WO2023024605A1 - 一种新型印刷材料及其制备方法 - Google Patents

一种新型印刷材料及其制备方法 Download PDF

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WO2023024605A1
WO2023024605A1 PCT/CN2022/094046 CN2022094046W WO2023024605A1 WO 2023024605 A1 WO2023024605 A1 WO 2023024605A1 CN 2022094046 W CN2022094046 W CN 2022094046W WO 2023024605 A1 WO2023024605 A1 WO 2023024605A1
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layer
solvent
printing material
free
upper layer
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PCT/CN2022/094046
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English (en)
French (fr)
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符晔
雷鹏飞
虞一浩
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浙江凯瑞博科技有限公司
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Publication of WO2023024605A1 publication Critical patent/WO2023024605A1/zh

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    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02—Forms or constructions

Definitions

  • the invention belongs to the field of printing materials, and in particular relates to a printing material and a preparation method thereof.
  • the printing material is, for example, a label material.
  • Coated cloth is mainly divided into two categories: dry coating and wet coating.
  • the wet coating mainly uses methanol as the solvent
  • the dry coating mainly uses N,N-2-methylformamide, ethyl acetate, butyl Organic solvents such as ketone and toluene are the main ones, all of which have great harm to the environment.
  • water-based resins such as water-based acrylic acid, water-based polyurethane and their modified resins are gradually used in the industry
  • the products obtained by wet coating with methanol as a solvent have a large number of penetrating and non-penetrating micropores on the surface. Structure, and high elasticity, so it is difficult to be completely replaced by water-based resin.
  • solvent-free polyurethane has occupied an important position in the material industry due to its characteristics of no solvent pollution and excellent comprehensive performance, and is widely used in synthetic leather, clothing, building materials and other fields. And because it can use water as a foaming agent at a certain temperature to form a large number of microporous structures, provide a certain elasticity of the material, and make the product have a soft feel, it has been widely used in the synthetic leather industry.
  • solvent-free polyurethane is mainly used to replace the "BASE layer" of the original oily polyurethane with DMF as the solvent, and to play the role of bonding the surface layer and the base fabric layer.
  • the base material is mostly polyester cotton cloth and all polyester flannelette , Microfiber cloth, etc., the basic thickness is between 200-1500 ⁇ m.
  • the base cloth mostly uses 60-160 ⁇ m polyester cloth, non-woven fabric, etc. as the base material, which is coated on the base material and finally used as a printing material.
  • solvent-free is still blank in the label printing industry as a printing medium.
  • the purpose of the present invention is to provide a technical solution for applying solvent-free polyurethane in the trademark cloth industry, which can replace the existing wet coating technology, solvent-based dry coating, and make up for the hard hand feeling of the existing water-based dry coating. Can't meet the deficiency of various printing methods. To achieve the above object, the present invention adopts the following technical solutions:
  • a new type of printing material characterized in that it includes an upper layer and a second layer; the upper layer is a solvent-free layer, the thickness of the upper layer is a solvent-free layer between 20 and 150 ⁇ m, and the solvent-free layer is pre-prepared by multiple OH groups.
  • Polymers and multi-NCO-based prepolymers are catalyzed to form an upper layer, or the upper layer is formed by the catalytic reaction of multi-NH 2 -based prepolymers and multi-NCO-based prepolymers, directly covering the surface of the second layer.
  • the upper layer does not contain any volatile components.
  • the thickness of the upper layer is controlled at 20 ⁇ m ⁇ 150 ⁇ m.
  • the thickness of the upper layer is controlled within 30 ⁇ m-100 ⁇ m.
  • the solvent-free layer does not contain any volatile components, and 100% of the components for preparing the solvent-free layer are converted into solids.
  • the volatile organic components refer to solvents that will not be released into the air due to temperature, ventilation and other conditions during processing, such as methanol, N, N-2-methylformamide, xylene, butylated Organic solvents such as ketones and toluene are within the undetectable range of GPC-MS and other detection instruments, that is, the limit value is ⁇ 5ppm.
  • the upper layer is a non-foaming or low-foaming solvent-free layer after coating and drying.
  • the non-foamed or insufficiently foamed layer refers to a pore size ⁇ 100 ⁇ m.
  • the solvent-free layer contains one or more additives among pigments, porogens, fillers, flame retardants, brighteners, antistatic agents, and anti-yellowing additives.
