CN112552540A - 合成纸用水性涂料及使用其的合成纸 - Google Patents
合成纸用水性涂料及使用其的合成纸 Download PDFInfo
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- CN112552540A CN112552540A CN201911174687.XA CN201911174687A CN112552540A CN 112552540 A CN112552540 A CN 112552540A CN 201911174687 A CN201911174687 A CN 201911174687A CN 112552540 A CN112552540 A CN 112552540A
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- Prior art keywords
- synthetic paper
- water
- based paint
- acrylate
- coating
- Prior art date
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003973 paint Substances 0.000 title claims abstract description 30
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- 238000000576 coating method Methods 0.000 claims abstract description 92
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000004005 microsphere Substances 0.000 claims abstract description 37
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- 229920000126 latex Polymers 0.000 claims abstract description 36
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- 239000000178 monomer Substances 0.000 claims description 30
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- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 16
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- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
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- 238000006243 chemical reaction Methods 0.000 description 24
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 239000002390 adhesive tape Substances 0.000 description 10
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
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- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- 229920000742 Cotton Polymers 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
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- 238000001816 cooling Methods 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
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- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
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- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开一种合成纸用水性涂料及使用其的合成纸,其中合成纸用水性涂料包括26wt%至75wt%的压克力乳液、2wt%至10wt%的中空乳胶微球以及26wt%至70wt%的无机吸墨材料,其中中空乳胶微球的粒径为500纳米至1100纳米,且包括一中空核心、一包覆所述中空核心的缓冲层以及一包覆所述缓冲层的外壳体。借此,合成纸用水性涂料可于合成纸基材上形成一表面涂层,以提高印刷性。
Description
技术领域
本发明涉及一种合成纸用涂料,特别是涉及一种合成纸用水性涂料,以及使用此性涂料的合成纸。
背景技术
传统的印刷基材为木浆制纸,但其防水性差、易刮破,使用受限。因此,日本王子油化公司以聚烯烃合成纸取代木浆制纸,以聚丙烯的双轴延伸薄膜为中间基材层,于其表面贴或涂布含有无机盐微细粉末的聚丙烯单轴延伸薄膜作为纸面层构成合成纸;日本特公昭46-40794号、日本特开昭56-141339号及日本特开昭56-118437号专利案揭露相关的技术内容。这些专利案的合成纸,虽具有防水、抗撕裂等优点,然而在印刷的过程吸墨性不甚理想,原因是塑料表面无法吸附油墨,故无法作为印刷介质。
为提高合成纸的凹版印刷性,日本特开昭50-10624号、特开昭50-161478号等专利案揭露在纸面上涂布剂量在0.005-0.1g/m2范围内的丙烯酸系共聚体或聚乙烯亚胺等的水溶液作为吸墨材;然而在印刷的过程中,油墨干燥速度不甚理想,故未能广泛作为适用于书写用、印刷用文化用纸。
南亚塑胶公司第I487822号专利案揭露于聚丙烯合成纸的双轴延伸工艺中,利用碳酸钙填充剂的不规则构造,使其拉伸出具微细孔隙的合成纸基材,再用凹版涂布轮对涂布素材膜片施以涂布厚度10微米以下的纸面层涂料,其包括压克力树脂8-20重量%、碳酸钙20-60重量%、白土0.1-5重量%、二氧化钛0.1-2重量%、水30-90重量%及抗静电剂0-2重量%,所制得的合成纸,其纸面微细空孔量及空孔串联程度与天然纸类产品极为接近。惟此合成纸纸面易吸水导致涂层澎润,对贴后容易互相沾黏、不易撕开,容易造成印刷面被破坏。涂层澎润的主因为水性压克力树脂具有亲水基团,其功能为稳定压克力树脂分散于水中,然而亲水基却导致降低树脂耐水性,造成合成纸面耐水性差,且经酒精擦拭易掉粉。
第CN102848768A号专利案中提到,在表面处理剂中添加氮丙啶交联剂,以提高涂层的完整性,使合成纸于印刷时不起粉,印刷的牢固度更好。惟此合成纸印刷后的色彩饱和度较差,原因为压克力树脂吸墨性差且不易渗透。
此外,现有技术的溶剂型涂料,因为在制造及加工过程中会排放大量的溶剂到大气中,不但造成了环境的严重污染,更导致温室效应的问题。
发明内容
本发明所要解决的技术问题在于,针对现有技术的不足提供一种合成纸用水性涂料,其能减少挥发性有机化合物(VOC)的排放,且所形成的表面涂层能提高油墨的印刷性和显色性;并且,提供一种使用此性涂料的合成纸。
为了解决上述的技术问题,本发明所采用的其中一技术方案是:一种合成纸用水性涂料,用以形成一表面涂层,所述合成纸用水性涂料包括26wt%至75wt%的压克力乳液、2wt%至10wt%的中空乳胶微球以及26wt%至70wt%的无机吸墨材料。所述中空乳胶微球的粒径为500纳米至1100纳米,且包括一中空核心、一包覆所述中空核心的缓冲层以及一包覆所述缓冲层的外壳体。
