JP7477258B2 - wallpaper - Google Patents
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- JP7477258B2 JP7477258B2 JP2019060351A JP2019060351A JP7477258B2 JP 7477258 B2 JP7477258 B2 JP 7477258B2 JP 2019060351 A JP2019060351 A JP 2019060351A JP 2019060351 A JP2019060351 A JP 2019060351A JP 7477258 B2 JP7477258 B2 JP 7477258B2
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- JP
- Japan
- Prior art keywords
- polyvinyl chloride
- chloride resin
- resin layer
- weight
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005989 resin Polymers 0.000 claims description 77
- 239000011347 resin Substances 0.000 claims description 77
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 75
- 239000004800 polyvinyl chloride Substances 0.000 claims description 75
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 53
- 239000004014 plasticizer Substances 0.000 description 23
- 238000005187 foaming Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000004049 embossing Methods 0.000 description 9
- 239000000123 paper Substances 0.000 description 8
- 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 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- -1 sebacate ester Chemical class 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 3
- 235000019399 azodicarbonamide Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 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
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 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
- ZDWGXBPVPXVXMQ-UHFFFAOYSA-N bis(2-ethylhexyl) nonanedioate Chemical compound CCCCC(CC)COC(=O)CCCCCCCC(=O)OCC(CC)CCCC ZDWGXBPVPXVXMQ-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 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 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 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
- 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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 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
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- KZJNRSVWTFBHGW-UHFFFAOYSA-J calcium dichlorozinc dichloride Chemical compound Cl[Ca]Cl.Cl[Zn]Cl KZJNRSVWTFBHGW-UHFFFAOYSA-J 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- LKPIKTXUOSKAHF-UHFFFAOYSA-J copper barium(2+) tetrachloride Chemical compound [Cu+2].[Cl-].[Ba+2].[Cl-].[Cl-].[Cl-] LKPIKTXUOSKAHF-UHFFFAOYSA-J 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-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
Landscapes
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、床、壁、天井等の建築物内装材等の用途に用い、特に意匠性及び耐傷付き性に優れた壁紙に関する。 The present invention relates to wallpaper that is used for interior building materials such as floors, walls, and ceilings, and is particularly excellent in terms of design and scratch resistance.
壁紙として、紙、織物、不織布等の基材上にポリ塩化ビニル系樹脂やオレフィン系樹脂からなる樹脂層が積層され、更に印刷処理やエンボス加工により意匠を付与した設計が知られている。特にエンボス加工の段階で樹脂層が厚い場合、起伏の大きいエンボス加工が可能になり意匠性が向上する。 Wallpapers are known to have a resin layer made of polyvinyl chloride resin or olefin resin laminated onto a base material such as paper, textile, or nonwoven fabric, and then a design is applied using printing or embossing. In particular, if the resin layer is thick at the embossing stage, embossing with large undulations is possible, improving the design.
しかしながら、樹脂層を単純に厚くすると質量が増加することで施工性や防火性が低下すると云う問題がある。 However, simply making the resin layer thicker increases the mass, which can lead to problems with ease of installation and reduced fire resistance.
そこで樹脂層に発泡剤を含有して加熱後の発泡厚、換言すれば発泡性を高くする手法が採られており、例えば特許文献1に開示されている。 Therefore, a method has been adopted in which the resin layer contains a foaming agent to increase the foam thickness after heating, in other words, the foaming ability, as disclosed in, for example, Patent Document 1.
しかし、発泡性を高くすると表面が柔らかくなり耐傷付き性が低下するという課題があった。 However, there was an issue that increasing the foaming rate made the surface softer and reduced scratch resistance.
即ち、本発明は発泡性を高くして起伏の高いエンボス加工を可能にしつつ優れた耐傷付き性も確保した壁紙を提供することを目的とする。 In other words, the objective of the present invention is to provide wallpaper that has high foaming properties, allowing for highly embossed finishes with high relief, while also ensuring excellent scratch resistance.
