TWI836004B - 氯乙烯系樹脂乳液、水性墨水及記錄用紙 - Google Patents
氯乙烯系樹脂乳液、水性墨水及記錄用紙 Download PDFInfo
- Publication number
- TWI836004B TWI836004B TW109104532A TW109104532A TWI836004B TW I836004 B TWI836004 B TW I836004B TW 109104532 A TW109104532 A TW 109104532A TW 109104532 A TW109104532 A TW 109104532A TW I836004 B TWI836004 B TW I836004B
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- Prior art keywords
- vinyl chloride
- resin emulsion
- water
- chloride resin
- mass
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000839 emulsion Substances 0.000 title claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229920001692 polycarbonate urethane Polymers 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000000976 ink Substances 0.000 abstract description 43
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011230 binding agent Substances 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 9
- 229920000515 polycarbonate Polymers 0.000 abstract description 8
- 239000004417 polycarbonate Substances 0.000 abstract description 8
- 239000000835 fiber Substances 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 239000011147 inorganic material Substances 0.000 abstract description 3
- 238000009877 rendering Methods 0.000 abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 238000007639 printing Methods 0.000 description 24
- -1 coatings Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- 238000012546 transfer Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
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- 238000001879 gelation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- 239000011254 layer-forming composition Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 238000001139 pH measurement Methods 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- WYDMEZZKAWHQFP-UHFFFAOYSA-N 1,1,6-trichloro-3-methylhex-1-ene Chemical compound ClC(Cl)=CC(C)CCCCl WYDMEZZKAWHQFP-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- 229920002799 BoPET Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明提供氯乙烯系樹脂乳液及其製造方法,該氯乙烯系樹脂乳液係包含(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物與(B)含有氯乙烯單體的單體組成物之聚合物的樹脂乳液,其中相對於上述(B)含有氯乙烯單體的單體組成物100質量份,含有40~500質量份的上述(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物。本發明之氯乙烯系樹脂乳液係當使用於水性墨水時,發揮優異的耐水性、耐濕性、高光澤、耐醇性、密著性、常溫成膜性,當使用於記錄用紙時,發揮優異的顯色性、耐水性、耐濕性、色的視覺辨認性、高光澤、密著性,可有利地利用於墨水、塗料、無機物質分散等之黏結劑、記錄用紙之接受層、纖維之處理劑、醫療機構之壁紙等。
Description
本發明關於可有效地利用於墨水、塗料、無機物質分散等之黏結劑、記錄用紙之接受層、纖維之處理劑等的氯乙烯系樹脂乳液。特別地,關於一種氯乙烯系樹脂乳液,其當使用於水性墨水時,發揮優異的耐水性、耐濕性、高光澤、耐醇性、密著力、常溫成膜性,當使用於記錄用紙時,發揮優異的顯色性、耐濕性、色的視覺辨認性、高光澤、密著性。
首先,陳述凹版印刷墨水,於一般的印刷中,藉由印刷墨水所具有的印刷適應性與印刷效果而決定其良否。所謂印刷適應性,就是與從將印刷機上的墨水轉移至被印刷物到形成印刷面為止的墨水之行為關聯的性質,主要的特性有墨水的流動性、界面適應性、乾燥性等。所謂印刷效果,就是形成有印刷面的墨水所顯示的印刷之做出成果,其特性有色調、光澤、耐水性、抗黏連性等。墨水的基本的組成係以色料(染料、顏料)、展色劑、輔助劑(流動性調整劑、乾燥性調整劑等)所構成,其中展色劑係對於印刷適應性或印刷效果造成大的影響。展色劑之基本組成為黏結劑、蠟、溶劑等,因此依照黏結劑之選擇而展色劑之性質大幅變化,藉此而大幅左右印刷適應性或印刷效果之良否。
作為黏結劑,大致區分為溶劑型黏結劑與水性黏結劑。作為溶劑型黏結劑,可舉出日本特開平9-12956號公報(專利文獻1)所提案之胺基甲酸酯樹脂。然而,最近由於大氣污染、火災的危險性、作業衛生方面等之掛慮,不使用有機溶劑之水性黏結劑係受到注目。
作為水性黏結劑,大致區分為以苯乙烯・丙烯酸系為代表之鹼可溶性樹脂、以聚乙烯醇為代表之水溶性樹脂及胺基甲酸酯系乳液(專利文獻2:日本特開平2-238015號公報)、以丙烯酸系乳液為代表之水分散型樹脂。
