JP2024024720A - Vinyl chloride-based resin composition and sheet made of vinyl chloride-based resin - Google Patents
Vinyl chloride-based resin composition and sheet made of vinyl chloride-based resin Download PDFInfo
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000011347 resin Substances 0.000 title claims abstract description 39
- 229920005989 resin Polymers 0.000 title claims abstract description 39
- 239000011342 resin composition Substances 0.000 title claims abstract description 29
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 33
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 11
- 238000002845 discoloration Methods 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- -1 medical care Substances 0.000 description 19
- 239000004014 plasticizer Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 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 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100035474 DNA polymerase kappa Human genes 0.000 description 1
- 101710108091 DNA polymerase kappa Proteins 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- YKGYQYOQRGPFTO-UHFFFAOYSA-N bis(8-methylnonyl) hexanedioate Chemical compound CC(C)CCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC(C)C YKGYQYOQRGPFTO-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N n-Decanedioic acid Natural products OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、塩化ビニル系樹脂組成物および塩化ビニル系樹脂製シートに関する。より詳しくは、成型加工時の着色を抑制する塩化ビニル系樹脂組成物および塩化ビニル系樹脂製シートに関する。 The present invention relates to a vinyl chloride resin composition and a vinyl chloride resin sheet. More specifically, the present invention relates to a vinyl chloride resin composition and a vinyl chloride resin sheet that suppress coloring during molding.
塩化ビニル系樹脂は、成形加工・二次加工性が優れていると共に、難燃性を有することから、建材、医療、農業用資材、家具類、日用品、包装用フィルム等広範な分野で使用されている。用途や要求される物性・性能により、塩化ビニル系樹脂に各種添加剤を添加した組成物が使用され、塩化ビニル系樹脂の添加剤として例えば各種界面活性剤がある。 PVC resin has excellent moldability and secondary processability as well as flame retardancy, so it is used in a wide range of fields such as building materials, medical care, agricultural materials, furniture, daily necessities, and packaging films. ing. Depending on the purpose and required physical properties and performance, compositions in which various additives are added to vinyl chloride resin are used, and additives for vinyl chloride resin include, for example, various surfactants.
界面活性剤は塩化ビニル樹脂に帯電防止性や親水性など各種機能性を付与するため添加される。たとえば、特許文献１には、非イオン系界面活性剤ならびに陰イオン系界面活性剤を含む塩化ビニル系樹脂組成物が開示されている。また特許文献２には、アニオン系界面活性剤からなる帯電防止剤を含有する塩化ビニル系樹脂組成物がロール加工工程を経て製膜された塩化ビニル系樹脂フィルムが開示されている。 Surfactants are added to vinyl chloride resin to impart various functionalities such as antistatic properties and hydrophilic properties. For example, Patent Document 1 discloses a vinyl chloride resin composition containing a nonionic surfactant and an anionic surfactant. Furthermore, Patent Document 2 discloses a vinyl chloride resin film in which a vinyl chloride resin composition containing an antistatic agent made of an anionic surfactant is formed through a roll processing process.
アニオン系界面活性剤を含む塩化ビニル系樹脂組成物は、成形する際の加熱により熱劣化が進行しやすく、その結果、成形体が変色する場合があった。
そこで上記のような状況に鑑み、成形加工による変色が改善された塩化ビニル系樹脂組成物を提供することを目的とする。
Vinyl chloride resin compositions containing anionic surfactants tend to undergo thermal deterioration due to heating during molding, and as a result, the molded products may change color.
Therefore, in view of the above-mentioned situation, the object of the present invention is to provide a vinyl chloride resin composition in which discoloration due to molding processing is improved.
前述の課題を解決するために本発明が用いた手段は、塩化ビニル系樹脂にアニオン系界面活性剤溶液を添加した樹脂組成物を用いることである。具体的には塩化ビニル系樹脂１００重量部に対し、アニオン系界面活性剤溶液を１～３０重量部含有する塩化ビニル系樹脂組成物とすることである。 The means used by the present invention to solve the above problems is to use a resin composition in which an anionic surfactant solution is added to a vinyl chloride resin. Specifically, the vinyl chloride resin composition contains 1 to 30 parts by weight of an anionic surfactant solution per 100 parts by weight of the vinyl chloride resin.