上記の課題に対して鋭意検証した結果、基材と、前記基材に積層された発泡性ポリ塩化ビニル系樹脂層と、前記発泡性ポリ塩化ビニル系樹脂層に積層されたトップコート層、とを備え、前記発泡性ポリ塩化ビニル系樹脂層がフタル酸ジイソノニルを含み、前記発泡性ポリ塩化ビニル系樹脂層に用いるポリ塩化ビニル系樹脂が、平均重合度が1200を超え1600以下であり、1次粒子の平均粒子径が0.02~20.0μmであるペースト加工用ポリ塩化ビニル系樹脂であり、前記発泡性ポリ塩化ビニル系樹脂層に炭酸カルシウムが前記ポリ塩化ビニル系樹脂100重量部に対し0重量部を超えて20重量部以下含有することで、解決できることを見出した。
As a result of intensive investigations into the above-mentioned problems, it has been found that the problems can be solved by providing a substrate, an expandable polyvinyl chloride-based resin layer laminated on the substrate, and a topcoat layer laminated on the expandable polyvinyl chloride-based resin layer, wherein the expandable polyvinyl chloride-based resin layer contains diisononyl phthalate, the polyvinyl chloride-based resin used in the expandable polyvinyl chloride-based resin layer is a polyvinyl chloride-based resin for paste processing having an average degree of polymerization of more than 1200 and not more than 1600 and an average particle size of primary particles of 0.02 to 20.0 μm , and the expandable polyvinyl chloride-based resin layer contains calcium carbonate in an amount of more than 0 part by weight and not more than 20 parts by weight per 100 parts by weight of the polyvinyl chloride-based resin.
更に、トップコート層がシリコーン-アクリレート系であることも好ましい。
Furthermore , it is also preferred that the topcoat layer is a silicone-acrylate type.
本発明は、意匠性及び耐傷付き性に優れる壁紙を提供する。 The present invention provides wallpaper with excellent design and scratch resistance.
本発明の基本構成は基材上に発泡性ポリ塩化ビニル系樹脂層、及びトップコート層を付与する壁紙である。以下に詳細に説明する。 The basic structure of this invention is a wallpaper that has a foamable polyvinyl chloride resin layer and a topcoat layer applied to a substrate. This is explained in detail below.
「発泡性ポリ塩化ビニル系樹脂層」
発泡性ポリ塩化ビニル系樹脂層はポリ塩化ビニル系樹脂からなる層を発泡させた層である。
発泡性ポリ塩化ビニル系樹脂層に用いるポリ塩化ビニル系樹脂には、平均重合度が1200を超えて1600以下のものとする。平均重合度を当該範囲内に限定することで高い発泡性と耐傷付き性を両立することが可能になる。平均重合度が1200以下の場合は耐傷付き性が不足し、1600を超えると発泡性が低下する。平均重合度の測定は「JIS K 6720-2:1999 プラスチック ― 塩化ビニルホモポリマー及びコポリマー(PVC) ― 第2部:試験片の作り方及び諸性質の求め方」を用いることができる。
"Foamable polyvinyl chloride resin layer"
The expandable polyvinyl chloride resin layer is a layer obtained by expanding a layer made of polyvinyl chloride resin.
The polyvinyl chloride resin used in the expandable polyvinyl chloride resin layer has an average degree of polymerization of more than 1200 and not more than 1600. By limiting the average degree of polymerization within this range, it is possible to achieve both high expandability and scratch resistance. If the average degree of polymerization is 1200 or less, scratch resistance is insufficient, and if it exceeds 1600, expandability decreases. The average degree of polymerization can be measured according to "JIS K 6720-2: 1999 Plastics - Vinyl chloride homopolymers and copolymers (PVC) - Part 2: Preparation of test pieces and determination of various properties".
発泡性ポリ塩化ビニル系樹脂層に用いるポリ塩化ビニル系樹脂としては、塩化ビニルを主たる構成成分とすればよいが、塩化ビニル以外の共重合成分を含んでもよい。具体的にはポリ塩化ビニル、エチレン-塩化ビニル共重合体、プロピレン-塩化ビニル共重合体、塩化ビニル-アクリル系樹脂共重合体、塩化ビニル-ウレタン共重合体、塩化ビニル-塩化ビニリデン共重合体、塩化ビニル-酢酸ビニル共重合体などが挙げられる。また、塩化ビニル系樹脂としては、ペースト加工用ポリ塩化ビニル系樹脂やサスペンジョンポリ塩化ビニル系樹脂を用いることができる。さらにこれらポリ塩化ビニル系樹脂を1種単独でも2種以上を組み合わせて使用してもよい。特にペースト加工用ポリ塩化ビニル系樹脂を用いるとペーストコーティングが可能となり、安価な設備で多様な配合剤の多量配合による多様な発泡製品が可能となり、更に少量多品種製品に適するなど好ましい。 The polyvinyl chloride resin used in the foamable polyvinyl chloride resin layer may contain vinyl chloride as the main component, but may also contain copolymer components other than vinyl chloride. Specific examples include polyvinyl chloride, ethylene-vinyl chloride copolymer, propylene-vinyl chloride copolymer, vinyl chloride-acrylic resin copolymer, vinyl chloride-urethane copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, etc. In addition, polyvinyl chloride resins for paste processing and suspension polyvinyl chloride resins can be used as the vinyl chloride resin. Furthermore, these polyvinyl chloride resins may be used alone or in combination of two or more. In particular, the use of polyvinyl chloride resins for paste processing is preferable because it enables paste coating, enables a variety of foamed products by blending a large amount of various compounding agents with inexpensive equipment, and is suitable for small-scale production of a wide variety of products.