  • the addition ratio of the additive is between 0.1% and 5% of the multi-OH group prepolymer or multi-NH 2 group prepolymer.
  • the filler includes one or more of calcium carbonate, kaolin, talc, dolomite, white carbon black, aluminum hydroxide, diatomaceous earth, and wood flour.
  • the mass ratio of multi-OH group prepolymer A to multi-NCO group prepolymer B is: 30-70:70-30;
  • the catalyst accounts for 0.0001-0.001% of the total amount of A and B.
  • the mass ratio of many NH2- based prepolymers A to many NCO-based prepolymers B is: 30-70:70-30;
  • the percentage of the catalyst in the total amount of A and B is 0.0001 ⁇ 0.001%
  • the catalyst may be one of amine catalysts, tin catalysts, zinc catalysts, and lead catalysts.
  • the catalyst is preferably an amine catalyst.
  • the upper layer can meet one or more methods of flexographic printing, thermal transfer printing, inkjet printing, and offset printing.
  • the second layer is plain weave or non-woven fabric woven by one or more of nylon, polyester, spandex and viscose.
  • the second layer is manufactured by one or more processes of air-jet weaving, water-jet weaving, spunlace, spunbond, and meltblown.
  • the thickness of the second layer is generally controlled between 60-160 ⁇ m.
  • the second layer is a base material obtained by performing a pretreatment process after various manufacturing processes.
  • the pretreatment process of the second layer includes the base material obtained through desizing, washing, shaping, dyeing, padding, calendering, surface coating and other processes.
  • the lower surface of the second layer is covered with a third layer
  • the third layer is a mixture of one or more of water-based polymers, hot melt adhesives, and pressure-sensitive adhesives.
  • the third layer is a solvent-free coating
  • the upper layer and the third layer are the same or different solvent-free layers
  • the upper layer and the third layer are both printable layers
  • the upper layer and the third layer are respectively covered on the upper layer of the second layer and lower level.
  • the new printing material complies with Oeko-Tex Standard 100 Class I testing standards and limit requirements.
  • the Oeko-Tex Standard 100 Class I test standard and limit requirements are no peculiar smell, pH value between 4.0 and 7.5, formaldehyde content ⁇ 16mg/kg, color fastness to washing ⁇ 3 grades, color fastness to dry rubbing and staining degree ⁇ 4 grades.
  • novel printing material of the present invention can be made into a continuous strip-shaped printing label material; Section by section label.
  • the solvent-free or solvent-free components mentioned in the present invention refer to organic solvent-free or organic solvent-free components, which are detected by GPC-MS and other detection instruments, and are in the undetected range, that is, the limit value is ⁇ 5ppm.
  • the present invention also discloses a preparation method of the above-mentioned printing material, and the preparation steps include the following:
  • the mass ratio of multi-OH group prepolymer A to multi-NCO group prepolymer B is 30-70:70-30, and the amine catalyst is a combination of A component and B component 0.0001 ⁇ 0.001% of mass sum;
  • the mass ratio of multi -NH2 -based prepolymer A to multi-NCO-based prepolymer B is 30-70:70-30, and the catalyst is 0.0001% to 0.001% of the mass sum of A component and B component;
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to the multi-OH-based prepolymer A, catalyst and additives, and the multi-NCO-based prepolymer B is dispersed in the second stirred tank. In the kettle, keep the temperature at 20-50°C;
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to many NH2 -based prepolymers A, catalysts and additives, and many NCO-based prepolymers B are dispersed in the second stirred tank , keep the temperature at 20 ⁇ 50°C;
  • step (3) (4) Cutting the semi-finished product obtained in step (3) to obtain a solvent-free printing material.
  • the mass ratio of multi -NH2 -based prepolymer A to multi-NCO-based prepolymer B is 30-70:70-30, and the catalyst is 0.0001% to 0.001% of the mass sum of A and B ;
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to the multi-OH group prepolymer A, catalyst and aluminum hydroxide, and the multi-NCO-based prepolymer B is in the second In the stirred tank, keep the temperature at 20-50°C;
  • step (1) the raw materials in step (1) are dispersed in the first stirred tank according to many NH base prepolymers A, catalyzer and aluminum hydroxide, and many NCO base prepolymers B are stirred in the second In the kettle, keep the temperature at 20-50°C;
  • the preparation method of the present invention has simple process, convenient operation and high degree of automation.