本発明の塩化ビニル系樹脂組成物によれば、成形加工による変色が改善された塩化ビニル系樹脂組成物を得ることが出来る。 According to the vinyl chloride resin composition of the present invention, a vinyl chloride resin composition with improved discoloration due to molding can be obtained.
以下、本発明について詳細を説明する。 The present invention will be explained in detail below.
本発明において、アニオン系界面活性剤溶液とは、アニオン系界面活性剤を溶媒に溶解し、溶液としたものである。これにより、樹脂組成物中におけるアニオン系界面活性剤の分散性が向上すると考えられる。 In the present invention, an anionic surfactant solution is a solution obtained by dissolving an anionic surfactant in a solvent. This is thought to improve the dispersibility of the anionic surfactant in the resin composition.
アニオン系界面活性剤溶液中のアニオン系界面活性剤としては、カルボン酸系化合物、スルホン酸系化合物、硫酸エステル系化合物、リン酸エステル系化合物等が挙げられる。 Examples of the anionic surfactant in the anionic surfactant solution include carboxylic acid compounds, sulfonic acid compounds, sulfuric acid ester compounds, and phosphoric acid ester compounds.
カルボン酸系化合物としては、例えば高級脂肪酸塩（石けん）、アルキルエーテルカルボン酸塩等が挙げられる。 Examples of carboxylic acid compounds include higher fatty acid salts (soaps), alkyl ether carboxylates, and the like.
スルホン酸系化合物としては、例えば直鎖アルキルベンゼンスルホン酸塩（ＬＡＳ）、α－スルホ脂肪酸メチルエステル塩（α－ＳＦ）、α－オレフィンスルホン酸塩（ＡＯＳ）、アルカンスルホン酸塩（ＳＡＳ）、ジアルキルスルホこはく酸塩、ナフタレンスルホン酸塩等が挙げられる。 Examples of sulfonic acid compounds include linear alkylbenzene sulfonates (LAS), α-sulfo fatty acid methyl ester salts (α-SF), α-olefin sulfonates (AOS), alkanesulfonates (SAS), dialkyl Examples include sulfosuccinate, naphthalene sulfonate, and the like.
硫酸エステル系化合物としては、例えばアルキル硫酸エステル塩（ＡＳ）、ポリオキシエチレンアルキル硫酸エステル塩（ＡＥＳ）等が挙げられる。 Examples of the sulfate-based compounds include alkyl sulfate salts (AS), polyoxyethylene alkyl sulfate salts (AES), and the like.
リン酸エステル系化合物としては、例えばアルキルリン酸エステル塩（ＭＡＰ）、ポリオキシエチレンアルキルエーテルリン酸塩等が挙げられる。 Examples of the phosphate compounds include alkyl phosphate ester salts (MAP), polyoxyethylene alkyl ether phosphates, and the like.
アニオン系界面活性剤溶液の溶媒としては、塩化ビニル系樹脂との親和性の面から有機溶媒が好ましい。さらに、溶解性の面から極性溶媒が好ましく、中でも分子内にヒドロキシ基（－ＯＨ）をもつアルコール類およびグリコール類がより好ましい。
アルコール類およびグリコール類としては、例えばメタノール、エタノール、プロパノール、エチレングリコール、プロピレングリコール、エチレングリコールモノエチルエーテル、トリエチレングリコールモノメチルエーテル、ポリエチレングリコール等が挙げられる。
As the solvent for the anionic surfactant solution, an organic solvent is preferable from the viewpoint of affinity with the vinyl chloride resin. Further, from the viewpoint of solubility, polar solvents are preferred, and alcohols and glycols having a hydroxy group (-OH) in the molecule are particularly preferred.
Examples of alcohols and glycols include methanol, ethanol, propanol, ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, triethylene glycol monomethyl ether, polyethylene glycol, and the like.