ペースト加工用ポリ塩化ビニル系樹脂とは、主に乳化重合法やミクロ懸濁重合法により得られる、1次粒子の平均粒子径が例えば0.02~20.0μmである微細なポリマー粒子であり、可塑剤の添加によりペースト状になるのが一般的な特徴である。サスペンジョンポリ塩化ビニル系樹脂とは、主に懸濁重合法により得られる、1次粒子の平均粒子径が例えば50~200μmでポーラスな不定形状の塩化ビニル系樹脂のことである。このポーラスな形状を有することで可塑剤等の液体を吸収できるため、ペースト状とならないのが特徴であり、押出加工やカレンダー加工で主に用いられる。 Polyvinyl chloride resin for paste processing is a fine polymer particle obtained mainly by emulsion polymerization or microsuspension polymerization, with the average primary particle diameter being, for example, 0.02 to 20.0 μm, and is generally characterized by becoming paste-like when a plasticizer is added. Suspension polyvinyl chloride resin is a porous, amorphous vinyl chloride resin obtained mainly by suspension polymerization, with the average primary particle diameter being, for example, 50 to 200 μm. This porous shape allows it to absorb liquids such as plasticizers, so it does not become paste-like, and is mainly used in extrusion processing and calendar processing.
発泡性ポリ塩化ビニル系樹脂層には、可塑剤としてフタル酸ジイソノニル(DINP)を用いる。また、フタル酸ジイソノニルに他の可塑剤を合わせて用いても良い。この様な可塑剤としては、ジ‐2‐エチルヘキシルフタレート(DOP)、ジイソデシルフタレート(DIDP)、ジオクチルテレフタレート(DOTP)等のフタル酸系可塑剤、二塩基酸とグリコールの重縮合を基本構造とし、その両末端を一塩基酸または一価アルコールにより停止することにより分子量を800~8000としたポリエステル系可塑剤、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(イソプロピル化フェニル)、リン酸トリス(ジクロロプロピル)等などのリン酸エステル系可塑剤、スルホン酸エステル系可塑剤を用いることができる。 Diisononyl phthalate (DINP) is used as a plasticizer for the foamable polyvinyl chloride resin layer. Diisononyl phthalate may also be used in combination with other plasticizers. Examples of such plasticizers include phthalic acid plasticizers such as di-2-ethylhexyl phthalate (DOP), diisodecyl phthalate (DIDP), and dioctyl terephthalate (DOTP), polyester plasticizers with a basic structure of polycondensation of dibasic acid and glycol and a molecular weight of 800 to 8,000 obtained by terminating both ends with monobasic acid or monohydric alcohol, and adipic acid esters such as DOA (di-2-ethylhexyl adipate) and DIDA (diisodecyl adipate). It is possible to use aliphatic dibasic acid ester plasticizers such as dibasic acid ester plasticizers, sebacate ester plasticizers such as DOS (di-2-ethylhexyl sebacate), azelaate ester plasticizers such as DOZ (di-2-ethylhexyl azelate), phosphate ester plasticizers such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, tris(isopropylated phenyl) phosphate, tris(dichloropropyl) phosphate, and sulfonate ester plasticizers.
フタル酸ジイソノニル(DINP)はジ‐2‐エチルヘキシルフタレート(DOP)と比較して耐傷付き性に優れるため好適に用いられる。したがって、可塑剤としてフタル酸ジイソノニル(DINP)を単独で用いるか、フタル酸ジイソノニル(DINP)を主な可塑剤として用いることが好ましい。さらに、フタル酸ジイソノニル(DINP)と合わせて用いる他の可塑剤の添加量は、フタル酸ジイソノニル(DINP)の添加量を超えないことが好ましい。 Diisononyl phthalate (DINP) is preferably used because it has superior scratch resistance compared to di-2-ethylhexyl phthalate (DOP). Therefore, it is preferable to use diisononyl phthalate (DINP) alone as a plasticizer, or to use diisononyl phthalate (DINP) as the main plasticizer. Furthermore, it is preferable that the amount of other plasticizers used in combination with diisononyl phthalate (DINP) does not exceed the amount of diisononyl phthalate (DINP) added.