在本发明的一实施例中,所述压克力乳液包含至少一种自架桥单体,其选自丙烯酸酯类聚合物、含烷基的疏水性(甲基)丙烯酸酯、含苯乙烯基的疏水性单体、含羧基的(甲基)丙烯酸酯、双丙酮丙烯酰胺以及已二酰肼。
在本发明的一实施例中,所述压克力乳液包含以下自架桥单体:
45wt%至75wt%的丙烯酸酯类聚合物;
0.1wt%至10wt%的含烷基的疏水性(甲基)丙烯酸酯;
10wt%至45wt%的含苯乙烯基的疏水性单体;
1wt%至20wt%的含羧基的(甲基)丙烯酸酯;
2wt%至10wt%的双丙酮丙烯酰胺;以及
2wt%至10wt%的已二酰肼。
在本发明的一实施例中,丙烯酸酯类聚合物的玻璃转移温度为12℃至130℃。
在本发明的一实施例中,所述无机吸墨材料以颗粒的形式存在,且具有介于200纳米至1500纳米之间的平均粒径。
在本发明的一实施例中,所述无机吸墨材料选自碳酸钙以及硫酸钡中的至少一种。
在本发明的一实施例中,所述无机吸墨材料包含碳酸钙以及硫酸钡,其重量比例为1:2.5-5。
在本发明的一实施例中,所述表面涂层具有介于0.1至1.5之间的表面粗糙度Ra。
为了解决上述的技术问题,本发明所采用的另外一技术方案是:一种合成纸,其包括一合成纸基材以及一表面涂层。所述表面涂层形成于所述合成纸基材的一表面上,其中所述表面涂层是由一具有前述组成的合成纸用水性涂料所形成;所述合成纸基材的厚度介于8微米至100微米之间,所述表面涂层的厚度介于1微米至10微米之间。
本发明的其中一有益效果在于,本发明的合成纸用水性涂料,其能通过“添加特定量的压克力乳液、中空乳胶微球及无机吸墨材料,其中中空乳胶微球的粒径为500纳米至1100纳米,且包括一中空核心、一包覆中空核心的缓冲层及一包覆缓冲层的外壳体”的技术方案,使印刷的油墨图案达到色彩饱和度高、清晰且不掉色的效果,以及提供合成纸应用所需的特性,例如高白度和亮度、高不透明性、良好的油墨吸收能力和耐水性等。
为使能更进一步了解本发明的特征及技术内容,请参阅以下有关本发明的详细说明与附图,然而所提供的附图仅用于提供参考与说明,并非用来对本发明加以限制。
附图说明
图1为本发明的合成纸的结构示意图。
图2为图1中II部分的局部放大图。
图3为本发明的合成纸用水性涂料中的中空乳胶微球的结构示意图。
图4为本发明的合成纸用水性涂料中的中空乳胶微球的制备方法的流程图。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开有关“合成纸用水性涂料及使用其的合成纸”的实施方式,本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节也可基于不同观点与应用,在不悖离本发明的构思下进行各种修改与变更。另外,本发明的附图仅为简单示意说明,并非依实际尺寸的描绘,事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容,但所公开的内容并非用以限制本发明的保护范围。
应当可以理解的是,虽然本文中可能会使用到“第一”、“第二”、“第三”等术语来描述各种组件或者信号,但这些组件或者信号不应受这些术语的限制。这些术语主要是用以区分一组件与另一组件,或者一信号与另一信号。另外,本文中所使用的术语“或”,应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
合成纸的用途十分广泛,至少包括标签、广告纸等。因此,本发明提供一种合成纸用水性涂料,用以提供合成纸应用所需的特性,例如高白度和亮度、高不透明性、良好的油墨吸收能力和耐水性等。本发明的合成纸用水性涂料采用水性系统,包括26wt%至75wt%的压克力乳液、2wt%至10wt%的中空乳胶微球以及26wt%至70wt%的无机吸墨材料。在一些实施例中,本发明的合成纸用水性涂料含有一定量的水,例如2.5wt%至5wt%,但不限于此。