  • the entire solvent-free coating is paved and solidified on the entire substrate surface to form a film by scraping or transfer coating, and there is no volatile group in the production process. Discharge, 100% conversion of raw materials into solids;
  • the label material of the present invention has the ability to meet various printing requirements, and meet the pH value in the range of 4.0 to 7.5, Oeko-Tex Standard 100 Class I testing standards and limit requirements.
  • the printing material of the present invention is convenient and quick to use, has strong extensibility, and can be used as hot-melt adhesive label material, pressure-sensitive adhesive label material, and water-washable label material.
  • Fig. 1 is a schematic structural diagram of the present invention; the markings in the figure illustrate: 1-upper layer, solvent-free layer, 2-second layer.
  • Fig. 2 is a cross-sectional SEM image of a trademark of jeans bought in the market as a comparative example.
  • FIG. 3 is a cross-sectional SEM image of a sample of a solvent-free printing material obtained after an experiment according to Example 2 of the present invention.
  • FIG. 4 is a cross-sectional SEM image of a sample of a solvent-free printing material obtained after an experiment according to Example 3 of the present invention.
  • Figure 5 is a drawing according to the applicant's internal standard KRB-ZC-202016 "Judging Standards for Thermal Transfer Printing Grades”.
  • Figures 6-8 are the photos of the printing effect of the comparative example, the photo of the printing effect of Example 1, and the photo of the printing effect of Example 2 in sequence.
  • the purpose of the present invention is exactly by simple scrape coating mode or transfer coating mode by the solvent-free layer catalytic reaction coating of many OH group prepolymers and many NCO group prepolymers, or by many NH 2 base prepolymers and many NCO
  • the solvent-free layer catalytic reaction coating based on prepolymer is coated on the surface of the substrate, no volatile components are emitted during the whole production process, and the raw materials are 100% converted, which endows it with excellent printing effect and prepares a new type of printing material .
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to the multi-OH group prepolymer A, catalyst and antistatic agent, and the multi-NCO-based prepolymer B is in the second In the stirred tank, keep the temperature at 43-46°C;
  • step (3) The semi-finished product obtained in step (3) can be further cut to obtain a new type of printing material, which can be used as a label material.
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to the multi-OH group prepolymer A, catalyst and antistatic agent, and the multi-NCO-based prepolymer B is in the second In the stirred tank, keep the temperature at 43-46°C;
  • step (3) Cutting the semi-finished product obtained in step (3) to obtain a new type of printing material, which can be used as a label material.
  • step (4) After the finished product obtained in step (4) is frozen and sectioned in liquid nitrogen, the cross-sectional view observed under an electron microscope is shown in FIG. 3 .
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • step (1) Under normal temperature and pressure, the raw materials in step (1) are dispersed in the first stirred tank according to Duoduo NH 2 base prepolymer A, catalyst, anti-phenol yellowing additive, porogen, and Duoduo NCO Base prepolymer B is kept in the second stirred tank at a temperature of 46-50°C;
  • the comparative example is a brand of jeans bought on the market, which is produced by a polyurethane coating process using DMF as a solvent. After being frozen and sectioned in liquid nitrogen, the SEM image of the cross-section is shown in Figure 2.
  • the test of rubbing fastness refers to GB/T 3920-2008 "Textiles Color Fastness Tests Color Fastness to Rubbing".
  • Stone washing test refer to the standard washing machine of the patent CN 103114472 B "Method of Stone Washing Soft Shaggy Fabric", 90°C water temperature, 0.6g soap flakes, 0.3g anhydrous sodium carbonate, 5-6 volcanic stones, 150ml Distilled water, washed for 150 minutes, and dried naturally.
  • Pretreatment (container: 125mm ⁇ 75mm, standard washing machine) 0.15g penetrant + 5g cloth (2g coated cloth + 3g cotton cloth) + 150ml distilled water, 90°C water temperature, wash for 30min.
  • pH value test 1Weigh 10 grams of sample, cut small pieces of about 1.5cm; 2Measure 250ml of distilled water, put it into a beaker and boil at a medium speed, boil for 10 minutes, put the cut sample, cover the beaker with a dish , and then boiled for 10 minutes; 3 After the completion, cool the beaker to room temperature, take out the water extract and pour it into a clean beaker to measure the pH value.