発泡性ポリ塩化ビニル系樹脂層に添加されるフタル酸ジイソノニル(DINP)の添加量はポリ塩化ビニル系樹脂100重量部に対して20~80重量部が好ましい。フタル酸ジイソノニル(DINP)の添加量が80重量部を超えると耐傷付き性が低下したり、壁紙表面からのフタル酸ジイソノニル(DINP)のブリードや壁紙のブロッキング等が生じたりする場合がある。また20重量部より少ないと塩化ビニル樹脂の可塑化が低下し加工性が低下するおそれがある。フタル酸ジイソノニル(DINP)の添加量は30重量部~60重量部がより好ましく、35重量部~45重量部がさらに好ましい。 The amount of diisononyl phthalate (DINP) added to the foamable polyvinyl chloride resin layer is preferably 20 to 80 parts by weight per 100 parts by weight of polyvinyl chloride resin. If the amount of diisononyl phthalate (DINP) added exceeds 80 parts by weight, scratch resistance may decrease, and bleeding of diisononyl phthalate (DINP) from the wallpaper surface or blocking of the wallpaper may occur. If the amount is less than 20 parts by weight, the plasticization of the polyvinyl chloride resin may decrease, resulting in a decrease in processability. The amount of diisononyl phthalate (DINP) added is more preferably 30 to 60 parts by weight, and even more preferably 35 to 45 parts by weight.
フタル酸ジイソノニル(DINP)と他の可塑剤を合わせて添加する場合、フタル酸ジイソノニル(DINP)と他の可塑剤との合計の可塑剤の添加量を総添加量として、総添加量はポリ塩化ビニル系樹脂100重量部に対して20~80重量部が好ましい。可塑剤の総添加量が80重量部を超えると壁紙からの可塑剤のブリードや壁紙のブロッキング等が起こったり発泡性ポリ塩化ビニル系樹脂層が充分に発泡しない場合がある。20重量部より少ないと発泡性ポリ塩化ビニル系樹脂層が荒れて平滑な表面が得られない場合がある。可塑剤の添加量は30重量部~60重量部がより好ましく、35重量部~55重量部がさらに好ましい。 When diisononyl phthalate (DINP) and other plasticizers are added together, the total amount of plasticizers added, including diisononyl phthalate (DINP) and other plasticizers, is considered to be the total amount added, and the total amount added is preferably 20 to 80 parts by weight per 100 parts by weight of polyvinyl chloride resin. If the total amount of plasticizer added exceeds 80 parts by weight, bleeding of the plasticizer from the wallpaper, blocking of the wallpaper, etc. may occur, and the expandable polyvinyl chloride resin layer may not expand sufficiently. If it is less than 20 parts by weight, the expandable polyvinyl chloride resin layer may become rough and a smooth surface may not be obtained. The amount of plasticizer added is more preferably 30 to 60 parts by weight, and even more preferably 35 to 55 parts by weight.
発泡性ポリ塩化ビニル系樹脂層には充填剤を実質的に含まないことが好適である。耐傷付き性は充填剤が添加される程低下するため、耐傷付き性を最大限向上させる場合は充填剤を含まないことが好適となる。 It is preferable that the foamable polyvinyl chloride resin layer contains substantially no filler. The more filler is added, the lower the scratch resistance becomes, so if you want to maximize scratch resistance, it is preferable to not contain any filler.
また、耐傷付き性の他に低廉化や難燃性の向上を求める場合は発泡性ポリ塩化ビニル系樹脂層に充填剤を用いることもできる。この場合、ポリ塩化ビニル系樹脂100重量部に対し、充填剤を0重量部を超えて20重量部以下とすることが好ましく、15重量部以下がさらに好ましい。 If cost reduction and improved flame retardancy are required in addition to scratch resistance, a filler can be used in the foamable polyvinyl chloride resin layer. In this case, it is preferable to use more than 0 parts by weight and not more than 20 parts by weight of the filler per 100 parts by weight of polyvinyl chloride resin, and more preferably not more than 15 parts by weight.
充填剤としては特に限定されないが、例えば炭酸カルシウム、炭酸マグネシウム、酸化チタン、ケイ酸マグネシウム、水酸化アルミニウム、水酸化アンモニウム、タルク、シリカ、珪藻土等が挙げられ、2種以上を併用してもよい。 The filler is not particularly limited, but examples include calcium carbonate, magnesium carbonate, titanium oxide, magnesium silicate, aluminum hydroxide, ammonium hydroxide, talc, silica, diatomaceous earth, etc., and two or more types may be used in combination.
発泡性ポリ塩化ビニル系樹脂層に安定剤を用いる場合は、ハロゲン化金属塩を含むことが好ましい。これにより熱安定性が向上し更に発泡が促進される。 When a stabilizer is used in the expandable polyvinyl chloride resin layer, it is preferable that it contains a metal halide salt. This improves the thermal stability and further promotes foaming.
