WO2021120637A1 - 一种低voc高亮耐磨水性环保油墨 - Google Patents

一种低voc高亮耐磨水性环保油墨 Download PDF

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WO2021120637A1
WO2021120637A1 PCT/CN2020/106977 CN2020106977W WO2021120637A1 WO 2021120637 A1 WO2021120637 A1 WO 2021120637A1 CN 2020106977 W CN2020106977 W CN 2020106977W WO 2021120637 A1 WO2021120637 A1 WO 2021120637A1
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water
agent
wear
brightness
parts
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PCT/CN2020/106977
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English (en)
French (fr)
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董留彬
韩琪
余尚军
赵祥
李进
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江苏正红彩印有限公司
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Publication of WO2021120637A1 publication Critical patent/WO2021120637A1/zh

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    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder

Definitions

  • the invention relates to the technical field of inks, in particular to a low-VOC, high-brightness and wear-resistant water-based environmentally friendly ink.
  • Inks are widely used in the printing industry, plastic films, and nylon products. They are mainly composed of binder resins, pigments, solvents, additives and other ingredients. Most of the inks currently used are solvent-based inks. Volatile organic solvents that are harmful to the human body and the environment, and some solvents are more toxic and will cause greater harm to the human body, especially some inks that directly contact the human body. To improve the environmental protection of the ink, it is necessary to change The ink formula is started, using new environmentally friendly materials to replace traditional toxic and harmful ingredients, while obtaining satisfactory drying speed, performance and good printing adaptability. At present, the solution to the environmental protection of inks mainly starts from two aspects. One is to replace solvent-based inks with water-based inks.
  • the second is to change the volatile organic solvent in solvent-based inks and use a single, basically non-toxic solvent.
  • water-based ink has been widely used in the printing of coated paper, white paperboard and plastic film, many packaging manufacturers are reluctant to use it due to its cost; and there are still some problems in the printing of water-based inks, such as water-based inks that are easy to dry.
  • On the anilox roller it affects the uniformity of ink transfer; ink is easy to foam and affects the color density; the water resistance, solvent resistance and abrasion resistance of ink are relatively poor.
  • the purpose of the present invention is to provide a low-VOC, high-brightness and wear-resistant water-based environmentally friendly ink, which can be fully ground and uniformly dispersed on a dispersing device, so that the pigments are firmly attached to the substrate, and the fluidity and viscosity of the ink are , Dryness is improved.
  • a low-VOC high-brightness and wear-resistant water-based environmental protection ink its innovation is that, calculated by mass percentage, it includes the following components: water-soluble resin 25-50%, dispersant 7-23%, Anti-sticking agent 4.5-10%, anti-scratch agent 4.5-10%, pigment 13-19%, pH regulator 1-2% and water 20-30%;
  • the pH regulator includes potassium hydroxide aqueous solution and sodium pyrophosphate
  • a mixture of aqueous solutions, the mixing ratio of the mixture of the potassium hydroxide aqueous solution and the sodium pyrophosphate aqueous solution is 1-2:2-7.
  • the water-soluble resin also includes a colloidal dispersion;
  • the colloidal dispersion includes a thickener, a coupling agent and a defoamer;
  • the mass ratio of the thickener to the colloidal dispersion is 43-53%, the coupling agent accounts for 20-40% of the mass ratio of the colloidal dispersion, and the defoamer accounts for 7-37% of the mass ratio of the colloidal dispersion.
  • the dispersant is composed of 14.0-32.0 parts by weight of methyl methacrylate, 0.4-3.0 parts of dimethylformamide, 0.6-4.0 parts of isocyanate, and 16.0-32.0 parts of vinyl acetate. Parts, 0.6 to 2.5 parts of catalyst, 3.0 to 12.0 parts of aldehyde and ketone resin, and 40.0 to 60.0 parts of ethyl acetate.
  • the catalyst is a mixture of dibutyltin dilaurate and benzoyl peroxide, and the mixing ratio is 1:1.