一般而言,使用以水分散型樹脂為黏結劑的水性墨水進行印刷時,在印刷機上於室溫下將墨水塗佈到被印刷面,然後在水分散型樹脂的玻璃轉移溫度以上乾燥而完工。如此地,若加溫至玻璃轉移溫度以上,則樹脂粒子彼此係全體發生熔黏,被均勻地皮膜化而展現及提高耐水性。於印刷適應性之中,若著眼於印刷機上的乾燥性,則印刷墨水必須在印刷機上儘可能地長時間不乾燥而保持流動性,即使溶劑型樹脂、鹼可溶性樹脂或水溶性樹脂一旦乾燥而皮膜化,也可溶解於溶劑、鹼水溶液或水中,保持原本的流動性而無問題,若水分散型樹脂乾燥而樹脂粒子彼此的表面發生熔黏,則由於在水中不復原而有無法印刷之問題。另一方面,鹼可溶性樹脂由於有耐鹼性差的問題,水溶性樹脂由於有耐水性差的問題,故以往的黏結劑有併用鹼可溶性樹脂或水溶性樹脂與水分散型樹脂而調製之情況,但實際狀況為若欲使印刷適應性成為良好,則耐鹼性或耐水性變差,若欲使耐鹼性或耐水性成為良好,則印刷適應性變不充分。
為了解決該問題,於日本特開平10-176132號公報(專利文獻3)中,提案一種水性墨水用黏結劑,其包含由氯乙烯、烷基的碳數為1~18的(甲基)丙烯酸烷酯類及單烯基苯類所選出的單體、由具有官能基的乙烯性不飽和單體所選出的單體及其他的乙烯性不飽和單體。然而,在耐濕性或光澤之點上有問題。
又,有提案氟樹脂者(專利文獻4:日本特開平11-35866號公報)。氟樹脂雖然耐候性、耐蝕性等各方面優異,但皆留下成本面之問題。
接著,陳述噴墨用墨水,噴墨記錄方式係肅靜性、記錄速度、印字品質、運轉成本優異,一般而言廣泛普及。此方式所使用的墨水,從墨水物性、安全性、操作容易性等之點來看,使用水性墨水。作為如此的墨水,已知在二醇系溶劑與水中溶解有酸性染料、直接染料、鹼性染料等之水溶性染料者(專利文獻5~7:日本特開昭53-61412號公報、日本特開昭54-89811號公報、日本特開昭55-65269號公報),但有耐水性差之缺點。
因此,亦檢討將顏料使用於著色成分,為了分散顏料,使用導入有羧基的丙烯酸系樹脂或苯乙烯・丙烯酸樹脂等(專利文獻8:日本特開昭61-235478號公報),或使用由丙烯酸、苯乙烯、α-甲基苯乙烯所成之三元共聚物水性樹脂(專利文獻9:日本特開平8-253716號公報)。然而,雖然看見耐水性或耐候性之提升,但是在顏料的分散性(隨著時間經過的變化)之點上有改善之餘地。
接著,陳述記錄用紙之接受層,尤其噴墨記錄用紙。近年來,於個人電腦等的OA機器用之印表機中,使用採用水性墨水的記錄方式之比率升高,隨著其而記錄材料的需求亦正在擴大,但另一方面,為了使印刷的品質、彩度、外觀、圖像成為更良好,而要求具有更高度的特性之記錄材料。其使用用途亦涉及多方面,耐水性、顯色性等的要求特性變更加嚴格。作為如此的接受層,有提案在原紙上摻合塗佈有非晶質二氧化矽與聚乙烯醇等高分子黏合劑之記錄片材(專利文獻10:日本特開昭55-51583號公報),或在原紙的表面背面設有含有多孔質顏料粒子的墨水接受層之記錄片材(專利文獻11:日本特開昭56-148584號公報)。與以往之使用上等紙的記錄片材相比,雖然大幅地提高彩度的鮮明度,但是若塗佈量少,則墨水不規則地擴展,印字的模糊大,若增多塗佈量則模糊變少,但有塗佈層剝離而掉粉之問題。
又,有提案使用使聚乙烯醇與丙烯酸與甲基丙烯酸甲酯反應而得之水不溶性樹脂而改善黏合強度之記錄片材(專利文獻12:日本特開昭62-2880786號公報),但由於水不溶性樹脂為陰離子性,同樣陰離子性的水性墨水的固定性差,無法解決如墨水的暈開或提高耐水性者。
再者,亦有提案含有聚陽離子高分子電解質之記錄片材(專利文獻13:日本特開昭56-84992號公報)或設有以具有墨水吸附性的陽離子性高分子黏合劑為主成分之墨水接受層之記錄片材(專利文獻14:日本特開昭58-24493號公報),更且含有陽離子性丙烯酸樹脂乳液之記錄片材(專利文獻15、16:日本特開平11-123867號公報、日本特開2001-199152號公報),但在顯色性或耐水性之點上為未必可令人滿足者。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開平9-12956號公報
[專利文獻2]日本特開平2-238015號公報
[專利文獻3]日本特開平10-176132號公報
[專利文獻4]日本特開平11-35866號公報
[專利文獻5]日本特開昭53-61412號公報