ハロゲン化金属塩としては塩化亜鉛、塩化鉄、塩化マグネシウム、塩化カルシウム、塩化バリウム塩化銅、フッ化亜鉛、フッ化鉄、フッ化マグネシウム、フッ化カルシウム、フッ化バリウム、フッ化銅等が挙げられるが、特に塩化亜鉛が好ましい。しかし、塩化亜鉛はポリ塩化ビニルの加工時の脱塩酸を促進し、いわゆるジンクバーニングと呼ばれる黒化をもたらすため多量の添加は好ましくない。したがって、ポリ塩化ビニル系樹脂に対しハロゲン化金属塩の添加量は0.05~0.25wt%であると充分な発泡促進性が得られ好ましい。 Examples of metal halide salts include zinc chloride, iron chloride, magnesium chloride, calcium chloride, barium chloride copper chloride, zinc fluoride, iron fluoride, magnesium fluoride, calcium fluoride, barium fluoride, and copper fluoride, with zinc chloride being particularly preferred. However, zinc chloride promotes dehydrochlorination during processing of polyvinyl chloride, and causes blackening known as zinc burning, so adding large amounts is not recommended. Therefore, it is preferable to add 0.05 to 0.25 wt% of metal halide salt to polyvinyl chloride resin, as this provides sufficient foaming promotion.
安定剤として更に、バリウム系化合物、カルシウム系化合物、バリウム系化合物、カルシウム系化合物、スズ系化合物、亜鉛系化合物、カリウム系化合物等を含んでもよく、特にカルシウム系化合物が好ましい。カルシウム系化合物の含有量は特に制限しないが、例えばポリ塩化ビニル系樹脂に対し0.10~0.60wt%であると充分な熱安定性効果と安定的な発泡性が得られ好ましい。 The stabilizer may further include a barium-based compound, a calcium-based compound, a barium-based compound, a calcium-based compound, a tin-based compound, a zinc-based compound, a potassium-based compound, etc., with calcium-based compounds being particularly preferred. There are no particular limitations on the amount of calcium-based compound contained, but for example, a content of 0.10 to 0.60 wt% relative to the polyvinyl chloride resin is preferred as this provides sufficient thermal stability and stable foaming properties.
本発明に用いる発泡剤としては公知のものを用いることができ、例えばアゾジカルボンアミド、アゾビスホルムアミド、オキシベンゼンスルホニルヒドラジド、パラトルエンスルホニルヒドラジド等が挙げられる。 The foaming agent used in the present invention may be any known foaming agent, such as azodicarbonamide, azobisformamide, oxybenzenesulfonylhydrazide, paratoluenesulfonylhydrazide, etc.
発泡性ポリ塩化ビニル系樹脂層には課題解決に支障を来さない限りにおいて、着色剤、加工助剤、抗菌剤、防カビ剤、防炎剤、脱泡剤、減粘剤等の各種添加剤を適宜加えてもよい。 Various additives such as colorants, processing aids, antibacterial agents, antifungal agents, flame retardants, defoamers, and viscosity reducers may be added to the foamable polyvinyl chloride resin layer as appropriate, provided that they do not interfere with the solution of the problem.
発泡性ポリ塩化ビニル系樹脂層の坪量としては特に限定されないが、隠ぺい性と施工性から130g/m2~200g/m2であると好ましい。130g/m2未満であると隠蔽性に欠けたり、施工性が低下したりする場合がある。200g/m2を超過すると防火性が低下する場合がある。 The basis weight of the expandable polyvinyl chloride resin layer is not particularly limited, but is preferably 130 g/m 2 to 200 g/m 2 in terms of concealment and workability. If it is less than 130 g/m 2 , the concealment may be lacking and workability may be reduced. If it exceeds 200 g/m 2 , the fire resistance may be reduced.
「トップコート層」
本発明では、発泡性ポリ塩化ビニル系樹脂層の上にトップコート層を付与する。トップコート層はシリコーン系化合物、フッ素系化合物、ウレタン系化合物、アクリル系化合物、塩化ビニル系化合物等が挙げられ、これらを2種以上組み合わせた共重合体や混合物でも構わないが、特にシリコーン-アクリレート系が好適である。
Top coat layer
In the present invention, a topcoat layer is applied on the expandable polyvinyl chloride resin layer. The topcoat layer may be made of a silicone compound, a fluorine compound, a urethane compound, an acrylic compound, a vinyl chloride compound, or the like. A copolymer or mixture of two or more of these may also be used, but a silicone-acrylate compound is particularly preferred.