  • the dispersant is made according to the following steps:
  • Connecting material preparation According to the formula ratio, add the weighed aldehyde and ketone resin to the above mixture III, stir evenly to prepare the dispersant.
  • the pigment is an organic pigment or an inorganic pigment
  • the inorganic pigment dispersant is a sulfonate formed by the reaction of a novolac resin and a sultone compound
  • the number average molecular weight of the inorganic pigment dispersant is 1800
  • the novolac resin has a linear structure with a number average molecular weight of 600.
  • an auxiliary agent including an acrylic shell polymer, an acrylic core polymer and a non-aqueous solvent; wherein the shell polymer encapsulates the acrylic core polymer to form core/shell polymer particles and The core/shell polymer particles are dispersed in a non-aqueous solvent; 90% of the acrylic core/shell polymer particles have a particle size of less than 3 microns; and at least 50% of the acrylic core/shell polymer particles have a particle size of less than 1.5 microns .
  • the dispersant is the reaction of an organic diepoxide or polyepoxide with a primary amine, amino alcohol, amino acid, hydroxy acid or alcohol containing a condensed or non-condensed aromatic imide group product.
  • the anti-sticking agent is composed of mineral spirits, modified polysiloxane and sorbitan fatty acid esters; in the anti-sticking agent, mineral spirits, modified polysiloxane and sorbitol are The fatty acid ester composition mass fraction is 20-28wt%, 30-40wt% and 30-50wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1-2:3.
  • the beneficial effects of the present invention are: the low-VOC, high-brightness, wear-resistant, and environmentally friendly water-based ink of the present invention, the pH of the water-based ink is accurately controlled, and through the use of the pH regulator of the present invention, the general pH is controlled between 8.0-9.5 to ensure that the ink It has good properties such as viscosity, dryness and abrasion resistance.
  • the PH value is higher than 9.5
  • the alkalinity is too strong, and the viscosity of the ink decreases too much, resulting in slower drying speed and poor water resistance.
  • the pH value is lower than 8.0, the alkalinity is too weak and the ink If the viscosity is too high, while the ink is easy to dry, it will cause dirty and paste problems, which is not conducive to printing.
  • This case proposes a low-VOC high-brightness and wear-resistant water-based environmentally friendly ink, calculated by mass percentage, including the following components: water-soluble resin 25-50%, dispersant 7-23%, anti-sticking agent 4.5-10%, anti-scratch agent 4.5-10%, pigment 13-19%, pH adjuster 1-2% and water 20-30%;
  • the pH adjuster includes a mixture of potassium hydroxide aqueous solution and sodium pyrophosphate aqueous solution, the potassium hydroxide aqueous solution and The mixing ratio of the mixture of the sodium pyrophosphate aqueous solution is 1 to 2:2 to 7.
  • the pH of the water-based ink is accurately controlled.
  • the pH is generally controlled between 8.0-9.5 to ensure that the ink has good properties such as viscosity, dryness and abrasion resistance.
  • the PH value is higher than 9.5, the alkalinity is too strong, and the viscosity of the ink decreases too much, resulting in slower drying speed and poor water resistance.
  • the pH value is lower than 8.0, the alkalinity is too weak and the ink If the viscosity is too high, while the ink is easy to dry, it will cause dirty and paste problems, which is not conducive to printing.
  • the water-soluble resin further includes a colloidal dispersion;
  • the colloidal dispersion includes a thickening agent, a coupling agent, and a defoaming agent; the thickening agent
  • the mass ratio of the colloidal dispersion is 43-53%, the mass ratio of the coupling agent to the colloidal dispersion is 20-40%, and the mass ratio of the defoamer to the colloidal dispersion is 7-37 %.
  • colloidal dispersion is added to make the ink The viscosity rebounded.
  • the dispersant in parts by weight, is composed of: 14.0-32.0 parts of methyl methacrylate, 0.4-3.0 parts of dimethylformamide, and 0.6 parts by weight of isocyanate. ⁇ 4.0 parts, 16.0-32.0 parts of vinyl acetate, 0.6 ⁇ 2.5 parts of catalyst, 3.0 ⁇ 12.0 parts of aldehyde and ketone resin, 40.0 ⁇ 60.0 parts of ethyl acetate.