[專利文獻6]日本特開昭54-89811號公報
[專利文獻7]日本特開昭55-65269號公報
[專利文獻8]日本特開昭61-235478號公報
[專利文獻9]日本特開平8-253716號公報
[專利文獻10]日本特開昭55-51583號公報
[專利文獻11]日本特開昭56-148584號公報
[專利文獻12]日本特開昭62-2880786號公報
[專利文獻13]日本特開昭56-84992號公報
[專利文獻14]日本特開昭58-24493號公報
[專利文獻15]日本特開平11-123867號公報
[專利文獻16]日本特開2001-199152號公報
[發明所欲解決的課題]
本發明係鑒於上述情事而完成者,目的在提供一種氯乙烯系樹脂乳液,當使用於水性墨水時,可發揮優異的耐水性、耐濕性、高光澤、耐醇性、密著性、常溫成膜性,當使用於記錄用紙時,可發揮優異的顯色性、耐水性、耐濕性、色的視覺辨認性、高光澤、密著性。
[解決課題的手段]
本發明者們為了達成上述目的而進行專心致力的檢討,結果發現:藉由在相對於(B)含有氯乙烯單體的單體組成物100質量份,存在40~500質量份之(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物下,使其乳化聚合而得之氯乙烯系樹脂乳液,係能克服前述課題,終於完成本發明。
因此,本發明提供下述之氯乙烯系樹脂乳液、水性墨水、記錄用紙及氯乙烯系樹脂乳液之製造方法。
1.一種氯乙烯系樹脂乳液,其係聚合物的樹脂乳液,該聚合物包含(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物與(B)含有氯乙烯單體的單體組成物,其特徵為:相對於上述(B)含有氯乙烯單體的單體組成物100質量份,含有40~500質量份的上述(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物。
2.一種水性墨水,其含有如上述1記載之氯乙烯系樹脂乳液。
3.一種記錄用紙,其具有如上述1記載之氯乙烯系樹脂乳液的塗膜。
4.一種氯乙烯系樹脂乳液之製造方法,其係藉由在相對於(B)含有氯乙烯單體的單體組成物100質量份,存在40~500質量份之(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物下,使其乳化聚合而得。
[發明的效果]
本發明之氯乙烯系樹脂乳液係當使用於水性墨水時,可發揮優異的耐水性、耐濕性、高光澤、耐醇性、密著性、常溫成膜性,且當使用於記錄用紙時,可發揮優異的顯色性、耐水性、耐濕性、色的視覺辨認性、高光澤、密著性,可有利地利用於墨水、塗料、無機物質分散等之黏結劑、記錄用紙之接受層、纖維之處理劑、醫療機構之壁紙等。
[實施發明的形態]
以下,具體地說明本發明之內容。
本發明之氯乙烯系水性墨水用黏結劑係在藉由相對於(B)含有氯乙烯單體的單體組成物100質量份,存在40~500質量份之數量平均分子量為5,000~50,000的(A)聚碳酸酯系胺基甲酸酯寡聚物下,使其乳化聚合而得之氯乙烯系樹脂乳液。
作為(A)成分的聚碳酸酯系胺基甲酸酯寡聚物,可使用市售品,例如可舉出ETERNACALL UW-1005E (宇部興產公司製)、Hydran WLS-207、Hydran WLS-230 (DIC公司製)等,惟不受其所限定,可使用1種或2種以上。
相對於(B)含有氯乙烯單體的單體組成物100質量份,上述(A)成分之摻合量為40~500質量份之範圍內,較佳為100~300質量份。若此摻合量未達40質量份,則有發生凝聚物之不良狀況,若超過500質量份則反應係鈍化,有發生無法安定生產之不良狀況。