トップコート層の塗布量は特に限定されないが、乾燥状態で0.5g/m2~6g/m2であると好ましい。0.5g/m2未満であると充分な耐傷付き性が得られない場合がある。また6g/m2を超過するとエンボス加工時にパンク等の不具合が発生する場合がある。 The coating amount of the topcoat layer is not particularly limited, but is preferably 0.5 g/ m2 to 6 g/ m2 in a dry state. If it is less than 0.5 g/ m2 , sufficient scratch resistance may not be obtained. If it exceeds 6 g/ m2 , defects such as punctures may occur during embossing.
必要に応じて発泡性ポリ塩化ビニル系樹脂層の上に印刷層又は機能層を付与してもよいが、その場合は印刷層又は機能層の上にトップコート層を付与する。 If necessary, a printed layer or a functional layer may be applied on the expandable polyvinyl chloride resin layer, in which case a topcoat layer is applied on the printed layer or the functional layer.
「基材」
本発明に用いる基材としては、普通紙(パルプ主体で公知のサイズ剤により処理したもの)、難燃紙(パルプ主体でスルファミン酸グアニジン、リン酸グアニジン等の難燃剤により処理したもの)、無機質紙(水酸化マグネシウム、水酸化アルミニウム等の無機添加剤を含むもの)、フリース紙(パルプとポリエステル等の合成繊維等を混合して抄紙したもの)が挙げられる。特に普通紙を用いると耐傷付き性、施工性が向上するため好ましい。
"Base material"
Examples of the substrates used in the present invention include plain paper (mainly pulp and treated with a known sizing agent), flame retardant paper (mainly pulp and treated with a flame retardant such as guanidine sulfamate or guanidine phosphate), inorganic paper (containing inorganic additives such as magnesium hydroxide or aluminum hydroxide), and fleece paper (made by mixing pulp and synthetic fibers such as polyester). Plain paper is particularly preferred because it improves scratch resistance and workability.
基材の坪量としては特に限定されないが、隠ぺい性と施工性から50g/m2~170g/m2であると好ましい。50g/m2未満であると隠蔽性に欠けたり、施工性が低下したりする場合がある。170g/m2を超過すると防火性が低下する場合がある。 The basis weight of the substrate is not particularly limited, but is preferably 50 g/m 2 to 170 g/m 2 in terms of hiding power and workability. If it is less than 50 g/m 2 , hiding power may be lacking and workability may be reduced. If it exceeds 170 g/m 2 , fire resistance may be reduced.
本発明の壁紙の製造方法としては公知の方法が用いることができるが、基材の上側にポリ塩化ビニル系樹脂を含有する発泡性ポリ塩化ビニル系樹脂層を積層する工程と、発泡性ポリ塩化ビニル系樹脂層の上側にトップコート層を付与する工程を有していればよい。例えばポリ塩化ビニル系樹脂に可塑剤、発泡剤等を配合しブレンダー等で混練して得られたポリ塩化ビニル系樹脂組成物を基材上にペーストコーティング法又はカレンダー法にて積層しポリ塩化ビニル系樹脂層を得る。次に、得られたポリ塩化ビニル系樹脂層に、グラビア印刷、フレキソ印刷、オフセット印刷又はシルクスクリーン印刷等を用いてトップコート層を積層し、ヒーターエンボス機または発泡エンボス機にてポリ塩化ビニル系樹脂層を発泡させ発泡性ポリ塩化ビニル系樹脂層を得る。さらに発泡性ポリ塩化ビニル系樹脂層にメカニカルエンボスを行うことで壁紙の表面にエンボスを施すことができる。
また基材にポリ塩化ビニル系樹脂層を積層する際にペーストコーティングを用いると多様な配合剤の多量配合にも適応可能となり好ましい。
The method for producing the wallpaper of the present invention may be a known method, but it is sufficient to have a step of laminating an expandable polyvinyl chloride resin layer containing a polyvinyl chloride resin on the upper side of the substrate, and a step of providing a topcoat layer on the upper side of the expandable polyvinyl chloride resin layer. For example, a polyvinyl chloride resin composition obtained by blending a plasticizer, a foaming agent, etc. with a polyvinyl chloride resin and kneading it with a blender or the like is laminated on a substrate by a paste coating method or a calendar method to obtain a polyvinyl chloride resin layer. Next, a topcoat layer is laminated on the obtained polyvinyl chloride resin layer using gravure printing, flexographic printing, offset printing, silk screen printing, etc., and the polyvinyl chloride resin layer is foamed with a heater embossing machine or a foaming embossing machine to obtain a foamable polyvinyl chloride resin layer. Furthermore, the surface of the wallpaper can be embossed by mechanical embossing the expandable polyvinyl chloride resin layer.