  • the printing clarity refers to the applicant's internal standard KRB-ZC-202016 "Judging Standards for Thermal Transfer Printing Grades", the model of the thermal transfer printer used for testing is X-3200, and the printing conditions are: density 12 .
  • the barcode is 2.9cm long and 1.2cm wide. Under the D65 light source, the distance of about 45°35cm is used for rating.
  • the criteria for judging are: if the breakpoint effect is the same as that of the grade 5 standard sample and there is no infiltration, then it will be rated as grade 5; If the effect is the same as that of the grade 3 standard sample, but without infiltration, then it is rated as grade 3; , it is rated as level 1.

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Abstract

一种印刷材料及其制备方法，包括上层（1）和第二层（2）；上层（1）是无溶剂层，上层（1）的厚度在20～150μm之间，无溶剂层由多OH基预聚体和多NCO基预聚体催化反应形成；上层（1）直接覆盖于第二层（2）表面。标签材料满足多种印刷需求，且符合pH值在4.0～7.5范围内，满足Oeko-Tex Standard 100第Ⅰ级别检测标准和限量要求，能够做热熔胶标签材料、压敏胶标签材料、水洗标签材料。印刷材料制备方法工艺简单，操作便利，自动化程度高，通过刮涂或转移涂的方式将整个无溶剂涂层铺平整个基材表面固化成膜得到，生产过程中无任何挥发组分排放，原料100％转化为固体。

Description

一种新型印刷材料及其制备方法 技术领域
本发明属于印刷材料领域，具体涉及一种印刷材料及其制备方法，所述印刷材料比如是标签材料。
背景技术
传统的印刷材料行业，以涂层工艺为主的涂层布占据主要地位。涂层布主要分为干法涂布和湿法涂布两大类，湿式涂布主要以甲醇为溶剂，干式涂布主要采用N，N-2-甲基甲酰胺、乙酸乙酯、丁酮、甲苯等有机溶剂为主，都对环境具有重大危害。虽然，目前水性树脂，例如水性丙烯酸、水性聚氨酯及其改性树脂在行业里面逐渐应用，但以甲醇为溶剂的湿法涂层所得到的产品由于表面具有大量的贯穿及未贯穿式的微孔结构，且富有弹性，从而难以被水性树脂所完全替代。
近年来，无溶剂聚氨酯由于其具有无溶剂污染、综合性能优良等特点，在材料工业中占有重要地位，广泛应用于合成革、服装、建材等领域。且由于其可以在一定温度下利用水作为发泡剂，形成大量的微孔结构，提供材料一定的弹性，使产品具有柔软的手感，在合成革行业已经广泛应用。在合成革行业中，无溶剂聚氨酯主要为代替原有以DMF为溶剂的油性聚氨酯的“BASE层”，起到粘合面层和基布层的作用，基材多用涤棉布、全涤纶起绒布、超纤布等，基本厚度在200-1500μm之间。然而，在商标布行业中基布多采用60-160μm的涤纶布、无纺布等作为基材，在基材上进行涂层，最终作为印刷材料使用。然而，无溶剂在标签印刷行业作为印刷的介质仍属于空白。
发明内容
本发明的目的是提供将无溶剂聚氨酯应用在商标布行业的技术方案，能够代替现有的湿法涂布技术、溶剂型干法涂布、并弥补现有水性干法涂布手感偏硬、无法满足 各种印刷方式的不足。为实现上述目的，本发明采用以下技术方案：
一种新型印刷材料，其特征在于包括上层和第二层；所述上层是无溶剂层，所述上层的厚度在20～150μm之间的无溶剂层，所述无溶剂层由多OH基预聚体和多NCO基预聚体催化反应形成；或由多NH 2基预聚体和多NCO基预聚体催化反应形成上层，直接覆盖于第二层表面。
进一步，所述上层无任何挥发组分。
进一步地，所述上层的厚度控制在20μm～150μm。
更进一步地，所述上层的厚度控制在30μm～100μm。