参阅图1所示,使用时,可将本发明的合成纸用水性涂料涂布于合成纸基材1的一面上,再以适当的温度进行热处理,使水性涂料干燥固化而形成表面涂层2;并且,可根据实际需要对合成纸P进行后加工如双轴拉伸,使合成纸P具有所需的机械特性。在一些实施例中,压克力乳液的含量可为30wt%、35wt%、40wt%、45wt%、50wt%、55wt%、60wt%、65wt%或70wt%;中空乳胶微球的含量可为4wt%、5wt%、6wt%、7wt%、8wt%或9wt%;无机吸墨材料的含量可为30wt%、35wt%、40wt%、45wt%、50wt%、55wt%、60wt%或65wt%。
进一步而言,压克力乳液作为涂料基材,且包含至少一种自架桥单体,其选自低玻璃转移温度(Tg)的丙烯酸酯类聚合物、含烷基的疏水性(甲基)丙烯酸酯、含苯乙烯基的疏水性单体、含羧基的(甲基)丙烯酸酯、双丙酮丙烯酰胺以及含二元或多元羧酸的酰肼。其中,丙烯酸酯类聚合物的玻璃转移温度为12℃至130℃,丙烯酸酯类聚合物可提高表面涂层2与合成纸基材1的密着性;原因在于,聚合物的Tg越低,分子链段越容易迁移至孔洞中,例如在拉伸聚合物产生的微孔洞。低Tg丙烯酸酯类聚合物的具体例包括:丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸异丁酯及丙烯酸异辛酯。
含烷基的疏水性(甲基)丙烯酸酯可防止水气渗入表面涂层2中造成涂层瓦解;含烷基的疏水性(甲基)丙烯酸酯的具体例包:(甲基)丙烯酸甲酯(MMA)、丙烯酸乙酯(EA)、(甲基)丙烯酸丙酯(PA)、丙烯酸正丁酯(BA)、(甲基)丙烯酸异丁酯(IBA)、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯(2-HEA)、(甲基)丙烯酸正辛酯(OA)、(甲基)丙烯酸异辛酯(IOA)、(甲基)丙烯酸壬酯(NA)、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯(LA)、(甲基)丙烯酸十八酯、(甲基)丙烯酸甲氧基乙酯(MOEA)、正丁基-丙烯酸甲酯(n-BMA)、丙烯酸2-乙基己酯(2-EHA)、(甲基)丙烯酸乙氧基甲酯(EOMAA)及双丙酮丙烯酰胺(DAAM)。
含苯乙烯基的疏水性单体可提高表面涂层2的内聚力和疏水性;含苯乙烯基的疏水性单体的具体例包:苯乙烯(SM)、甲基苯乙烯(MSM)及乙烯基甲苯。含羧基的(甲基)丙烯酸酯可提高表面涂层2的黏结力,且可增强分子间作用力,使表面涂层2的机械强度得到提高;含羧基的(甲基)丙烯酸酯的具体例包:丙烯酸(AA)、甲基丙烯酸(MAA)、顺丁烯二酸(MA)、反丁烯二酸(FA)、衣康酸(IA)、丁烯酸(BA)及马来酸酐(MAH)。
双丙酮丙烯酰胺可与二元或多元羧酸的酰肼脱水架桥,而含二元或多元羧酸的酰肼有助于形成高分子网状结构,进而可提高表面涂层2的耐水性和耐酒精性;此外,含二元或多元羧酸的酰肼也有助于降低表面涂层2的沾黏性,以及提高表面涂层2的耐擦伤性。含二元或多元羧酸的具体例包:碳酸二酰肼、草酸二酰肼、丁二酸二酰肼及己二酸二酰肼。
在本实施例中,压克力乳液的组成和配比如下:
45wt%至75wt%的丙烯酸酯类聚合物;
0.1wt%至10wt%的含烷基的疏水性(甲基)丙烯酸酯;
10wt%至45wt%的含苯乙烯基的疏水性单体;
1wt%至20wt%的含羧基的(甲基)丙烯酸酯;
2wt%至10wt%的双丙酮丙烯酰胺;以及
2wt%至10wt%的已二酰肼。
参阅图2并配合图3所示,中空乳胶微球21包括一中空核心211、一包覆中空核心211的多孔结构的缓冲层212及一包覆缓冲层212的外壳体213;中空乳胶微球21的粒径的优选范围为500纳米至1100纳米。值得注意的是,中空乳胶微球21不仅具有优异的吸水速干性能,而且粒子结构完整不易破损;使用时,印刷墨水可藉由毛细管现象流入中空乳胶微球21的中空核心211。因此,在中空乳胶微球21的存在下,表面涂层2的耐水性和印刷性均得以提升,进而在表面涂层2上印刷的油墨图案可以达到色彩饱和度高、清晰且不掉色的效果。