  • the catalyst is a mixture of dibutyltin dilaurate and benzoyl peroxide, and the mixing ratio is 1:1.
  • the dispersant of the present invention can uniformly disperse the compound and make the pigment adhere firmly on the substrate.
  • the dispersant is prepared in the following steps:
  • Connecting material preparation According to the formula ratio, add the weighed aldehyde and ketone resin to the above mixture III, stir evenly to prepare the dispersant.
  • the pigment is an organic pigment or an inorganic pigment
  • the inorganic pigment dispersant is a sulfonate formed by the reaction of a novolac resin and a sultone compound
  • the number average molecular weight of the inorganic pigment dispersant is 1800; the novolac resin has a linear structure, and the number average molecular weight is 600.
  • an auxiliary agent is further included.
  • the auxiliary agent includes an acrylic shell polymer, an acrylic core polymer and a non-aqueous solvent; wherein the shell polymer encapsulates the acrylic core polymer to form a core/
  • the shell polymer particles and the core/shell polymer particles are dispersed in a non-aqueous solvent; 90% of the acrylic core/shell polymer particles have a particle size of less than 3 microns; and at least 50% of the acrylic core/shell polymer particles The particle size is less than 1.5 microns.
  • the dispersant of the present invention can also be an organic diepoxide or polyepoxide and a primary amine containing a condensed or non-condensed aromatic imide group. , Amino alcohol, amino acid, hydroxy acid or alcohol reaction product.
  • the anti-sticking agent is composed of solvent oil, modified polysiloxane and sorbitan fatty acid ester; among the anti-sticking agent, solvent oil, modified The composition mass fraction of polysiloxane and sorbitan fatty acid ester is 20-28 wt%, 30-40 wt% and 30-50 wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1-2:3.
  • a low-VOC high-brightness and wear-resistant water-based environmentally friendly ink calculated by mass percentage, including the following components: water-soluble resin 25%, dispersant 7%, anti-sticking agent 4.5%, anti-scratch agent 4.5%, pigment 19%, PH
  • the regulator is 1% and water is 20%;
  • the pH regulator includes a mixture of potassium hydroxide aqueous solution and sodium pyrophosphate aqueous solution, and the mixing ratio of the mixture of potassium hydroxide aqueous solution and sodium pyrophosphate aqueous solution is 1:2.
  • the water-soluble resin also includes a colloidal dispersion; the colloidal dispersion includes a thickener, a coupling agent and a defoamer; the thickener accounts for 43% of the mass ratio of the colloidal dispersion, and the The mass ratio of the coupling agent to the colloidal dispersion is 20%, and the mass ratio of the defoaming agent to the colloidal dispersion is 37%.
  • the dispersant is composed of 14.0 parts by weight parts of methyl methacrylate, 0.4 parts of dimethylformamide, 0.6 parts of isocyanate, 16.0 parts of vinyl acetate, 0.6 parts of catalyst, 3.0 parts of aldehyde and ketone resin, and acetic acid. 40.0 parts of ethyl ester.
  • the catalyst is a mixture of dibutyltin dilaurate and benzoyl peroxide, and the mixing ratio is 1:1.
  • the above dispersant is made by the following steps:
  • Connecting material preparation According to the formula ratio, add the weighed aldehyde and ketone resin to the above mixture III, stir evenly to prepare the dispersant.
  • the pigment is an inorganic pigment; the inorganic pigment dispersant is a sulfonate formed by the reaction of a linear phenolic resin and a sultone compound; the number average molecular weight of the inorganic pigment dispersant is 1800; the linear phenolic resin is The linear structure has a number average molecular weight of 600.