塩化ビニル系樹脂に対するアニオン系界面活性剤溶液の添加量としては、塩化ビニル系樹脂１００重量部に対し１～３０重量部であり、好ましくは１～１０重量部である。
アニオン系界面活性剤溶液が１重量部未満ではアニオン界面活性剤による各種機能性の付与効果が乏しくなる。上限については特に限定されないが加工性の面から３０重量部以下が好ましい。
また、アニオン系界面活性剤溶液中のアニオン系界面活性剤の割合は、アニオン界面活性剤による各種機能性の付与効果や加工性の面から、４０～７０％であることが好ましい。
The amount of the anionic surfactant solution added to the vinyl chloride resin is 1 to 30 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the vinyl chloride resin.
If the anionic surfactant solution is less than 1 part by weight, the effects of imparting various functionalities by the anionic surfactant will be poor. The upper limit is not particularly limited, but from the viewpoint of processability, it is preferably 30 parts by weight or less.
Further, the proportion of the anionic surfactant in the anionic surfactant solution is preferably 40 to 70% from the viewpoint of the effect of imparting various functionalities by the anionic surfactant and processability.
塩化ビニル系樹脂としては、例えば塩化ビニル単独重合体（ポリ塩化ビニル樹脂）、塩化ビニルモノマーと塩化ビニルモノマーと共重合可能な不飽和結合を有するモノマーとの共重合体、共重合体を含む塩化ビニル以外の他のポリマーに塩化ビニルを共重合させたグラフト共重合体等が挙げられる。
なお、これら塩化ビニル系樹脂は単独で使用しても良いが、二種類以上を併用しても良い。さらに必要に応じ、塩化ビニル系樹脂を塩素化しても良い。
塩化ビニル系樹脂を塩素化する方法としては特に限定されないが、例えば光塩素化方法、熱塩素化方法等が挙げられる。
また、本発明に用いる塩化ビニル系樹脂の重合度としては、実質的に成形加工が可能であれば、特に制限されるものではないが、平均重合度５００～２０００の範囲が好ましく、平均重合度７００～１３００の範囲がさらに好ましい。平均重合度５００未満では溶融時の粘度が低いため加工し難く、平均重合度２０００を超える場合は溶融時の粘度が高いため加工し難くなる可能性がある。
Examples of vinyl chloride resins include vinyl chloride homopolymers (polyvinyl chloride resins), copolymers of vinyl chloride monomers and monomers having unsaturated bonds that are copolymerizable with vinyl chloride monomers, and chloride containing copolymers. Examples include graft copolymers in which vinyl chloride is copolymerized with polymers other than vinyl.
Note that these vinyl chloride resins may be used alone, or two or more types may be used in combination. Furthermore, if necessary, the vinyl chloride resin may be chlorinated.
The method for chlorinating the vinyl chloride resin is not particularly limited, and examples thereof include photochlorination methods, thermal chlorination methods, and the like.
Further, the degree of polymerization of the vinyl chloride resin used in the present invention is not particularly limited as long as it can be substantially molded, but the average degree of polymerization is preferably in the range of 500 to 2000. A range of 700 to 1300 is more preferred. If the average degree of polymerization is less than 500, the viscosity when melted is low, making it difficult to process, and if the average degree of polymerization exceeds 2000, the viscosity when melting is high, which may make it difficult to process.