参阅图4所示,在本实施例中,中空乳胶微球21采用以下步骤制成:步骤S100,制备种子乳液,本步骤的目的在于提供中空乳胶微球21的基础,并控制中空乳胶微球21的粒径和中空度。本步骤主要使用丙烯酸系单体、过硫酸盐作为起始剂与阴离子、非离子或反应型乳化剂,并控制在适当的搅拌速度下进行反应一定时间。本步骤的实施细节说明如下:甲基丙烯酸与甲基丙烯酸甲酯按1:2的比例混合,再加入丙烯酸丁酯,丙烯酸丁酯的用量为甲基丙烯酸甲酯重量的6-8倍,然后加入十二烷基硫酸钠作为阴离子乳化剂,乳化剂的用量小于丙烯酸酯系单体重量的0.5%进行反应,形成种子乳液。
步骤S100中,甲基丙烯酸甲酯与丙烯酸丁酯分别可用以下单体中的至少一种来取代:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸乙基己基酯及甲基丙烯酸甲酯。
步骤S102,制备酸性聚合物粒子,本步骤为制备中空乳胶微球21的关键步骤,用以确保粒子结构性和孔洞的完整性。本步骤使用特定的单体组合物与步骤一得到的种子乳液进行乳化聚合反应,所得到的产物中含有酸性聚合物粒子,其以缓冲层212包覆中空核心211,缓冲层212呈海绵状而有利于孔洞的形成。本步骤的实施细节说明如下:本步骤所用的单体组合物包含丙烯酸酯系单体及(甲基),丙烯酸酯系单体的用量为种子乳液总重的1-5倍;乳化聚合反应在乙二醇二甲基丙烯酸酯的存在下进行,乙二醇二甲基丙烯酸酯的用量相对于100重量份的单体组合物为0.2至3重量份;藉由调整单体组合物与种子乳液的用量比,缓冲层212可具有所需的厚度为0.05纳米至0.1纳米。
步骤S104,粒子成型及碱处理步骤,本步骤的目的在于形成疏水性的外壳体213。本步骤使用疏水性的乙烯基单体来包覆酸性聚合物粒子,并使用多官能基丙烯酸交联单体来形成核壳之间的交联结构,以及提高疏水性单体的包覆率。本步骤的实施细节说明如下:取步骤S102得到的产物与苯乙烯单体进行乳化聚合,其重量比例为1:10,再加入氨水进行碱处理,形成聚合物乳液,其含有多个粒径均一且分散性佳的中空乳胶微球21。
于碱处理时,碱分子可进入内部与羧基反应,使胶粒体积不断膨胀,最终形成空心结构的中空乳胶微球21。碱处理温度的优选范围为40℃至90℃,但不限于此;例如,碱处理可在一高于外壳体聚合物的玻璃转移温度的温度下进行,此温度条件可提供能量使碱分子扩散进入内部。
参阅图1并配合图2所示,无机吸墨材料22有助于提高表面涂层2的油墨吸收能力,另外也可提供合成纸P应用所需的特性,例如提高白度和雾度。在本实施例中,无机吸墨材料22以颗粒的形式存在,并且无机吸墨材料的平均粒径为20纳米至1500纳米;优选的无机吸墨材料为粒径介于1.2微米至5微米之间的碳酸钙。碳酸钙颗粒具多孔隙与高表面积等特性,添加于涂料中不仅可提高遮蔽性,还可增加吸墨速度。值得一提的是,本发明的合成纸用水性涂料将中空乳胶微球21、无机吸墨材料22(如碳酸钙颗粒)与压克力乳液配合使用,可直接产生快速吸墨与高色彩饱和度的效果。
本发明的合成纸用水性涂料视需要可包含0.05wt%至0.1wt%的添加剂,其可选自平坦剂、湿润剂、消泡剂、稳定剂、抗菌剂、抗氧化剂、分散剂、消光剂、密着促进剂及增稠剂中的至少一种。
复参阅图1及图2所示,本发明还提供一种合成纸P,其包括一合成纸基材1及一表面涂层2,其中表面涂层2形成于合成纸基材1的一表面上。进一步而言,合成纸P材料可包含聚丙烯(PP)及无机填料,无机填料可选自氧化硅、氧化钛、氧化锆、氧化铝、氢氧化铝、碳酸钙、碳酸镁及硫酸钡中的至少一种;表面涂层2是由一具有前述组成的水性涂料所形成,表面涂层2上因为均匀分布有预定粒径的中空乳胶微球21及无机吸墨材料22,而具有介于0.1至1.5之间的表面粗糙度Ra。
使用时,墨水可沿着无机吸墨材料22(如碳酸钙颗粒)间的孔隙被导引流入中空乳胶微球21的中空核心211内,以提高单点的色彩浓度,进而提高印刷色彩饱和度。为了提高印刷墨水的填充率,使色彩饱和度获得提高,小粒径的中空乳胶微球21可均匀分布大粒径的无机吸墨材料22之间,形成最佳堆积状态。
本发明的合成纸P的制备:
将水与架桥剂均匀混合后,加入水性压克力乳液,再加入中空乳胶微球21与无机吸墨材料22混合均匀,然后使用200目滤网过滤,形成水性涂料。将水性涂料涂布于合成纸基材1的一表面上,涂布厚度为约5微米,再以95度烘箱干燥,所得到的成品再进行涂层密着性、对贴沾黏性、耐酒精性、耐擦等物性测试。