(A)聚碳酸酯系胺基甲酸酯寡聚物之數量平均分子量較佳為5,000~50,000,更佳為8,000~25,000。若此胺基甲酸酯寡聚物之數量平均分子量未達5,000,則有發生凝聚物之不良狀況,若超過50,000,則凝聚物係大量地發生,最差的情況為發生凝膠化的不良狀況之情況。上述之數量平均分子量係以GPC所測定之聚苯乙烯換算值,於本發明中,將50,000以下者稱為寡聚物。
本發明之(B)成分係含有氯乙烯單體的單體組成物。於此單體組成物中,亦可僅使用氯乙烯單體作為單體(monomer)成分,或者也可混合氯乙烯單體及與其能共聚合的(C)含有乙烯性不飽和的單體而使用。
作為上述(C)成分之與氯乙烯單體能共聚合之含有乙烯性不飽和基的單體,例如可舉出醋酸乙烯酯、乙烯、丙烯、偏二氯乙烯,還有丙酸乙烯酯等之羧酸乙烯酯單體類、苯乙烯、α-甲基苯乙烯等之芳香族乙烯基單體類、1,3-丁二烯、2-甲基-1,3-丁二烯等之共軛二烯系單體類、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、甲基丙烯酸甲酯等之乙烯性不飽和單羧酸酯類、伊康酸二甲酯、馬來酸二乙酯、馬來酸單丁酯、富馬酸單乙酯、富馬酸二丁酯等之乙烯性不飽和多羧酸酯類、丙烯酸、甲基丙烯酸、巴豆酸等之乙烯性不飽和單羧酸類、伊康酸、馬來酸、富馬酸等之乙烯性不飽和二羧酸類、甲基丙烯酸環氧丙酯等之含有環氧基的單體類、甲基丙烯酸2-羥基乙酯等之含有醇性羥基的單體類、甲氧基乙基丙烯酸酯等之含有烷氧基的單體類、丙烯腈等之含有腈基的單體類、丙烯醯胺等之含有醯胺基的單體類、甲基丙烯酸二甲基胺基乙酯等之含有胺基的單體類、二乙烯基苯、甲基丙烯酸烯丙酯等之在1分子中具有的2個以上的乙烯性不飽和基之單體等,選擇其中的1種或2種以上,但較佳為醋酸乙烯酯、乙烯性不飽和單羧酸酯類、乙烯性不飽和單羧酸類。
此時,(B)氯乙烯單體與和其能共聚合的(C)含有乙烯性不飽和基的單體之比例,以質量比表示較佳為50:50~100:0,特佳為70:30~100:0。若氯乙烯量過少,則有發生凝聚物的不利之虞。
於上述乳化聚合中,可採用眾所周知的一切乳化聚合法。可在初期一併添加單體、聚碳酸酯系胺基甲酸酯寡聚物及其他的聚合助劑(例如烷基硫酸酯鹽等之乳化劑、過硫酸銨等之聚合起始劑、硫醇類等之鏈轉移劑、碳酸鈉等之pH調整劑、各種消泡劑等),也可連續地添加,亦可將其一部分在聚合中連續或分割地添加。
又,於不損害本發明的效果之範圍內,亦可併用非離子系界面活性劑或陰離子系乳化劑。例如,聚氧乙烯烷基苯基醚、聚氧乙烯烷基醚、聚氧乙烯脂肪酸酯、山梨醇酐脂肪酸酯、聚氧乙烯山梨醇酐脂肪酸酯、聚氧化烯烷基醚、聚氧乙烯衍生物、甘油脂肪酸酯、聚氧乙烯硬化蓖麻油、聚氧乙烯烷基胺、烷基烷醇醯胺,或乙炔醇、乙炔二醇及彼等之環氧乙烷加成物等之界面活性劑。
作為上述乳化聚合所用之聚合起始劑,可舉出過硫酸銨、過硫酸鉀等之過硫酸鹽、2,2’-二脒基-2,2’-偶氮丙烷二鹽酸鹽、偶氮雙異丁腈等之偶氮化合物、異丙苯氫過氧化物、過氧化苯甲醯、過氧化氫等之過氧化物、酒石酸等。又,亦可舉出眾所周知的氧化還原系起始劑,例如過硫酸鉀與亞硫酸氫鈉等。相對於上述單體,聚合起始劑之使用量通常為0.1~2.0質量%,較佳為0.2~1.0質量%。
進行上述乳化聚合之聚合溫度通常為40~80℃,宜為50~70℃。聚合時間只要適宜設定即可,但較佳為10~15小時。此聚合宜在氮氣等之惰性氣體的環境中進行。
蒸發殘分較佳為10~50質量%,更佳為20~40質量%。若未達10質量%,則有發生凝聚物之情況,若超過50質量%則有大量發生凝聚物之情況。
還有,於聚合結束後,在不損害本發明的水性墨水用黏結劑之性能的範圍內,亦可添加可塑劑、無機或有機填充劑、增黏劑等。
關於藉由上述乳化聚合而得的本發明之氯乙烯系樹脂乳液,其平均粒徑較佳為10~1000nm,更佳為20~800nm,其黏度(23℃)較佳為1~1800mPa・s,更佳為可得到5~1000mPa者。