本発明の塩化ビニル系樹脂組成物には、各種可塑剤を添加することができる。可塑剤の種類としては特に制限はないが、例えばＤＯＰ（ジ‐２‐エチルヘキシルフタレート）、ＤＩＮＰ（ジイソノニルフタレート）、ＤＩＤＰ（ジイソデシルフタレート）、ＤＯＴＰ（ジオクチルテレフタレート）などのフタル酸エステル系可塑剤や、ＤＯＡ（ジ‐２‐エチルヘキシルアジペート）、ＤＩＤＡ（ジイソデシルアジペート）などのアジピン酸エステル系可塑剤、ＤＯＳ（ジ‐２‐エチルヘキシルセバケート）などのセバシン酸エステル系可塑剤、ＤＯＺ（ジ‐２‐エチルヘキシルアゼレート）などのアゼライン酸エステル系可塑剤といった脂肪族二塩基酸エステル系可塑剤、リン酸トリクレジル、リン酸トリキシレニル、リン酸クレジルジフェニル、リン酸トリス（イソプロピルフェニル）、リン酸トリス（ジクロロプロピル）などのリン酸エステル系可塑剤、ポリエステル系可塑剤、エポキシ系可塑剤、スルホン酸エステル系可塑剤などが使用できる。中でもポリエステル系可塑剤は低揮発性で、油および各種溶剤による抽出量が少なく、接触する各種樹脂への非移行性に優れていることから好ましく用いられる。 Various plasticizers can be added to the vinyl chloride resin composition of the present invention. There are no particular restrictions on the type of plasticizer, but examples include phthalate ester plasticizers such as DOP (di-2-ethylhexyl phthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate), DOTP (dioctyl terephthalate), Adipic acid ester plasticizers such as DOA (di-2-ethylhexyl adipate) and DIDA (diisodecyl adipate), sebacic acid ester plasticizers such as DOS (di-2-ethylhexyl sebacate), DOZ (di-2-ethylhexyl Aliphatic dibasic acid ester plasticizers such as azelate ester plasticizers such as tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, tris(isopropylphenyl) phosphate, tris(dichloropropyl) phosphate ), polyester plasticizers, epoxy plasticizers, sulfonate plasticizers, etc. can be used. Among them, polyester plasticizers are preferably used because they have low volatility, are less extracted by oil and various solvents, and have excellent non-migration properties to various resins with which they come into contact.
可塑剤の添加量は、塩化ビニル系樹脂１００重量部に対し４０重量部以下が好ましい。なお、可塑剤の添加量が少ない硬質または半硬質の塩化ビニル系樹脂組成物（可塑剤の添加量が２０重量部以下）の方がアニオン系界面活性剤の添加による着色などの影響を受けやすいため、硬質または半硬質の塩化ビニル系樹脂組成物については本発明の効果がより大きい傾向がある。 The amount of plasticizer added is preferably 40 parts by weight or less per 100 parts by weight of the vinyl chloride resin. In addition, hard or semi-rigid vinyl chloride resin compositions with a small amount of plasticizer added (the amount of plasticizer added is 20 parts by weight or less) are more susceptible to the effects of coloring due to the addition of anionic surfactants. Therefore, the effects of the present invention tend to be greater for hard or semi-hard vinyl chloride resin compositions.
本発明において、塩化ビニル系樹脂に対し、充填剤、紫外線吸収剤、光安定剤、酸化防止剤、滑剤、紫外線遮蔽剤、帯電防止剤、難燃剤、蛍光剤、抗菌剤、防カビ剤、難燃剤、防炎剤などの各種添加剤を適宜添加してもよい。 In the present invention, fillers, ultraviolet absorbers, light stabilizers, antioxidants, lubricants, ultraviolet shielding agents, antistatic agents, flame retardants, fluorescent agents, antibacterial agents, antifungal agents, and retardants are added to vinyl chloride resins. Various additives such as a flame retardant and a flame retardant may be added as appropriate.
本発明の塩化ビニル系樹脂組成物は、塩化ビニル系樹脂とアニオン系界面活性剤溶液を混合する工程を用いることで、塩化ビニル系樹脂中のアニオン系界面活性剤の分散性を向上することができる。混合方法としては、機械撹拌力で混合する容器固定型と、容器を回転させ混合する容器回転型があるが界面活性剤の分散が良好な状態になるのであればどちらの方法を用いてもよい。容器固定型としてはヘンシェルミキサー等があり、容器回転型としてコンテナブレンダー等の公知の設備を用いることができる。 The vinyl chloride resin composition of the present invention can improve the dispersibility of the anionic surfactant in the vinyl chloride resin by using a step of mixing the vinyl chloride resin and an anionic surfactant solution. can. There are two mixing methods: fixed container type, which uses mechanical stirring power, and container rotating type, which mixes by rotating the container, but either method can be used as long as the surfactant is well dispersed. . As a container fixed type, a Henschel mixer etc. can be used, and as a container rotating type, a known equipment such as a container blender can be used.