本发明的合成纸P与同类产品相比具有显著的进步,其中表面涂层2的密着性、耐沾黏性、耐溶剂性和耐擦伤性均有较大程度的提高。进一步而言,由于压克力单体中含有甲基丙烯酸甲酯与丙烯酸丁酯,其具有氢键,能增加高分子间作用力,大幅提高表面涂层2的坚牢度,并提高对无机吸墨材料22的黏结力。再者,由于涂料中含有反应型架桥剂,成膜后能形成高分子网状结构,大幅提高表面涂层2的耐水性与耐酒精性,解决泡水沾黏与易擦伤等问题。此外,由于涂料中含有中空乳胶微球21与无机吸墨材料22,能提高油墨吸收能力,而提高印刷质量。
吸墨球乳液(即中空乳胶微球)的制备
首先合成吸墨球乳液,如下步骤:取20克甲基丙烯酸(MAA)、40克甲基丙烯酸甲酯(MMA)、280克丙烯酸丁酯(BA),倒入含60克去离子水、1.5克十二烷基苯磺酸钠的瓶内,并高速搅拌成混合液(I)。将2000克去离子水及60.4克前述的混合液(I)加入反应釜内,搅拌并加热至78℃。另取60克去离子水溶解5克过硫酸铵起始剂,倒入反应釜开始反应。半小时后,将剩余的混合液(I)以1.5小时滴加完成,并持续反应4小时。最后,制得pH=2.3,平均粒径170nm,固体含量13.5%的乳液A。
175克乳液A及1700克去离子水加入反应釜内,搅拌并加热至80℃。另取490克甲基丙烯酸、210克甲基丙烯酸甲酯、7克乙二醇二甲基丙烯酸酯与3100克去离子水,并高速搅拌成混合液(II),并以3小时速度滴加入反应釜,同时另取70克去离子水溶解8.4克过硫酸铵起始剂以3.5小时速度滴加入反应釜,混合液(II)滴加完成后,维持80℃续反应2小时。制得pH=2.3,平均粒径324nm,固体含量12.5%的乳液B。
将1350克乳液B及2200克去离子水加入反应釜内,搅拌并加热至80℃。另取1000克苯乙烯、24克乙二醇二甲基丙烯酸酯及3克十二烷基硫酸钠,并高速搅拌成混合液(III),并以3小时速度滴加入反应釜,同时另取300克去离子水溶解10克过硫酸铵起始剂以3.5小时速度滴加入反应釜,混合液(II)滴加完成后,维持80℃续反应1小时。之后升温至90℃,加入150克9.5%氨水,降温至86℃,恒温2小时候,降至室温,过滤除去凝结物,制得pH=9.5,平均粒径856nm,固体含量24.4%的吸墨球乳液。
水性压克力乳液的制备
制造例1:
将乳化剂SDS0.7克加入装有110克去离子水的反应釜,持续搅拌并升温至摄氏76℃。另取30克去离子水、56克丙烯酸丁酯(BA)、5克甲基丙烯酸甲酯(MMA)、36克苯乙烯(ST)、5克丙烯酸(AA)、5克乳化剂SDS、1克双丙酮丙烯酰胺(DAAM),并高速搅拌成混合液(IV)。取前述混合液(IV)10克加入反应釜,维持76℃搅拌。同时取10克去离子水溶解0.5克偶氮二异丁腈(AIBN)起始剂加入反应釜开始反应。10分钟后,开始滴加剩余的混合液(IV),滴加时间为4小时。滴加结束后,持续反应2小时。反应结束后添加0.5克己二酸二酰肼(ADH),经200目滤网过滤得到水性压克力乳液1。
制造例2:
反应流程与制造例1相同,使用的单体改为:丙烯酸丁酯56克、甲基丙烯酸甲酯5克、苯乙烯36克、甲基丙烯酸(MAA)5克、1.5克双丙酮丙烯酰胺(DAAM)。反应结束后添加0.75克己二酸二酰肼(ADH),经200目滤网过滤得到水性压克力乳液2。
制造例3:
反应流程与制造例1相同,使用的单体改为:丙烯酸丁酯48克、甲基丙烯酸甲酯10克、苯乙烯48克、丙烯酸(AA)1克、2克双丙酮丙烯酰胺(DAAM)。反应结束后添加1克己二酸二酰肼(ADH),经200目滤网过滤得到水性压克力乳液3。
制造例4:
反应流程与制造例1相同,使用的单体改为:丙烯酸丁酯70克、甲基丙烯酸甲酯0.15克、苯乙烯12克、丙烯酸(AA)20克、2.5克双丙酮丙烯酰胺(DAAM)。反应结束后添加1.25克己二酸二酰肼(ADH),经200目滤网过滤得到水性压克力乳液4。
评估方法
密着性测试方法为:以四维胶带贴在涂布面上,再以2公斤滚筒压合,随后由一端快速撕起,观察涂布层是否破损。