藉由上述乳化聚合而得的本發明之氯乙烯系樹脂乳液係可使用於各種的用途,但尤其當使用於記錄用紙時,發揮優異的顯色性、耐水性、耐濕性、高光澤、密著性、常溫成膜性,當使用於水性墨水時,賦予耐水性、耐濕性、色的視覺辨認性、高光澤、優異的耐醇性、密著性。
此時,將本發明之氯乙烯系樹脂乳液使用於水性墨水時,可在此氯乙烯系樹脂乳液中摻合著色劑、水可溶性有機溶劑、各種添加劑、水等,藉由眾所周知的分散機、混合機、混煉機等進行分散、混合而製造。氯乙烯系樹脂乳液在水性墨水中的含量,以固體成分表示,較佳為2~30質量%,特佳為5~20質量%。作為著色劑,可使用染料、顏料等,於水性墨水中較佳為5~40質量%含有,特佳3~30質量%含有。作為水可溶性有機溶劑,可使用乙二醇單醚、二乙二醇單醚、丙二醇單醚、乙二醇二甲基醚、二乙二醇二甲基醚、乙二醇、二乙二醇、丙二醇、甘油、甲醇、乙醇、異丙醇、甲基乙基酮、甲基賽珞蘇、乙基賽珞蘇、丙酮、醋酸乙酯、二丙酮醇等,於水性墨水中較佳為0~60質量%,特佳為0~50質量%之含量。水係於水性墨水中較佳為5~95質量%,特佳為10~90質量%之含量。還有,作為添加劑,可舉出顏料分散劑、調平劑、消泡劑等,此等添加劑可以水性墨水的常用量使用。
又,將本發明之氯乙烯系樹脂乳液使用於記錄用紙時,尤其可適用於記錄用紙的接受層之形成。此時,於用於形成接受層之包含氯乙烯系樹脂乳液的接受層形成用組成物中,作為顏料,可摻合非晶質合成二氧化矽、矽酸鋁、矽酸鎂、沈降性碳酸鈣、重質碳酸鈣、矽酸鈣、氫氧化鋁、沸石、燒成黏土、高嶺土黏土、滑石、白碳等。此等成分之摻合量較佳為10~90質量%,特佳為20~80質量%。作為其他添加劑,可摻合顏料分散劑、消泡劑、著色劑、抗氧化劑、紫外線吸收劑、黏度調整劑、脫模劑等。
上述接受層形成用組成物可以刷毛塗佈、刮板塗佈機、氣刀塗佈機、簾式塗佈機、馬亞棒塗佈機、凹版塗佈機、輥塗機等之塗佈方式,以塗佈量成為3~25g/m2
(乾燥聚合固體成分)之方式,塗佈於市售的紙或壁紙材等之支撐體及乾燥而製造。
[實施例]
以下,顯示製造例與實施例及比較例,具體地說明本發明,惟本發明不受下述的實施例所限制。還有,於下述之例中,份及%分別表示質量份、質量%。
[實施例1]
於具備攪拌機、冷凝器、溫度計及氮氣導入口之聚合容器中,在氮氣置換後,加入去離子水44份、氯乙烯13份、ETERNACALL UW-1005E(宇部興產公司製的水系聚碳酸酯系胺基甲酸酯樹脂)42份(有效成分30%),邊攪拌邊加溫至60℃。再者,使過硫酸銨(起始劑)0.1份溶解於去離子水1份中,添加而進行聚合反應。
於聚合內壓成為0MPa之時間點,在真空中去除殘存單體直到成為1000ppm為止,然後冷卻到40℃以下而得到聚合物。固體成分30%、pH8.0、B型黏度計黏度(23℃) 10mPa・s。表1中顯示其結果。還有,藉由GPC確認所得之乳液為氯乙烯系樹脂者。
[實施例2~7、比較例1~8]
以如表1、2所示之組成,實施與實施例1同樣之聚合,得到氯乙烯系樹脂乳液。比較例1、2、4、5、7、8係發生凝聚物,無法性能評價。還有,實施例3之(C)成分係與氯乙烯單體一起地同時加入。
[評價方法]
<固體成分測定方法>
於鋁箔製之皿中量取氯乙烯系樹脂乳液約1g,置入經保持在105~110℃的乾燥器內,加熱1小時後,從乾燥器取出,在乾燥器之中放置冷卻。測量試料的乾燥後之重量,藉由下式算出固體成分。
【數1】
此處,R:固體成分(%)
W:裝有乾燥前的試料之鋁箔皿的質量(g)
A:鋁箔皿的質量(g)
D:裝有乾燥後的試料之鋁箔皿的質量(g)
鋁箔皿之尺寸:70φ・12h(mm)
依照JIS Z8802(pH測定方法),使用pH計,直接測定氯乙烯系樹脂乳液。
將氯乙烯系樹脂乳液溫保持在23±0.5℃,以BM型黏度計(No.1轉子、6rpm)測定。
使用光散射型粒徑測定裝置進行測定。
樣品調製
1.於量杯中採集樣品,以25℃純水進行稀釋。