本発明の塩化ビニル系樹脂組成物は、塩化ビニル系樹脂とアニオン系界面活性剤溶液を溶融混練する工程を用いることで塩化ビニル系樹脂中のアニオン系界面活性剤の分散性を向上することができる。溶融混練が可能であればいずれの装置でも良くバンバリーミキサー、ニーダー、二本ロール機、押出機等の公知の設備を用いることができる。溶融混合後、直ちに成形してもよいし、溶融混合した後、一旦ペレット化し、その後成形してもよい。 The vinyl chloride resin composition of the present invention can improve the dispersibility of the anionic surfactant in the vinyl chloride resin by using a step of melt-kneading the vinyl chloride resin and an anionic surfactant solution. can. Any device that can perform melt-kneading may be used, and known equipment such as a Banbury mixer, kneader, two-roll machine, and extruder can be used. After melt-mixing, it may be molded immediately, or after melt-mixing, it may be pelletized once and then molded.
本発明の塩化ビニル系樹脂製シートは、ロール成形装置、カレンダー成形装置、一軸又は二軸押出装置、インフレーション成形装置、インジェクション成形装置、熱成形装置、スラッシュモールド装置、ペーストコーター装置、ディッピング成形装置等の公知の設備で成形される。 The vinyl chloride resin sheet of the present invention can be applied to roll molding equipment, calendar molding equipment, single-screw or twin-screw extrusion equipment, inflation molding equipment, injection molding equipment, thermoforming equipment, slush molding equipment, paste coater equipment, dipping molding equipment, etc. It is molded using known equipment.
本発明の塩化ビニル系樹脂組成物の用途としては、特に限定されないが、例えばシート、床材、壁紙、フィルム、衣服用生地、容器、パイプ、玩具等が挙げられる。 Applications of the vinyl chloride resin composition of the present invention are not particularly limited, but include, for example, sheets, flooring materials, wallpaper, films, clothing fabrics, containers, pipes, toys, and the like.
本発明を実施例によって、さらに詳しく説明するが本発明はこれらの実施例によって限定されるものではない。
［塩化ビニル系樹脂組成物］
実施例および比較例に使用した各配合剤の具体的な物質名は以下の通りである。
塩化ビニル系樹脂１：ポリ塩化ビニル樹脂 平均重合度 ７００
塩化ビニル系樹脂２：ポリ塩化ビニル樹脂 平均重合度 １０００
可塑剤１：ポリエステル系可塑剤 粘度 １５０ｍＰａ・ｓ／２５℃
可塑剤２：ポリエステル系可塑剤 粘度 ４５０～７５０ｍＰａ・ｓ／２５℃
安定剤：金属石鹸
アニオン系界面活性剤溶液：アルキルベンゼンスルホン酸Ｎａ溶液 アニオン系界面活性剤の割合５５％
（商品名；ＬＡ－０３５５、大協化成工業社製）
アニオン系界面活性剤：アルキルベンゼンスルホン酸Ｎａ 純度９０％
（商品名；ＮＡＮＳＡ（登録商標） ＨＳ９０／Ｓ、ハンツマン・ジャパン社製）
The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
[Vinyl chloride resin composition]
The specific substance names of each compounding agent used in Examples and Comparative Examples are as follows.
Vinyl chloride resin 1: Polyvinyl chloride resin Average degree of polymerization 700
Vinyl chloride resin 2: Polyvinyl chloride resin Average degree of polymerization 1000
Plasticizer 1: Polyester plasticizer Viscosity 150mPa・s/25℃
Plasticizer 2: Polyester plasticizer Viscosity 450-750mPa・s/25℃
Stabilizer: Metal soap Anionic surfactant solution: Sodium alkylbenzenesulfonate solution Ratio of anionic surfactant 55%
(Product name: LA-0355, manufactured by Daikyo Kasei Kogyo Co., Ltd.)
