤维、玻璃纤维、碳纤维、芳族聚酰胺纤维等。
作为前述阻燃剂或阻燃助剂的例子，可以列举：含三嗪环的化合物、金属氢氧化物、其他无机磷、卤素系阻燃剂、硅系阻燃剂、磷酸酯系阻燃剂、缩合磷酸酯系阻燃剂、膨胀系阻燃剂、三氧化二锑等氧化锑、其他无机系阻燃助剂、有机系阻燃助剂等。
作为前述含三嗪环的化合物，例如可以列举：三聚氰胺、三聚氰酸二酰胺(ammeline)、苯代三聚氰胺(benzoguanamine)、乙酰胍胺(acetoguanamine)、酞酰二胍胺(phthalodiguanamine)、氰尿酸三聚氰胺、焦磷酸三聚氰胺、丁撑基二胍胺、降冰片烯二胍胺(norbornene diguanamine)、亚甲基二胍胺、乙撑二(三聚氰胺)、三亚甲基二(三聚氰胺)、四亚甲基二(三聚氰胺)、六亚甲基二(三 聚氰胺)、1，3-己撑二(三聚氰胺)等。
作为前述金属氢氧化物，可以列举：氢氧化镁、氢氧化铝、氢氧化钙、氢氧化钡、氢氧化锌、Kisuma 5A(氢氧化镁，协和化学工业(株)制造)等。
作为前述磷酸酯系阻燃剂的例子，例如可以列举：磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三丁氧基乙基酯、磷酸三氯乙酯、磷酸三(二氯丙基)酯、磷酸三苯酯、磷酸三甲苯酯、磷酸甲苯二苯酯、磷酸三(二甲苯)酯、磷酸辛基二苯基酯、磷酸二甲苯二苯酯、磷酸三异丙基苯基酯、磷酸-2-乙基己基二苯基酯、磷酸叔丁基苯基二苯基酯、磷酸双-(叔丁基苯基)苯基酯、磷酸三-(叔丁基苯基)酯、磷酸异丙基苯基二苯基酯、磷酸双-(异丙基苯基)二苯基酯、磷酸三-(异丙基苯基)酯等。
作为前述缩合磷酸酯系阻燃剂的例子，可以列举：1，3-亚苯基双(二苯基磷酸酯)、1，3-亚苯基双(二甲苯基磷酸酯)、双酚A双(二苯基磷酸酯)等，作为膨胀系阻燃剂，可以列举聚磷酸等的铵盐或胺盐。
作为前述其他无机系阻燃助剂，例如可以列举：氧化钛、氧化铝、氧化镁、滑石等无机化合物及其表面处理品，例如可以使用TIPAQUE R-680(氧化钛，石原产业(株)制造)、Kyowa MAG 150(氧化镁，协和化学工业(株)制造)等各种市售品。
另外，作为前述其他有机系阻燃助剂，例如可以列举季戊四醇。
本发明的透明制品用氯乙烯系树脂组合物中，可以在无损本发明效果的范围内添加通常氯乙烯系树脂中使用的稳定助剂。作为该稳定助剂，例如可以列举：二苯基硫脲、苯胺基二硫代三嗪、三聚氰胺、苯甲酸、肉桂酸、对叔丁基苯甲酸、沸石、过氯酸盐等。
此外，本发明的透明制品用氯乙烯系树脂组合物中，根据需要可以在无损本发明效果的范围内混合通常氯乙烯系树脂中使用的添加剂，例如：交联剂、抗静电剂、防雾剂、防渗出剂、表面处理剂、防雾剂、荧光剂、防霉剂、杀菌剂、发泡剂、金属钝化剂、脱模剂、颜料、加工助剂、抗氧化剂、光稳定剂等。
本发明的透明制品用氯乙烯系树脂组合物可以与氯乙烯系树脂的加工方法无关地使用，例如可以优选用于：滚筒加工、挤压成型加工、熔融流延法、加压成型加工等。
以下，通过实施例及比较例对本发明进行更详细说明，但本发明不受这些 例子的任何限制。
[实施例1～实施例7以及比较例1～比较例4]
使用亨舍尔混合机将下述表1及表2所记载的各配方混合后，以170℃×30rpm×0.6mm×3min的条件进行滚筒混练而制作成片材。将所得的片材放入到190℃的齿轮烘箱(gear oven)中，测定黑化时间(分钟)作为热稳定性试验的评价。结果示于表1及表2中。
将由上述操作而获得的0.6mm厚的片材贴合并在190℃下进行5分钟压制加工，制作1mm厚的片材和2mm厚的片材。并且，另在190℃下进行30分钟压制加工而制作1mm厚的片材。使用所得的片材，按照以下方法来进行着色性试验以及透明性试验。
<着色性试验>
对上述在190℃下压制加工5分钟及30分钟而成的1mm厚的片材测定黄色度(Y.I.)。结果示于表1及表2中
<透明性试验>
对上述在190℃下压制加工5分钟而成的1mm厚及2mm厚的片材测定Haze值。结果示于表1及表2中。
[表1]
[表2]
*1：ZEST1000Z(Shin Dai-Ichi Enbi(株)制造的商品名)
*2：四[亚甲基-3-(3′，5′-二叔丁基-4′羟基苯基)丙酸酯]甲烷
*3：月桂酸锌
*4：组成式Mg3.0ZnAl2(OH)12(CO3)·3H2O
(若以权利要求2的记载方法来表示，则为：
Mg3/6Zn1/6Al2/6(OH)2(CO3)1/6·0.5H2O
*5：组成式Mg3.5Zn0.5Al2(OH)12(CO3)·3H2O
(若以权利要求2的记载方法来表示，则为：
Mg3.5/6Zn0.5/6Al2/6(OH)2(CO3)1/6·0.5H2O
*6：G-72高分子复合酯(Cognis Oleochemicals Japan(株)制造)
*7：水滑石(协和化学工业(株)制造)Mg4.2Al2(OH)13(CO3)·3H2O
*8：水滑石(协和化学工业(株)制造)Mg4.5Al2(OH)13(CO3)·3.5H2O
由表1及表2的结果证明，本案发明的透明制品用氯乙烯系树脂组合物不仅透明性优异，而且对于短时间加热的耐着色性也优异。
[实施例8～实施例14]