耐沾黏性测试方法为:将涂布的合成纸浸泡于纯水12小时,将涂布面对贴后,样品放置摄氏35度循环烘箱干燥。完全干燥后,观察对贴面是否会沾黏。表2中,以○表示不沾黏,╳表示会沾黏。
耐酒精性测试方法为:以棉花棒沾20-95%浓度的酒精擦拭合成纸的涂布面10次,观察涂布层是否有破损或起粉,并记录无破损下最高酒精浓度。
耐溶剂性测试方法为:以棉花棒沾丙酮或去渍油擦拭合成纸的涂布面10次,观察涂布层是否有破损或起粉,并记录是否破损。
耐刮性(耐擦伤性)测试方法为:将涂布的合成纸浸泡于纯水1小时,再以500克砝码重压的砂纸擦拭涂布面,反复10次,观察涂布层是否有破损或起粉。
印刷色浓度的评估方法为:以符合印刷色浓度量测标准DIN 16536的色浓度计TECHKON R410e量测印刷色浓度,浓度愈高,印刷性愈佳。
实施例1:
如表2所示,将4克吸墨球乳液、40克水性压克力乳液1与70克碳酸钙混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料1。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果不沾黏。
实施例2:
如表2所示,将4克吸墨球乳液、40克水性压克力乳液2与70克碳酸钙混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料2。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果不沾黏。
实施例3:
如表2所示,将5克吸墨球乳液、40克水性压克力乳液1与70克碳酸钙混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料3。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果不沾黏。
实施例4:
如表2所示,将2克吸墨球乳液、70克水性压克力乳液3与26克碳酸钙混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料4。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果不沾黏。
比较例1:
如表2所示,将40克水性压克力乳液1与70克碳酸钙及14克压克力中空球混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料5,并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果有沾黏。
比较例2:
如表2所示,将40克水性压克力乳液2与70克碳酸钙及14克压克力中空球混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料6。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果有沾黏。
比较例3:
如表2所示,将40克水性压克力乳液1与70克碳酸钙及14克压克力中空球混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料7。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果会沾黏。
比较例4:
如表2所示,将40克水性压克力乳液1与70克碳酸钙及14克压克力中空球混合,搅拌均匀后,经200目滤网过滤得到PP纸涂料8。并以涂布棒涂布于PP合成纸上,摄氏95度下烘烤15秒,其干燥后厚度为5微米,以四维胶带测试涂层密着度,结果不脱落。将样品泡水,以500克下压砂纸测试耐刮性,结果不起粉。再将样品对贴后干燥,测试沾黏性,结果会沾黏。
结论:
1.本发明的水性压克力因具有羧酸官能基,增加吸墨材的黏结力,并加强分子间作用力,大幅提升涂层坚牢度。
2.另实施例1及2在涂料,成膜后形成高分子网状结构,大幅提高涂层的耐水性与耐酒精性,解决对贴沾黏与涂层易擦伤等问题,但含三个碳二亚胺官能基及含有三个异氰酸酯官能基的架桥剂则对沾黏性无明显改善。