2.以300篩目濾布,過濾經稀釋的樣品。
測定液溫 25℃
累計次數 100次
測定次數 1次
確認適當濃度,於上述測定條件下測定。
確認測定結果為良好。
於熱梯度試驗裝置ASTM-2354-65T(理學工業股份有限公司)上鋪設鋁箔,以0.1密耳的塗佈機塗佈氯乙烯系乳液,3小時後的成膜狀態係以單筒鏡(8×30 6° PENTAX
製),確認看到龜裂的溫度條件。MFT的較佳範圍為0~20℃。
以6密耳的刮刀,將氯乙烯系樹脂乳液塗佈於玻璃板,目視確認有無發生凝聚物。
○:凝聚物係無法確認。
△:發生少量的凝聚物。
×:發生大量的凝聚物。
以棒塗機No.4塗佈在PET薄膜(東麗Lumirror L-75)上,在105℃乾燥120秒。
目視及以顯微鏡((股)KEYENCE製)觀察於上述條件下所得之塗佈薄膜的外觀,實施成膜狀態及互斥程度之確認,依照下述之基準進行判断。
○:對於基材,潤濕性良好,形成連續皮膜。
△:對於基材,潤濕性不良,或不形成連續皮膜。
×:對於基材,潤濕性不良,且不形成連續皮膜。
將所得之塗佈薄膜設置於學振形染色摩擦堅牢度試驗機(安田精機製作所製),使用經水潤濕的紗布,實施25次摩擦試驗,依照下述基準進行判定。
○:沒有往紗布的色移。
△:看見色移。
×:完全地色移,印刷面掉色。
c.耐濕性
將所得之塗佈薄膜在50℃、濕度90%下靜置1日,依照下述基準進行判定。
○:未看到皮膜之白化。
△:在皮膜到處看到白化。
×:皮膜全體係完全地白化。
d.耐醇性
將所得之塗佈薄膜設置於學振形染色摩擦堅牢度試驗機(安田精機製作所製),使用經調整至30%的乙醇所潤濕的紗布,實施25次摩擦試驗,依照下述基準進行判定。
○:沒有往紗布的色移。
△:看見色移。
×:完全地色移,印刷面掉色。
e.密著性
貼附透明膠帶(NICHIBAN公司製,註冊商標)後剝離,依照下述基準進行判定。
○:無剝離
△:有一部分剝離
×:完全剝離
II.作為墨水的性能評價
對於氯乙烯系樹脂乳液100份,添加10份的碳黑之MA100(三菱化學),添加1份的調平劑之Olfine E1010(日信化學工業公司製)後,填充於200mL的塑膠瓶,添加10g的分散促進目的之氧化鋯珠(φ5mm),以塗料搖晃機(淺田鐵工(股)製)分散2小時後,用棒塗機No.36塗佈,進行105℃×360秒乾燥後的塗膜之評價。
f.分散性(隨著時間經過的安定性)
依照下述基準,判斷是否看到所得之墨水的分散後的5日後之黏度的急激上升、墨水的凝膠化及沈降物。
○:亦看不到急激的黏度上升,看不到沈降物及凝膠化。
△:看到急激的黏度上升。
×:看到沈降物及墨水的凝膠化。
g.分散性(粒子均勻性)
以照明等透過所得之塗佈品,以目視及用下述基準判斷因分散不足所致的2次粒子所造成的塗膜不均勻性。
○:無漏光或色斑。
△:看到一部分或部分的漏光或色斑。
×:看到全體漏光或色斑。
h.光澤
以光澤計PG-1M(日本電色工業公司製)測定所得之塗佈品,讀取60℃之值,依照下述基準進行判定。
○:光澤度為30°以上
△:光澤度為20°以上~未達30°
×:光澤度未達20°
i:明度
對於所得之塗佈品,以簡易型分光色差計NF333(日本電色工業公司製)測定明度(△L),依照下述基準進行判定(由於黑色,明度值愈低為愈良好之結果)。
○:明度(△L)未達15
△:明度(△L)為15以上~未達18
×:明度(△L)為18以下
III.作為壁紙的性能評價
於氯乙烯系之壁紙原材上,以棒塗機No.36塗佈氯乙烯系樹脂乳液,進行105℃×360秒乾燥後的塗膜之評價。
j:密著性(壁紙)
貼附透明膠帶(NICHIBAN公司製,註冊商標)後剝離,以下述基準進行判定。
○:無剝離
△:有一部分剝離
×:完全剝離
・ETERNACOLL UW-1005E:宇部興產製水系胺基甲酸酯寡聚物、聚碳酸酯系、數量平均分子量10000 Tg=-30℃