和前述实施例1～实施例7同样地使用亨舍尔混合机将下述表3所记载的配方混合后，以170℃×30rpm×0.6mm×3分钟的条件进行滚筒混练而制作片材。
将所得的片材放入到190℃的齿轮烘箱中，测定黑化时间(分钟)作为热稳定性试验的评价。结果示于表3中。
和前述实施例1～实施例7同样地将由上述操作而获得的0.6mm厚的片材贴合，在190℃下进行5分钟压制加工，制作1mm厚的片材与2mm厚的片材。并且，另在190℃下进行30分钟压制加工而制作1mm厚的片材。
使用这些片材，按照以下方法进行着色性试验以及透明性试验。
<着色性试验>
对上述在190℃下压制加工5分钟及30分钟而成的1mm厚的片材测定黄色度(Y.I.)。将结果示于表3中。
<透明性试验>
对上述在190℃下压制加工5分钟而成的1mm厚及2mm厚的片材测定Haze值。将结果示于表3中。
[表3]
(混合为重量份)
*9：G-32脂肪酸酯(Cognis Oleochemicals Japan(株)制造)
*10：G-60二元酸酯(Cognis Oleochemicals Japan(株)制造)
*11：G-70S高分子复合酯系(Cognis Oleochemicals Japan(株)制造)
*12：GH-4多元醇酯(Cognis Oleochemicals Japan(株)制造)
根据表3的结果确认，通过混合润滑剂，可以提高热稳定性而不影响初期的耐着色性以及透明性。
工业实用性
本发明的透明制品用氯乙烯系树脂组合物特别适合于硬质或者半硬质用途的透明的成形品用，可以用于需要玻璃那样的透明性的容器类、工业板、装饰板、托盘、膜、收缩膜(shrink film)、片材、建材、给排水管、板、接头、汽车用材料、软管、集成电路盒、瓶子等。
Claims (6)
1.一种透明制品用氯乙烯系树脂组合物，其特征在于：其是相对于氯乙烯系树脂100重量份而含有0.001重量份～10重量份的（A）有机酸锌盐的至少一种、0.001重量份～10重量份的（B）锌改性水滑石系化合物的至少一种、0.001重量份～10重量份的（C）脂肪酸醇酯系润滑剂、以及β-二酮化合物而成。
2.根据权利要求1所述的透明制品用氯乙烯系树脂组合物，其特征在于：所述（B）锌改性水滑石系化合物是以下述通式（I）所示，
My1Zny2Alx(OH)2(CO3)x/2·mH2O （I）
其中，式中的M表示镁、或者镁及钙，x、y1以及y2分别表示满足下式所示条件的数，m表示0或者任意的正数；
0＜x≤0.5，y1＋y2＝1－x，y1≥y2，0.3≤y1＜1，0＜y2＜0.5。
3.根据权利要求1至2中任意一项所述的透明制品用氯乙烯系树脂组合物，其特征在于：所述组合物不含有机锡系化合物。
4.根据权利要求1至2中任意一项所述的透明制品用氯乙烯系树脂组合物，其特征在于：所述组合物进一步含有0重量份～50重量份的增塑剂成分。
5.根据权利要求4所述的透明制品用氯乙烯系树脂组合物，其特征在于：所述增塑剂的含量为10重量份～50重量份。
6.一种透明成形品，其特征在于：其是将根据权利要求1至5中任意一项所述的透明制品用氯乙烯系树脂组合物成形而成。
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| JP2012167232A (ja) * | 2011-02-16 | 2012-09-06 | Adeka Corp | 塩化ビニル系樹脂組成物 |
| JP2012241119A (ja) * | 2011-05-20 | 2012-12-10 | Adeka Corp | 射出成形用塩化ビニル系樹脂組成物 |
| KR101505241B1 (ko) * | 2012-03-16 | 2015-03-23 | (주)엘지하우시스 | Ｐｖｃ 무독 창호용 합성수지 조성물 및 ｐｖｃ 무독 창호 |
| CN103965563A (zh) * | 2013-01-28 | 2014-08-06 | 潘朝宗 | 防火阻燃膨胀材料 |
| WO2014150743A1 (en) * | 2013-03-15 | 2014-09-25 | The Lubrizol Corporation | Heavy metal free halogenated polymer compounds |
| JP2016053133A (ja) * | 2014-09-04 | 2016-04-14 | 株式会社Adeka | 塩化ビニル系樹脂用安定剤組成物、該安定剤組成物を用いた塩化ビニル系樹脂組成物及び該樹脂組成物から得られる成形品 |
| CN104927235A (zh) * | 2015-06-08 | 2015-09-23 | 安徽省金正塑业有限公司 | 一种pvc热收缩膜用料及其制备方法 |
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| JPH0639560B2 (ja) * | 1986-08-14 | 1994-05-25 | 協和化学工業株式会社 | ポリ塩化ビニル系樹脂の安定化組成物 |
| JP2909748B2 (ja) * | 1989-07-10 | 1999-06-23 | 旭電化工業株式会社 | 食品包装用ポリ塩化ビニル系樹脂組成物 |