3.本发明选用碳酸钙、吸墨球乳液及压克力乳液为涂料,再以大小粒径的最佳排列组合,印刷后可提高印刷色浓度(高色彩饱和度)的合成纸涂料,且具印刷干燥性佳与色彩坚牢度好。
4.与同类产品相比,本发明同时具有显著耐水性与优良印刷性。涂层的密着性、耐擦伤性、耐沾黏性、更有大程度的提高。
表1压克力乳液的组成和特性
表1中,BA表示丙烯酸丁酯;MMA表示甲基丙烯酸甲酯;ST表示苯乙烯;AA表示丙烯酸;MAA表示甲基丙烯酸;DAAM表示双丙酮丙烯酰胺;ADH表示己二酸二酰肼。
表2水性涂料及其物性
实施例的有益效果
本发明的其中一有益效果在于,本发明的合成纸用水性涂料,其能通过“添加特定量的压克力乳液、中空乳胶微球及无机吸墨材料,其中中空乳胶微球的粒径为500纳米至1100纳米,且包括一中空核心、一包覆中空核心的缓冲层及一包覆缓冲层的外壳体”的技术方案,使印刷的油墨图案达到色彩饱和度高、清晰且不掉色的效果,以及提供合成纸应用所需的特性,例如高白度和亮度、高不透明性、良好的油墨吸收能力和耐水性等。
更进一步地说,采用本发明的合成纸用水性涂料,可有效减少挥发性有机化合物(VOC)的排放。
更进一步地说,压克力乳液所含单体具有自架桥的能力,不但不需要使用额外的架桥剂,而且还可以改善表面涂层的性能,例如提高表面涂层的密着性、内聚力、疏水性、耐水性和耐酒精性,以及降低表面涂层的沾黏性。
更进一步地说,本发明采用特殊的三步骤乳液聚合法制成含中空乳胶微球的产品乳液,其稳定性高且起泡性低,而有利于快速涂布。
以上所公开的内容仅为本发明的优选可行实施例,并非因此局限本发明的申请专利范围,所以凡是运用本发明说明书及附图内容所做的等效技术变化,均包含于本发明的申请专利范围内。
Claims (10)
1.一种合成纸用水性涂料,用以形成一表面涂层,其特征在于,所述合成纸用水性涂料包括:
26wt%至75wt%的压克力乳液;
2wt%至10wt%的中空乳胶微球,其中所述中空乳胶微球的粒径为500纳米至1100纳米,且包括一中空核心、一包覆所述中空核心的缓冲层以及一包覆所述缓冲层的外壳体;以及
26wt%至70wt%的无机吸墨材料。
2.根据权利要求1所述的合成纸用水性涂料,其特征在于,所述压克力乳液包含至少一种自架桥单体,其选自丙烯酸酯类聚合物、含烷基的疏水性(甲基)丙烯酸酯、含苯乙烯基的疏水性单体、含羧基的(甲基)丙烯酸酯、双丙酮丙烯酰胺以及已二酰肼。
3.根据权利要求2所述的合成纸用水性涂料,其特征在于,丙烯酸酯类聚合物的玻璃转移温度为12℃至130℃。
4.根据权利要求1所述的合成纸用水性涂料,其特征在于,所述压克力乳液包含以下自架桥单体:
45wt%至75wt%的丙烯酸酯类聚合物;
0.1wt%至10wt%的含烷基的疏水性(甲基)丙烯酸酯;
10wt%至45wt%的含苯乙烯基的疏水性单体;
1wt%至20wt%的含羧基的(甲基)丙烯酸酯;
2wt%至10wt%的双丙酮丙烯酰胺;以及
2wt%至10wt%的已二酰肼。
5.根据权利要求2所述的合成纸用水性涂料,其特征在于,丙烯酸酯类聚合物的玻璃转移温度为12℃至130℃。
6.根据权利要求1所述的合成纸用水性涂料,其特征在于,所述无机吸墨材料以颗粒的形式存在,且具有介于200纳米至1500纳米之间的平均粒径。
7.根据权利要求6所述的合成纸用水性涂料,其特征在于,所述无机吸墨材料选自碳酸钙以及硫酸钡中的至少一种。
8.根据权利要求7所述的合成纸用水性涂料,其特征在于,所述无机吸墨材料包含碳酸钙以及硫酸钡,其重量比例为1:2.5-5。
9.根据权利要求1所述的合成纸用水性涂料,其特征在于,所述表面涂层具有介于0.1至1.5之间的表面粗糙度Ra。
10.一种合成纸,其特征在于,所述合成纸包括:
一合成纸基材;以及
一表面涂层,其形成于所述合成纸基材的一表面上,其中所述表面涂层是由根据权利要求1所述的合成纸用水性涂料所形成;
其中,所述合成纸基材的厚度介于8微米至100微米之间,所述表面涂层的厚度介于1微米至10微米之间。
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