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WO2018120018A1 - 一种pvc表/里面印刷热复合水墨涂料 - Google Patents

一种pvc表/里面印刷热复合水墨涂料 Download PDF

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Publication number
WO2018120018A1
WO2018120018A1 PCT/CN2016/113495 CN2016113495W WO2018120018A1 WO 2018120018 A1 WO2018120018 A1 WO 2018120018A1 CN 2016113495 W CN2016113495 W CN 2016113495W WO 2018120018 A1 WO2018120018 A1 WO 2018120018A1
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Prior art keywords
pvc
acrylic resin
water
following components
watch
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PCT/CN2016/113495
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English (en)
French (fr)
Inventor
谈志刚
Original Assignee
鹤山市怡信化工厂有限公司
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Application filed by 鹤山市怡信化工厂有限公司 filed Critical 鹤山市怡信化工厂有限公司
Priority to PCT/CN2016/113495 priority Critical patent/WO2018120018A1/zh
Priority to CN201680027456.4A priority patent/CN107690459A/zh
Publication of WO2018120018A1 publication Critical patent/WO2018120018A1/zh

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the invention relates to an ink paint, in particular to a PVC watch/inside printed thermal composite ink paint.
  • Polyvinyl chloride resin is one of the earliest general-purpose resins with industrialization and large output, and it has an undoubted importance in material engineering.
  • PVC has excellent properties such as flame retardancy, corrosion resistance, insulation and wear resistance. It is an important thermoplastic with low price and wide range of raw materials.
  • PVC has good mechanical properties and transparency, and has a wide range of applications in the fields of medicine, food, and packaging.
  • the traditional home furnishing decorative film uses a PVC film as a substrate and uses a solvent-based ink to print the decorative layer.
  • a PVC film is required to have high transparency, high strength, low temperature resistance, good self-adhesiveness, and a certain oxygen permeability and moisture permeability, it is necessary to add a large amount of Plasticizers, stabilizers, and a certain amount of monomers and decomposition products will remain in the process of producing PVC film. These decomposed chlorinated products will form an unpleasant odor and cause various harms to the human body.
  • Hazardous auxiliaries currently reported are mainly phthalates used as plasticizers and bisphenol A in antioxidants and solvents (benzenes, esters, ketones) in printing inks.
  • VOC Volatile organic gases are recognized as one of the major sources of atmospheric pollution in the world today, and solvent-based inks emit large amounts of low-concentration VOCs. Moreover, due to the characteristics of the material itself, such as the unclear printing plate and the low heat-bonding fastness, the PVC film also limits the development of PVC ink.
  • the object of the present invention is to provide a PVC table/inside printing thermal composite ink coating with clear layers, bright colors and high heat bonding fastness.
  • a PVC watch/inside printed thermal composite ink paint which is composed of the following components and contents by weight percentage:
  • the acrylic resin is calculated by weight percent and is made up of the following components:
  • the pigment is titanium dioxide and/or carbon black.
  • the PVC surface/inside printed thermal composite ink coating is composed of the following components and contents:
  • acrylic resin is made of the following components:
  • the invention only needs water as a solvent, is harmless to the environment, has a clear layer on the printing plate, has bright colors, and has high heat bonding fastness.
  • the PVC watch/inside printed thermal composite ink paint of the present invention is calculated by weight percentage, and is composed of the following components and contents:
  • the acrylic resin is calculated by weight percent and is made up of the following components:
  • acrylic acid functions to increase water solubility
  • methyl methacrylate functions to provide a group to increase hardness
  • butyl acrylate can increase flexibility and water solubility
  • isooctyl acrylate The effect is to increase adhesion
  • benzoyl peroxide (TBPB) acts to initiate monomer reaction as an initiator
  • water acts as a solvent.
  • TBPB benzoyl peroxide
  • the role of ethanol is to increase the compatibility of the components in water.
  • the acrylic resin is prepared by polymerization of acrylic acid, methyl methacrylate, butyl acrylate and isooctyl acrylate.
  • the benzoyl peroxide is used as an initiator, ethanol is used as a solvent, and water is used as a solvent. .
  • the acrylic resin has the advantages of good weather resistance, adhesion, light resistance and film-forming property, and can effectively solve the problem that the heat-bonding fastness of the ordinary water-based ink on the PVC substrate is not high and the combination with other components can effectively solve the problem.
  • the version is not clear.
  • the average molecular weight of the acrylic resin is moderate, and between 10,000 and 20,000, the printed plate can be made clear and non-sticky; the acrylic resin has good thermoplasticity, and the heat bonding fastness of the printing can be high.
  • titanium dioxide and/or carbon black can be selected for the pigment, and black and white printing can be performed.
  • pigments can also be selected from other colors, such as lily fast, light fast yellow, phthalocyanine, and the like.
  • a polydimethylsiloxane type leveling agent can be selected, which can increase the gloss and make the printing leveling better.
  • a stearic acid monoglyceride type dispersing agent can be selected which makes the acrylic resin dispersion more uniform and makes the printing uniformity better.
  • the wetting agent may, for example, be selected as a wetting agent for the acetylene glycol gemini surfactant, which acts to better adhere the aqueous ink coating to the PVC film or substrate.
  • Water acts as a dissolving carrier, and it emits almost no VOC to the atmosphere, either during its production or when it is used for printing. This is unmatched by solvent-based inks.
  • the preparation method of the PVC surface/inside printing thermal composite ink coating of the invention is as follows:
  • the PVC watch/inside printed thermal composite ink paint of the present embodiment is composed of the following components and contents by weight percentage:
  • Acrylic resins are made from the following components:
  • the preparation method refers to the steps S1 and S2 of the previous preparation method, and details are not described herein again.
  • the PVC watch/inside printed thermal composite ink paint of the present embodiment is composed of the following components and contents by weight percentage:
  • the PVC watch/inside printed thermal composite ink paint of the present embodiment is composed of the following components and contents by weight percentage:
  • Example 1 The PVC watch/inside printed thermal composite ink paint prepared in Example 1 - Example 3 was subjected to performance test.
  • test result is: All users are rated as A.
  • the test result is that the PVC watch/inside printed thermal composite ink paint prepared by the invention has better heat bonding fastness.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