| JPH0570649A (ja) * | 1991-09-11 | 1993-03-23 | Sakai Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
| US5352723A (en) * | 1992-09-15 | 1994-10-04 | Synthetic Products Company | Stabilized vinyl halide compositions containing hydrotalcites |
| JPH06100749A (ja) | 1992-09-22 | 1994-04-12 | Asahi Denka Kogyo Kk | 食品包装用ポリ塩化ビニル系樹脂組成物 |
| JP3563168B2 (ja) * | 1995-09-01 | 2004-09-08 | 旭電化工業株式会社 | 塩化ビニル系樹脂組成物 |
| JP2004193138A (ja) * | 1997-09-08 | 2004-07-08 | Mitsui Chemicals Inc | 塩化ビニル系樹脂被覆電線 |
| JP3958436B2 (ja) * | 1998-04-21 | 2007-08-15 | 水澤化学工業株式会社 | 塩素含有重合体用安定剤及び塩素含有重合体組成物 |
| DE10254863A1 (de) * | 2002-11-25 | 2004-06-03 | Cognis Deutschland Gmbh & Co. Kg | Verwendung von Zusammensetzungen bei der Herstellung von Formteilen auf Basis von Polyvinylchlorid zur Verbesserung der Benetzbarkeit der Formteile |
| JP2004224937A (ja) * | 2003-01-23 | 2004-08-12 | Sakai Chem Ind Co Ltd | 塩化ビニル系樹脂組成物 |
| JP2006124502A (ja) * | 2004-10-28 | 2006-05-18 | Sakai Chem Ind Co Ltd | ハロゲン含有樹脂用安定化剤及びハロゲン含有樹脂組成物 |
| JP2008056506A (ja) * | 2006-08-29 | 2008-03-13 | Toda Kogyo Corp | 珪酸被覆ハイドロタルサイト類化合物粒子粉末、該粒子粉末を用いた含塩素樹脂安定剤及び含塩素樹脂組成物 |
| WO2009122681A1 (ja) * | 2008-03-31 | 2009-10-08 | 戸田工業株式会社 | ハイドロタルサイト型化合物粒子粉末、該ハイドロタルサイト型化合物粒子粉末を用いた含塩素樹脂安定剤及び含塩素樹脂組成物 |
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- 2009-09-17 KR KR1020117007855A patent/KR20110079637A/ko not_active Ceased
- 2009-09-17 EP EP09818918.6A patent/EP2336237A4/en not_active Withdrawn
- 2009-09-17 US US13/123,249 patent/US8598259B2/en not_active Expired - Fee Related
- 2009-09-17 CN CN200980139867.2A patent/CN102177203B/zh active Active
- 2009-09-17 WO PCT/JP2009/004675 patent/WO2010041378A1/ja active Application Filing
- 2009-09-17 JP JP2010532784A patent/JP5580742B2/ja active Active
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| EP2336237A1 (en) | 2011-06-22 |
| JPWO2010041378A1 (ja) | 2012-03-01 |
| CN102177203A (zh) | 2011-09-07 |
| EP2336237A4 (en) | 2014-05-21 |
| KR20110079637A (ko) | 2011-07-07 |
| US20110201741A1 (en) | 2011-08-18 |
| WO2010041378A1 (ja) | 2010-04-15 |
| US8598259B2 (en) | 2013-12-03 |
| JP5580742B2 (ja) | 2014-08-27 |
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