进一步，所述无溶剂层无任何挥发组分，制备无溶剂层的组分100％转化为固体。具体的，所述有机挥发组分指的是在加工过程中因温度、通风等条件下不会散发至空气中的溶剂，如甲醇、N，N-2-甲基甲酰胺、二甲苯、丁酮、甲苯等有机溶剂，在GPC-MS等检测仪器未检出范围内，即极限值≤5ppm。
进一步，所述上层为经过涂布、烘干后为不发泡或低发泡的无溶剂层。具体的，所述不发泡或不充分发泡层指的是孔径≤100μm。
进一步，所述无溶剂层包含颜料、致孔剂、填料、阻燃剂、增白剂、抗静电剂、抗黄变助剂中的一种或多种添加剂。
进一步，所述添加剂，添加比例为占多OH基预聚体或多NH 2基预聚体的0.1～5％之间。
进一步，所述填料包括碳酸钙、高岭土、滑石粉、白云石、白炭黑、氢氧化铝、硅藻土、木质粉中的一种或多种。
更进一步，所述上层，配方主剂为：
多OH基预聚体A与多NCO基预聚体B的质量比为：30-70:70-30；
催化剂占A和B总量的百分比0.0001～0.001％。
或者：
多NH 2基预聚体A与多NCO基预聚体B的质量比为：30-70:70-30；
催化剂占A和B总量的百分比0.0001～0.001％
更进一步，所述催化剂，可以为胺类催化剂、锡类催化剂、锌催化剂、铅催化剂中的一种。
更进一步，所述催化剂，优选胺类催化剂。
更进一步，所述上层，能满足柔版印刷、热转印印刷、喷墨印刷、胶印的一种或多种方式。
进一步，所述第二层为尼龙、涤纶、氨纶、黏胶纤维中的一种或多种织造的平纹布或非织造布。
进一步，所述第二层由喷气织造、喷水织造、水刺法、纺黏法、熔喷法的一种或多种工艺制造。
进一步，所述第二层的厚度一般控制在60-160μm之间。
进一步，所述第二层为经过多种制造工艺后，进行预处理工序产生所得到的基材。
进一步，所述第二层经过的预处理工序包括退浆、水洗、定型、染色、浸轧、轧光、表涂等工序得到的基材。
进一步，所述在于第二层的下表面覆盖第三层，第三层为水性高分子聚合物、热熔胶、压敏胶的一种或多种的混合物。第三层为无溶剂涂层时，上层和第三层为同种或为不同种无溶剂层，上层和第三层均为可印刷层，上层和第三层分别覆盖于第二层的上层和下层。
进一步，所述新型印刷材料，符合Oeko-Tex Standard 100第Ⅰ级别检测标准和限量要求。所述Oeko-Tex Standard 100第Ⅰ级别检测标准和限量要求为无异味，pH值在4.0～7.5之间，甲醛含量≤16mg/kg，耐水洗色牢度≥3级，耐干摩擦沾色牢度≥4级。
本发明的新型印刷材料可以做成连续的带状印刷标签材料；或做成连续的片形印刷标签材料，在制备完成后可以再被裁切为带状，在被印刷后，再裁切为一段一段的 标签。
本发明中所述的无溶剂或无溶剂成分是指无有机溶剂或无有机溶剂成分，采用在GPC-MS等检测仪器检测，处在未检出范围内，即极限值≤5ppm。
为了更好的实现本发明的目的，本发明还公开了上述印刷材料的制备方法，制备步骤包括如下：
方法1：
(1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，胺类催化剂是A组分和B组分的质量和的0.0001～0.001％；
或多NH 2基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A组分和B组分的质量和的0.0001～0.001％；
(2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B分散在第二搅拌釜中，保持温度20～50℃；
在常温常压件下，将步骤(1)中的原料按照多NH 2基预聚体A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B分散在第二搅拌釜中，保持温度20～50℃；
(3)将第一搅拌釜和第二搅拌釜的浆料在涂布装置前端直接混合，投入第二层并在2～5分钟之内通过涂布装置，使混合浆料直接涂布于第二层上表面，经过100～180℃烘烤，收卷得到无溶剂印刷材料。
(4)将步骤(3)中得到的半成品，进行分切，得到一种无溶剂印刷材料。
方法2：
(1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A和B的质量和的0.0001～0.001％；
或按百分比选取上层各原材料比例：多NH 2基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A和B的质量和的0.0001～0.001％；
(2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体A、催化剂及氢氧化铝分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度20～50℃；