Furthermore, when a polyvinyl chloride resin layer is laminated on a substrate, paste coating is preferably used, which allows for the use of large amounts of a variety of compounding agents.
以下に、本発明を実施例により詳細に説明するが、本発明はこれら実施例に制限されるものではない。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
実施例1では、表1に示す如く基材として坪量65g/m2の普通紙を用い、平均重合度1210のポリ塩化ビニル樹脂、フタル酸ジイソノニル、カルシウム・塩化亜鉛系安定剤、アゾジカルボンアミドを所定量で混合したペーストゾルを、ペーストコーターで塗布することで基材上にポリ塩化ビニル系樹脂層を付与した。次いで、グラビア印刷機を用いてシリコーン-アクリレート系トップコート層を乾燥状態の塗布量0.9g/m2で付与した。その後ギアオーブンにて215℃、40秒で加熱発泡させ、メカニカルエンボス機を用いてエンボスを施した。 In Example 1, as shown in Table 1, plain paper with a basis weight of 65 g/ m2 was used as the substrate, and a paste sol in which a polyvinyl chloride resin with an average degree of polymerization of 1210, diisononyl phthalate, a calcium-zinc chloride stabilizer, and azodicarbonamide were mixed in predetermined amounts was applied with a paste coater to provide a polyvinyl chloride resin layer on the substrate. Next, a silicone-acrylate top coat layer was applied with a dry coating amount of 0.9 g/ m2 using a gravure printing machine. After that, the substrate was heated and foamed at 215°C for 40 seconds in a gear oven, and embossed using a mechanical embossing machine.
実施例2では平均重合度1300のポリ塩化ビニル樹脂を使用し、フタル酸ジイソノニルを減量した他は実施例1に準拠した。 In Example 2, polyvinyl chloride resin with an average degree of polymerization of 1300 was used, and the amount of diisononyl phthalate was reduced, but the rest of the experiment was similar to Example 1.
実施例3では平均重合度1550のポリ塩化ビニル樹脂を使用した他は実施例1に準拠した。 Example 3 conforms to Example 1 except that a polyvinyl chloride resin with an average degree of polymerization of 1550 was used.
実施例4では発泡性ポリ塩化ビニル系樹脂層に炭酸カルシウムを含有し、フタル酸ジイソノニルを増量した他は実施例1に準拠した。 Example 4 was similar to Example 1 except that the expandable polyvinyl chloride resin layer contained calcium carbonate and the amount of diisononyl phthalate was increased.
比較例1では、表2に示す如く平均重合度1050のポリ塩化ビニル樹脂を使用した他は実施例1に準拠した。 Comparative Example 1 was similar to Example 1 except that a polyvinyl chloride resin with an average degree of polymerization of 1050 was used, as shown in Table 2.
比較例2では平均重合度1700のポリ塩化ビニル樹脂を使用した他は実施例1に準拠した。 Comparative Example 2 conforms to Example 1 except that a polyvinyl chloride resin with an average degree of polymerization of 1700 was used.
比較例3ではフタル酸ビス(2-エチルヘキシル)、炭酸カルシウムを使用した他は実施例2に準拠した。 Comparative Example 3 was similar to Example 2 except that bis(2-ethylhexyl) phthalate and calcium carbonate were used.
比較例4ではハロゲン化金属塩を含まないバリウム・亜鉛系安定剤を使用した他は実施例1に準拠した。 Comparative Example 4 was similar to Example 1 except that a barium-zinc stabilizer that did not contain a metal halide salt was used.
比較例5では平均重合度1700のポリ塩化ビニル樹脂を使用し、炭酸カルシウムを増量した他は実施例4に準拠した。 Comparative Example 5 was similar to Example 4 except that a polyvinyl chloride resin with an average degree of polymerization of 1700 was used and the amount of calcium carbonate was increased.
実施例1乃至4及び比較例1乃至5について、以下評価を行った。 The following evaluations were performed for Examples 1 to 4 and Comparative Examples 1 to 5.
[発泡性評価]
エンボスを施す前のギアオーブンにて215℃、40秒で加熱発泡させた際の発泡倍率(発泡後の発泡性ポリ塩化ビニル系樹脂層厚さ÷発泡前の発泡性ポリ塩化ビニル系樹脂層厚さ)が5.1以上であれば合格、5.1未満であれば不合格とした。
各厚さはJIS P 8118:2014「紙及び板紙-厚さ,密度及び比容積の試験方法」の9.3.1「厚さの測定」に準拠し、調湿しない室温で測定した。
[Foaming evaluation]
When the film was heated and foamed in a Geer oven at 215° C. for 40 seconds before embossing, the film was rated as passed if the foaming ratio (thickness of the foamable polyvinyl chloride resin layer after foaming ÷ thickness of the foamable polyvinyl chloride resin layer before foaming) was 5.1 or more, and was rated as failed if it was less than 5.1.