一种PVC表/里面印刷热复合水墨涂料，按重量百分比算，由如下组分组成：丙烯酸类树脂50％-70％，颜料8％-25％，流平剂1％-3％，分散剂3％-8％，润湿剂3％-8％，水余量；所述丙烯酸类树脂由如下组分制成：丙烯酸5％-25％，甲基丙烯酸甲酯10％-20％，丙烯酸丁酯6％-15％，丙烯酸异辛酯1％-5％，过氧化苯甲酰叔丁酯1％-5％，水10％-30％，乙醇20％-40％。

Description

一种PVC表/里面 印刷 热复合水墨涂料 一种PVC表/里面 印刷 热复合水墨涂料
技术领域
本发明涉及一种水墨涂料，具体涉及一种PVC表/里面印刷热复合水墨涂料。
背景技术
聚氯乙烯树脂(PVC)是最早实现工业化、产量较大的通用树脂之一，在材料工程中占据勿庸置疑的重要地位。PVC具有阻燃、耐腐蚀、绝缘、耐磨损等优良性能，价格低廉、原材料来源广泛是一种重要的热塑性塑料。PVC其具有良好的力学性能和透明性，在医药、食品、包装领域有广泛的应用。普通PVC膜（管）、 PVC台布、PVC户外广告膜、PVC封圈、PVC器皿、PVC物品的包装等越来愈多的需要PVC表面油墨印刷。
例如，随着人们对装饰家居的需求量越来越大，对环保材料亦越来越重视。传统的家居行业装饰膜以PVC膜为基材，采用溶剂型油墨来印刷饰层。而为了提高PVC膜作为印刷基材及贴合面膜的性能，如要求PVC膜透明度高、强度大、耐受低高温、自粘性好、具有一定的透氧和透湿能力等，需要添加大量的增塑剂、稳定剂，同时在生产PVC膜过程中会残留一定量的单体和分解产物，这些分解的氯化产物释放出来后会形成难闻的气味，并对人体造成多种危害。目前报道的有危害的助剂主要是用作增塑剂的邻苯二甲酸酯类和抗氧化剂双酚A及印刷油墨中的溶剂（苯，酯，酮）等。
VOC( 挥发性有机气体)被公认为当今全球大气污染的主要污染源之一，溶剂型油墨会散发出大量的低浓度VOC。且由于PVC膜因其材料本身具有的特性，如印刷上版不清晰和热贴合牢度不高等，也限制了PVC水墨的发展。
发明内容
为解决上述技术问题，本发明的目的在于提出一种上版层次清晰，颜色鲜艳，热贴合牢度高的PVC表/里面印刷热复合水墨涂料。
所采用的技术方案为：
一种PVC表/里面印刷热复合水墨涂料，按重量百分比算，其由如下组分和含量组成：
丙烯酸类树脂 50%-70%；
颜料 8%-25%；
流平剂 1%-3%；
分散剂 3%-8%；
润湿剂 3%-8%；
水 余量；
所述丙烯酸类树脂按重量百分比算，其由如下组分制成：
丙烯酸 5%-25%；
甲基丙烯酸甲酯 10%-20%；
丙烯酸丁酯 6%-15%；
丙烯酸异辛酯 1%-5%；
过氧化苯甲酰叔丁酯1%-5%；
水 10%-30%；
乙醇 20%-40% 。
进一步地，所述颜料为钛白粉和/或炭黑。
进一步地，PVC表/里面印刷热复合水墨涂料由如下组分和含量组成：
丙烯酸类树脂 60%；
颜料 8%-25%；
流平剂 2%；
分散剂 5%；
润湿剂 5%；
水 余量。
进一步地，所述丙烯酸类树脂由如下组分制成：
丙烯酸 20%；
甲基丙烯酸甲酯 15%；
丙烯酸丁酯 10%；
丙烯酸异辛酯 2%；
过氧化苯甲酰叔丁酯3%；
水 20%；
乙醇 30% 。
本发明的有益效果在于：
本发明只需要用水作为溶剂，对环境无害，印刷上版层次清晰，颜色鲜艳，热贴合牢度高。
具体实施方式
下面对本发明进行清楚、完整地描述，使本发明的目的、技术方案及效果更加清楚、明确。应当理解，具体实施方式用以解释本发明，并不用于将保护范围限定于此。
本发明的PVC表/里面印刷热复合水墨涂料，按重量百分比算，其由如下组分和含量组成：
丙烯酸类树脂 50%-70%；
颜料 8%-25%；
流平剂 1%-3%；
分散剂 3%-8%；
润湿剂 3%-8%；
水 余量。
在PVC表/里面印刷热复合水墨涂料的组分中，丙烯酸类树脂按重量百分比算，由如下组分制成：
丙烯酸 5%-25%；
甲基丙烯酸甲酯 10%-20%；
丙烯酸丁酯 6%-15%；
丙烯酸异辛酯 1%-5%；
过氧化苯甲酰叔丁酯1%-5%；
水 10%-30%；
乙醇 20%-40% 。