或在常温常压件下，将步骤(1)中的原料按照多NH 2基预聚体A、催化剂及氢氧化铝分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度20～50℃；
(3)将第一搅拌釜和第二搅拌釜的浆料通过涂布装置，直接涂布于离型材料上，经过100～160℃烘烤，得带涂层胶离型材D；
(4)通过温度80～100℃压辊将第二层与带涂层胶离型材D进行轧合，经过120～170℃烘干，将离型材D上的涂层胶转移至第二层上面，并将离型材料和带无溶剂胶的第二层进行剥离后单独收卷，制得一种新型印刷材料；
(5)将(4)中得到的半成品，进行分切，得到一种新型印刷材料。
本发明的有益效果主要体现在如下几个方面：
(1)本发明的制备方法工艺简单，操作便利，自动化程度高，通过刮涂或转移涂的方式将整个无溶剂涂层铺平整个基材表面固化成膜得到，生产过程中无任何挥发组分排放，原料100％转化为固体；
(2)本发明的标签材料具有满足多种印刷需求，且符合pH值在4.0～7.5范围内，Oeko-Tex Standard 100第Ⅰ级别检测标准和限量要求。
(3)本发明的印刷材料使用方便快捷，且延伸性强，能够做热熔胶标签材料、压敏胶标签材料、水洗标签材料。
附图说明
以下用构成本申请的一部分的附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1为本发明的结构示意图；图中标记说明：1-上层，无溶剂层，2-第二层。
图2为对比例为市场上买回来的牛仔裤的商标的断面SEM图。
图3为本发明按照实施例2实验后，得到的无溶剂印刷材料样品的断面SEM图。
图4为本发明按照实施例3实验后，得到的无溶剂印刷材料样品的断面SEM图。
图5为按照申请人内部标准KRB-ZC-202016《热转印打印等级评判标准》附图。
图6—8依次为对比例打印效果照片、实施例1打印效果照片、实施例2打印效果照片。
具体实施方式
本发明的目的就是通过简单的刮涂方式或转移涂方式将由多OH基预聚体和多NCO基预聚体的无溶剂层催化反应涂层、或由多NH 2基预聚体和多NCO基预聚体的无溶剂层催化反应涂层涂布至基材表面，整个生产过程中无挥发组分排放，且原料做到100％转化，赋予其优异的印刷效果，制备一种新型印刷材料。
下面结合附图和具体实施例对本发明进行详细说明。显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
以下实施例中，如无特别说明，则表明所采用的均为本领域的常用技术或常规市售原料。
实施例1:
(1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为70:30，催化剂是A组分和B组分的质量和的0.001％，填料占A比例为40％；
(2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体A、催化剂及抗静电剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度43-46℃；
(3)将第一搅拌釜和第二搅拌釜的浆料在涂布装置前端直接混合，投入第二层 并在2～5分钟之内通过涂布装置，使混合浆料直接涂布于第二层上表面，通过控制刮刀与基布之间的距离，从而控制涂层厚度为20μm以下，经过165～175℃烘烤，烘烤60s，使并不进行发泡或者不充分发泡，收卷得到新型印刷材料的半成品。
(4)可进一步将步骤(3)中得到的半成品，进行分切，得到一种新型印刷材料，可以作为标签材料使用。
实施例2:
(1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为70:30，催化剂是A组分和B组分的质量和的0.001％，填料占A比例为40％；
(2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体A、催化剂及抗静电剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度43-46℃；
(3)将第一搅拌釜和第二搅拌釜的浆料在涂布装置前端直接混合，投入第二层并在2～5分钟之内通过涂布装置，使混合浆料直接涂布于第二层上表面，通过控制刮刀与基布之间的距离，控制涂层厚度为20-30μm，经过165～175℃烘烤，烘烤90s，使其不进行发泡或者不充分发泡，收卷得到新型印刷材料的半成品。
(4)将步骤(3)中得到的半成品，进行分切，得到一种新型印刷材料，可以作为标签材料使用。