・Hydran WLS-213:DIC製水系胺基甲酸酯寡聚物、聚碳酸酯系、數量平均分子量25000 Tg=-30℃
・Hydran WLS-201:DIC製水系胺基甲酸酯寡聚物、聚醚系、數量平均分子量20000
・Adeka Bontighter HUX-210:ADEKA製水系胺基甲酸酯寡聚物、聚醚系、數量平均分子量6000
・Adeka Bontighter HUX-232:ADEKA製水系胺基甲酸酯寡聚物、聚醚系、數量平均分子量2000
・Noigen XL-6190:第一工業製藥(股)製、非離子乳化劑
・Pelex SS-L:花王(股)製、陰離子系乳化劑
Claims (4)
- 一種氯乙烯系樹脂乳液,其係聚合物的樹脂乳液,該聚合物包含(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物與(B)含有氯乙烯單體的單體組成物,其特徵為:相對於上述(B)含有氯乙烯單體的單體組成物100質量份,含有40~500質量份的上述(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物,上述樹脂乳液之平均粒徑為10~1000nm,上述樹脂乳液之黏度(23℃)為1~1800mPa‧s。
- 一種水性墨水,其含有如請求項1之氯乙烯系樹脂乳液。
- 一種記錄用紙,其具有如請求項1之氯乙烯系樹脂乳液的塗膜。
- 一種氯乙烯系樹脂乳液之製造方法,其係藉由在相對於(B)含有氯乙烯單體的單體組成物100質量份,存在40~500質量份之(A)數量平均分子量為5,000~50,000的聚碳酸酯系胺基甲酸酯寡聚物下,使其乳化聚合而得,上述樹脂乳液之平均粒徑為10~1000nm,上述樹脂乳液之黏度(23℃)為1~1800mPa‧s。
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US (1) | US20220127476A1 (zh) |
EP (1) | EP3925992A4 (zh) |
JP (1) | JP7173177B2 (zh) |
KR (1) | KR20210132086A (zh) |
CN (1) | CN113423748B (zh) |
TW (1) | TWI836004B (zh) |
WO (1) | WO2020166660A1 (zh) |
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- 2020-02-13 US US17/430,934 patent/US20220127476A1/en active Pending
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- 2020-02-13 JP JP2020572308A patent/JP7173177B2/ja active Active
- 2020-02-13 TW TW109104532A patent/TWI836004B/zh active
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WO2020166660A1 (ja) | 2020-08-20 |
EP3925992A4 (en) | 2022-11-09 |
US20220127476A1 (en) | 2022-04-28 |
CN113423748B (zh) | 2024-05-10 |
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KR20210132086A (ko) | 2021-11-03 |
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