丙烯酸类树脂的组分中，丙烯酸的作用在于可以增加水溶性，甲基丙烯酸甲酯的作用在于可以提供基团增加硬度，丙烯酸丁酯的作用可以增加柔韧性和水溶性；丙烯酸异辛酯的作用在于可以增加附着力，过氧化苯甲酰叔丁酯（TBPB）的作用在于作为引发剂引发单体反应；水的作用在于作为溶剂。乙醇的作用在于增加组分之间在水中的相溶。
本丙烯酸类树脂由丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸异辛酯经聚合反应而制成，以过氧化苯甲酰叔丁酯为引发剂，乙醇为助溶剂，以水为溶剂。
本丙烯酸类树脂由于具有良好的耐候性、粘接性、耐光性以及成膜性能等优点，与其他组分配合能有效地解决普通水性油墨在PVC基材上热贴合牢度不高和上版不清晰的问题。本丙烯酸类树脂的平均分子量适中，在10000-20000之间，可以使印刷上版清晰不黏糊；本丙烯酸类树脂的热塑性较好，可以使印刷的热贴合牢度高。
颜料例如可以选择钛白粉和/或炭黑，可以进行黑白印刷。当然颜料也可以选择其他颜色，例如百合化工的耐晒红、耐晒黄、酞青兰等等。
流平剂例如可以选择聚二甲基硅氧烷类流平剂，其可以增加光泽度，使印刷流平性更好。
分散剂例如可以选择硬脂酸单甘油酯类分散剂，其使丙烯酸类树脂分散更均匀，使印刷均匀度更好。
润湿剂例如可以选择润湿流平剂为炔二醇双子基表面活性剂，其作用在于使本水性油墨涂料更好附着在PVC膜或基材上。
水作溶解载体，无论是在其生产过程中，还是被用于印刷时，几乎不会向大气散发VOC。这是溶剂型油墨所无法比拟的。
本发明的PVC表/里面印刷热复合水墨涂料的制备方法如下：
S1. 制备丙烯酸类树脂：
在反应釜中加入水、乙醇后，加入丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸异辛酯，通氮气保护，使用蒸汽将反应釜内升温至90℃，加入引发剂过氧化苯甲酰叔丁酯，引发聚合反应，控制反应温度90-110℃，反应3-5小时后，再控制10小时保温缓慢反应，即得丙烯酸类树脂。
S2. 将称量备好的丙烯酸类树脂、颜料、流平剂、分散剂与润湿剂加入水中搅拌均匀。
下面通过实施例进一步说明。
实施例1
本实施例的PVC表/里面印刷热复合水墨涂料，按重量百分比算，由如下组分和含量组成：
丙烯酸类树脂 60%；
颜料 10%；
流平剂 2%；
分散剂 5%；
润湿剂 5%；
水 余量。
丙烯酸类树脂由如下组分制成：
丙烯酸 20%；
甲基丙烯酸甲酯 15%；
丙烯酸丁酯 10%；
丙烯酸异辛酯 2%；
过氧化苯甲酰叔丁酯3%；
水 20%；
乙醇 30% 。
制备方法参照前面制备方法的S1和S2步骤，此处不再赘述。
实施例2
参照实施例1，与实施例1不同的是，本实施例的PVC表/里面印刷热复合水墨涂料，按重量百分比算，由如下组分和含量组成：
丙烯酸类树脂 50%；
颜料 15%；
流平剂 3%；
分散剂 6%；
润湿剂 6%；
水 余量。
实施例3
参照实施例1，与实施例1不同的是，本实施例的PVC表/里面印刷热复合水墨涂料，按重量百分比算，由如下组分和含量组成：
丙烯酸类树脂 70%；
颜料 10%；
流平剂 2%；
分散剂 3%；
润湿剂 3%；
水 余量。
将实施例1-实施例3制得的PVC表/里面印刷热复合水墨涂料，进行性能测试。
用PVC表/里面印刷热复合水墨涂料在PVC户外广告膜上印刷，使用凹印轮转印刷，然后随机选择30个用户，评价上版是否清晰，如果清晰则评为A，如果稍微模糊则评为B，如果非常不清晰则评为C。
测试结果为：所有的用户都评价为A。
热贴合牢度与附着力呈正相关关系。按GB/T13217.7-2009《液体油墨附着牢度检验方法》对上述实施例1-3制得的PVC表/里面印刷热复合水墨涂料进行水性油墨附着力性能测试，其测试结果如下表1：
表1
测试样品 油墨附着牢度(％)
实施例1 99.5
实施例2 99.3
实施例3 99.2
测试结果为，本发明制备出的PVC表/里面印刷热复合水墨涂料具有较好的热贴合牢度。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施例的具体说明，它们并非用以限制本发明的保护范围，凡未脱离本发明技艺精神所作的等效实施例或变更均应包含在本发明的保护范围之内。