(5)将步骤(4)所得成品，在液氮中冷冻切片后，在电子显微镜下观察到的断面图，如图3所示。
实施例3:
(1)按百分比选取上层各原材料比例：多NH 2基预聚体A与多NCO基预聚体B的质量比为55:45，催化剂是A和B的质量和的0.0003％，填料占A比例为10％，抗酚黄变助剂占A比例为3％，致孔剂占A比例为1％；
(2)在常温常压件下，将步骤(1)中的原料按照多多NH 2基预聚体A、催化剂及抗酚黄变助剂、致孔剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度46-50℃；
(3)将第一搅拌釜和第二搅拌釜的浆料通过涂布装置，直接涂布于离型材料上，通过控制刮刀与离型纸之间的距离，涂布厚度控制为30-100μm，在120～130℃烘烤条件下60s，使其不充分发泡，得带涂层胶离型材D；
(4)通过温度85～95℃压辊将第二层与带涂层胶离型材D进行轧合，经过155～165℃烘干，将离型材D上的涂层胶转移至第二层上面，并将离型材料和带无溶剂胶的第二层进行剥离后单独收卷，制得无溶剂印刷材料半成品；
(5)将(4)中得到的半成品，进行分切，得到一种新型印刷材料，可以作为标签材料使用。
(6)将(5)中得到的成品，在液氮中冷冻切片后，在电子显微镜下观察到的断面图，如图4所示。
为了更好地体现本发明的有益性，下面对本发明实施例1和实施例2得到的一种新型印刷材料进行性能测试，测试结果如表1所述：
表1实施例1—3与对比例性能测试结果
Figure PCTCN2022094046-appb-000001
Figure PCTCN2022094046-appb-000002
其中：
1.对比例为市场上买回来的牛仔裤的商标，为以DMF为溶剂的聚氨酯涂层工艺生产，将在其液氮中冷冻切片后，断面SEM图如图2所示。
2.测试方法
(1)耐摩擦牢度测试是参照GB/T 3920-2008《纺织品色牢度试验耐摩擦色牢度》。
(2)耐水洗色牢度测试是参照GB/T3920-2008《纺织品色牢度试验耐皂洗色牢度》。
(3)酚黄变色牢度是参考GB/T 29778—2013《纺织品色牢度潜在酚黄变的评估》。
(4)pH值测试参考GB T 7573-2009《纺织品水萃取液pH值的测定标准》。
(5)石洗测试：参考专利CN 103114472 B《石洗柔软粗毛纺织物的方法》标准水洗机，90℃水温，0.6g皂片，0.3g无水碳酸钠，5-6个火山石，150ml蒸馏水，水洗150分钟，自然晾干。
(6)染色测试：
①前处理：(容器:125mm×Φ75mm，标准水洗机)0.15g渗透剂+5g布(2g涂层布+3g棉布)+150ml蒸馏水，90℃水温，洗30min。
②染色：再加0.05g活性染料+9g元明粉(无水硫酸钠)，90℃水温，洗1.5h，冲洗干净，自然晾干。将水洗后的样品，与水洗前的样品进行比较，主要考察水洗样品的表面变色情况
(6)pH值测试：①称10克样品，剪1.5cm左右的小碎片；②量取250ml蒸馏水，放入烧杯以中等速度煮沸，再煮10min，放入剪好的样品，用皿覆盖烧杯，再煮沸10min；③完成后将烧杯冷却至室温，取出水萃取液倒入干净的烧杯中测pH值。
(7)热转印印刷测试，打印清晰度参考申请人内部标准KRB-ZC-202016《热转印打印等级评判标准》，测试用热转印打印机型号为X-3200，打印条件为：浓度12。打印完成后，条码长2.9cm宽1.2cm，在D65光源下，45°35cm左右的距离进行评级。如图4，判别标准为：断点效果与5级标样相同、无渗化，则评定为5级；断点效果与4级标样相同、无渗化，则评定为4级；断点效果与3级标样相同、无渗化，则评定为3级；断点效果与2级标样相同、无渗化，则评定为2级；断点效果与1级标样相同、无渗化，则评定为1级。
3.经过本发明的实验发现：以本发明的无溶剂层作为印刷层，涂层厚度达到20μm以上时，抗染色性能达4.0级，抗砂洗性能达4.0级，pH至在4.0-7.5之间，过程中无有害物质排放，进一步结合图8可知，印刷可达4.0级以上，且该工艺能够满足Oeko-Tex Standard 100的要求。
以上仅是本发明的优选实施方式，应当指出的是，上述优选实施方式不应视为对本发明的限制，本发明的保护范围应当以权利要求所限定的范围为准。对于本技术领域的普通技术人员来说，在不脱离本发明的精神和范围内，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (13)

  1. 一种新型印刷材料，其特征在于包括上层和第二层；