Anionic surfactant: Sodium alkylbenzenesulfonate purity 90%
(Product name: NANSA (registered trademark) HS90/S, manufactured by Huntsman Japan)
＜塩化ビニル系樹脂組成物および塩化ビニル系樹脂製シートの製造方法＞
表１～表３に示した実施例及び比較例の配合物を１８０℃に設定した二本ロールにて１０分間混練して塩化ビニル系樹脂組成物としたものを、厚さ０．２ｍｍのシート状に成型し、塩化ビニル系樹脂製シートを作製した。各塩化ビニル系樹脂製シートについて加工性及び黄色度の評価を行った。
なお、表１は半硬質配合、表２は硬質配合、表３は軟質配合である。
<Method for producing vinyl chloride resin composition and vinyl chloride resin sheet>
The formulations of the Examples and Comparative Examples shown in Tables 1 to 3 were kneaded for 10 minutes with two rolls set at 180°C to form a vinyl chloride resin composition, and a sheet of 0.2 mm thick was prepared. A sheet made of vinyl chloride resin was produced. Processability and yellowness of each vinyl chloride resin sheet were evaluated.
Note that Table 1 is a semi-hard formulation, Table 2 is a hard formulation, and Table 3 is a soft formulation.
＜加工性＞
上記の製造方法により塩化ビニル系樹脂製シートの成型を行った際の加工性について評価した。
[評価基準]
○・・・ロールへの粘着がなく、加工性に優れる。
△・・・ロールへの粘着があるが、加工することができる。
×・・・ロールへの粘着が大きく、加工性に劣る。
<Workability>
Processability when molding a vinyl chloride resin sheet using the above manufacturing method was evaluated.
[Evaluation criteria]
○: No adhesion to rolls, excellent workability.
Δ: Adhesive to the roll, but can be processed.
×: Adhesion to the roll is large and processability is poor.
＜黄色度（ＹＩ）＞
スガ試験機製ＳＭカラーコンピュータ（型番：ＳＭ－４－２）を用いて黄色度（ＹＩ）の測定を行った。実施例または比較例の成型後のシートをＳＭカラーコンピュータの測定開口部の上に置き、更にシートの上に白色校正標準板（セラミック製、三刺激値・・・Ｘ：７７．２５、Ｙ：７９．９７、Ｚ：９２．７１）を被せて黄色度（ＹＩ）の測定を行った。
<Yellowness (YI)>
Yellowness index (YI) was measured using an SM color computer manufactured by Suga Test Instruments (model number: SM-4-2). Place the molded sheet of the example or comparative example on the measurement opening of the SM color computer, and then place a white calibration standard plate (made of ceramic, tristimulus value...X: 77.25, Y: 79.97, Z: 92.71), and the yellowness index (YI) was measured.
表１の実施例１と比較例２、表２の実施例４と比較例３、表３の実施例５と比較例４をそれぞれ比べると、本発明の範囲のアニオン系界面活性剤溶液を含有する塩化ビニル系樹脂組成物とすることで、加工による変色が軽減されていることがわかる。
さらに、可塑剤の添加量が少ない半硬質（表１）または硬質（表２）の配合では、軟質（表３）の配合と比較して変色の軽減効果がより大きいことがわかる。
また、表１の実施例１～３を比較すると、アニオン系界面活性剤溶液の添加量が増えても加工時に変色しにくいことがわかる。
Comparing Example 1 and Comparative Example 2 in Table 1, Example 4 and Comparative Example 3 in Table 2, and Example 5 and Comparative Example 4 in Table 3, it was found that the anionic surfactant solution contained within the scope of the present invention. It can be seen that discoloration due to processing is reduced by using a vinyl chloride resin composition.
Furthermore, it can be seen that the effect of reducing discoloration is greater in semi-rigid (Table 1) or hard (Table 2) formulations in which a small amount of plasticizer is added compared to soft (Table 3) formulations.
Further, when comparing Examples 1 to 3 in Table 1, it can be seen that even if the amount of anionic surfactant solution added increases, discoloration is difficult to occur during processing.
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