Each thickness was measured in accordance with 9.3.1 “Measurement of thickness” of JIS P 8118:2014 “Paper and paperboard-Test methods for thickness, density and specific volume” at room temperature without humidity conditioning.
[耐傷付き性]
壁紙工業会規定の規格「表面強化壁紙性能規定」に準じ、30mm×250mmの試験体表面を荷重200gfとした摩擦子を装備したJIS L 0849で規定する摩擦試験機II型を用いて毎分30回往復の速度で引掻き、比較的大きな表面層の破れが見られなければ合格、表面層の破れが明確に見えたら不合格とした。
[Scratch resistance]
In accordance with the "Surface-reinforced wallpaper performance standard" set forth by the Wallpaper Industry Association, the surface of a 30 mm x 250 mm test specimen was scratched at a speed of 30 reciprocations per minute using a friction tester type II specified in JIS L 0849 equipped with a friction element with a load of 200 gf. If no relatively large tears in the surface layer were observed, the specimen was rated as passing, and if tears in the surface layer were clearly visible, the specimen was rated as failing.
[評価結果]
実施例1乃至は4は何れも良好な発泡性と耐傷付き性を示し、本発明の望ましい形態である。
[Evaluation results]
All of Examples 1 to 4 exhibit good foaming properties and scratch resistance, and are desirable embodiments of the present invention.
これに対し、比較例1及び3ではそれぞれ、ポリ塩化ビニル樹脂の平均重合度が低い又はフタル酸ジイソノニルを使用しないことにより耐傷付き性が不足した。比較例2ではポリ塩化ビニル樹脂の平均重合度が高く発泡性が低下した。比較例4及び5ではそれぞれ、ハロゲン化金属塩を含む安定剤を使用しない且つトップコート層を付与しない、又はポリ塩化ビニル樹脂の平均重合度が高い且つ炭酸カルシウム含有量が多いことにより、発泡性、耐傷付き性共に不合格となった。 In contrast, in Comparative Examples 1 and 3, the average degree of polymerization of the polyvinyl chloride resin was low or diisononyl phthalate was not used, resulting in insufficient scratch resistance. In Comparative Example 2, the average degree of polymerization of the polyvinyl chloride resin was high, resulting in reduced foamability. In Comparative Examples 4 and 5, the foamability and scratch resistance were both unsatisfactory, due to the absence of a stabilizer containing a metal halide salt and the absence of a topcoat layer, or the high average degree of polymerization of the polyvinyl chloride resin and the high calcium carbonate content, respectively.
Claims (2)
前記基材に積層された発泡性ポリ塩化ビニル系樹脂層と、
前記発泡性ポリ塩化ビニル系樹脂層に積層されたトップコート層、とを備え、
前記発泡性ポリ塩化ビニル系樹脂層がフタル酸ジイソノニルを含み、
前記発泡性ポリ塩化ビニル系樹脂層に用いるポリ塩化ビニル系樹脂が、平均重合度が1200を超え1600以下であり、1次粒子の平均粒子径が0.02~20.0μmであるペースト加工用ポリ塩化ビニル系樹脂であり、
前記発泡性ポリ塩化ビニル系樹脂層に炭酸カルシウムが前記ポリ塩化ビニル系樹脂100重量部に対し0重量部を超えて20重量部以下含有する壁紙。 A substrate;
A foamable polyvinyl chloride resin layer laminated on the substrate;
and a top coat layer laminated on the expandable polyvinyl chloride resin layer,
the foamable polyvinyl chloride resin layer contains diisononyl phthalate,
The polyvinyl chloride resin used in the expandable polyvinyl chloride resin layer is a polyvinyl chloride resin for paste processing having an average degree of polymerization of more than 1200 and not more than 1600 and an average particle size of primary particles of 0.02 to 20.0 μm ,
The wallpaper comprises in the expandable polyvinyl chloride resin layer more than 0 part by weight and not more than 20 parts by weight of calcium carbonate per 100 parts by weight of the polyvinyl chloride resin.
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JP2000158607A (en) | 1998-11-30 | 2000-06-13 | Okamoto Ind Inc | Wall covering material produced by laminated polyvinyl chloride film |
JP2000178394A (en) | 1998-12-16 | 2000-06-27 | Shin Etsu Polymer Co Ltd | Vinyl chloride resin composition |
JP2000211049A (en) | 1999-01-22 | 2000-08-02 | Toppan Printing Co Ltd | Foamed decorative material |
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