    所述上层是无溶剂层，所述上层由多OH基预聚体和多异氰酸酯基预聚体催化反应形成，得到厚度在20～150μm的无溶剂层；或者，所述上层由多NH 2基预聚体和多异氰酸酯基预聚体催化反应形成，得到厚度在20～150μm的无溶剂层；
    上层直接涂布或贴合于第二层表面。
  2. 根据权利要求1所述的印刷材料，其特征在于所述上层无任何有机挥发组分，有机挥发组分检测极限≤5ppm。
  3. 根据权利要求1所述的印刷材料，其特征在于所述无溶剂层为不发泡或不充分发泡层，所述不发泡或不充分发泡层指的是其孔径≤100μm。
  4. 根据权利要求1所述的印刷材料，其特征在于所述无溶剂层还含有颜料，所述无溶剂层无任何有机挥发组分，制备无溶剂层的组分100％转化为固体。
  5. 根据权利要求1所述的印刷材料，其特征在于，所述上层为可印刷层。
  6. 根据权利要求1所述的印刷材料，其特征在于，所述上层还含有添加剂，所述添加剂包括颜料、增白剂、致孔剂、填料、阻燃剂、抗静电剂、抗黄变助剂中的至少一种。
  7. 根据权利要求1所述的印刷材料，其特征在于所述第二层为尼龙、涤纶、氨纶、黏胶纤维中的一种或多种织造的平纹布或非织造布。
  8. 根据权利要求1所述的印刷材料，其特征在于所述第二层由喷气织造、喷水织造、水刺法、纺黏法、熔喷法的一种或多种工艺制造。
  9. 根据权利要求1所述的印刷材料，其特征在于所述第二层其厚度一般控制在60-160μm。
  10. 根据权利要求1所述的印刷材料，其特征在于第二层的下表面覆盖第三层，第三层为水性高分子聚合物、热熔胶、压敏胶的一种或多种的混合物。
  11. 根据权利要求1所述的印刷材料，其特征在于第三层为无溶剂涂层时，上层和第三层为同种或为不同种无溶剂层，上层和第三层均为可印刷层，上层和第三层分别覆盖于第二层的上层和下层。
  12. 权利要求1所述的一种新型印刷材料的制造方法，其特征在于包括以下步骤：
    (1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A组分和B组分的质量和的0.0001～0.001％；或多NH 2基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A组分和B组分的质量和的0.0001～0.001％；
    (2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度20～50℃；或在常温常压件下，将步骤(1)中的原料按照多NH 2基预聚体A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度20～50℃；
    (3)将第一搅拌釜和第二搅拌釜的浆料在涂布装置前端直接混合，投入第二层并在2～5分钟之内通过涂布装置，通过刮刀与基材之间的距离，使混合浆料直接涂布于第二层上表面，经过100～180℃烘烤30～90s之间，使无溶剂层不发泡或不充分发泡，收卷得到无溶剂印刷材料；
    (4)将步骤(3)中得到的半成品，进行分切，得到一种无溶剂印刷材料。
  13. 权利要求1所述的一种新型标签的制造方法，其特征在于包括以下步骤：
    (1)按百分比选取上层各原材料比例：多OH基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A和B的质量和的0.0001～0.001％；或多NH 2基预聚体A与多NCO基预聚体B的质量比为30-70:70-30，催化剂是A组分和B组分的质量和的0.0001～0.001％；
    (2)在常温常压件下，将步骤(1)中的原料按照多OH基预聚体或A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度 20～50℃；或将步骤(1)中的原料按照多NH 2基预聚体或A、催化剂及添加剂分散在第一搅拌釜中，多NCO基预聚体B在第二搅拌釜中，保持温度20～50℃；
    (3)将第一搅拌釜和第二搅拌釜的浆料通过涂布装置，通过刮刀与基材之间的距离，直接涂布于离型材料上，经过100～160℃烘烤30～90s之间，使无溶剂层不发泡或不充分发泡，得带涂层胶离型材D；
    (4)通过温度80～100℃压辊将第二层与带涂层胶离型材D进行轧合，经过120～170℃烘干，将离型材D上的涂层胶转移至第二层上面，并将离型材料和带无溶剂胶的第二层进行剥离后单独收卷，制得无溶剂印刷材料半成品；
    (5)将(4)中得到的半成品，进行分切，得到一种无溶剂印刷材料。
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