Claims (4)

  1. 一种PVC表/里面印刷热复合水墨涂料，其特征在于，按重量百分比算，其由如下组分和含量组成：
    丙烯酸类树脂 50%-70%；
    颜料 8%-25%；
    流平剂 1%-3%；
    分散剂 3%-8%；
    润湿剂 3%-8%；
    水 余量；
    所述丙烯酸类树脂按重量百分比算，其由如下组分制成：
    丙烯酸 5%-25%；
    甲基丙烯酸甲酯 10%-20%；
    丙烯酸丁酯 6%-15%；
    丙烯酸异辛酯 1%-5%；
    过氧化苯甲酰叔丁酯1%-5%；
    水 10%-30%；
    乙醇 20%-40% 。
  2. 根据权利要求1所述的PVC表/里面印刷热复合水墨涂料，其特征在于，所述颜料为钛白粉和/或炭黑。
  3. 根据权利要求1所述的PVC表/里面印刷热复合水墨涂料，其特征在于，其由如下组分和含量组成：
    丙烯酸类树脂 60%；
    颜料 8%-25%；
    流平剂 2%；
    分散剂 5%；
    润湿剂 5%；
    水 余量。
  4. 根据权利要求1所述的PVC表/里面印刷热复合水墨涂料，其特征在于，所述丙烯酸类树脂由如下组分制成：
    丙烯酸 20%；
    甲基丙烯酸甲酯 15%；
    丙烯酸丁酯 10%；
    丙烯酸异辛酯 2%；
    过氧化苯甲酰叔丁酯3%；
    水 20%；
    乙醇 30% 。
PCT/CN2016/113495 2016-12-30 2016-12-30 一种pvc表/里面印刷热复合水墨涂料 WO2018120018A1 (zh)

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