  • the anti-sticking agent is composed of mineral spirits, modified polysiloxane and sorbitan fatty acid ester; the composition of the solvent oil, modified polysiloxane and sorbitan fatty acid ester in the anti-sticking agent is The fractions are 22wt%, 30wt%, and 48wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1-2.
  • a low-VOC high-brightness and wear-resistant water-based environmentally friendly ink calculated by mass percentage, including the following components: water-soluble resin 50%, dispersant 7%, anti-sticking agent 4.5%, anti-scratch agent 4.5%, pigment 13%, PH
  • the regulator is 2% and water is 20%;
  • the pH regulator includes a mixture of a potassium hydroxide aqueous solution and a sodium pyrophosphate aqueous solution, and the mixing ratio of the mixture of the potassium hydroxide aqueous solution and the sodium pyrophosphate aqueous solution is 1:7.
  • the water-soluble resin also includes a colloidal dispersion; the colloidal dispersion includes a thickener, a coupling agent and a defoaming agent; the thickener accounts for 53% of the mass ratio of the colloidal dispersion, and the The mass ratio of the coupling agent to the colloidal dispersion is 40%, and the mass ratio of the defoaming agent to the colloidal dispersion is 7%.
  • the dispersant is composed of 32.0 parts by weight parts of methyl methacrylate, 3.0 parts of dimethylformamide, 4.0 parts of isocyanate, 32.0 parts of vinyl acetate, 2.5 parts of catalyst, 12.0 parts of aldehyde and ketone resin, and acetic acid. 60.0 parts of ethyl ester.
  • the catalyst is a mixture of dibutyltin dilaurate and benzoyl peroxide, and the mixing ratio is 1:1.
  • the above dispersant is made by the following steps:
  • Connecting material preparation According to the formula ratio, add the weighed aldehyde and ketone resin to the above mixture III, stir evenly to prepare the dispersant.
  • the pigment is an organic pigment.
  • the anti-sticking agent is composed of mineral spirits, modified polysiloxane and sorbitan fatty acid ester; the composition of the solvent oil, modified polysiloxane and sorbitan fatty acid ester in the anti-sticking agent is The fractions are 28wt%, 40wt%, and 32wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1-3.
  • an auxiliary agent is further included, and the auxiliary agent includes an acrylic shell polymer, an acrylic core polymer and a non-aqueous solvent; wherein the shell polymer encapsulates the acrylic core polymer to form core/shell polymer particles And the core/shell polymer particles are dispersed in a non-aqueous solvent; 90% of the acrylic core/shell polymer particles have a particle size of less than 3 microns; and at least 50% of the acrylic core/shell polymer particles have a particle size of less than 1.5 Micrometers.
  • a low-VOC high-brightness and wear-resistant water-based environmentally friendly ink calculated by mass percentage, including the following components: water-soluble resin 25%, dispersant 11%, anti-sticking agent 10%, anti-scratch agent 10%, pigment 13%, PH
  • the regulator is 1% and water is 30%;
  • the pH regulator includes a mixture of potassium hydroxide aqueous solution and sodium pyrophosphate aqueous solution, and the mixing ratio of the mixture of potassium hydroxide aqueous solution and sodium pyrophosphate aqueous solution is 1:1.
  • the water-soluble resin also includes a colloidal dispersion; the colloidal dispersion includes a thickener, a coupling agent and a defoaming agent; the thickener accounts for 45% of the mass ratio of the colloidal dispersion, and the The mass ratio of the coupling agent to the colloidal dispersion is 30%, and the mass ratio of the defoaming agent to the colloidal dispersion is 25%.
  • the dispersing agent of this embodiment can also be an organic diepoxide or polyepoxide and a primary amine, amino alcohol, amino acid, hydroxy acid or fused or non-fused aromatic imide group.
  • the reaction product of alcohol can also be an organic diepoxide or polyepoxide and a primary amine, amino alcohol, amino acid, hydroxy acid or fused or non-fused aromatic imide group.
  • the pigment is an inorganic pigment; the inorganic pigment dispersant is a sulfonate formed by the reaction of a linear phenolic resin and a sultone compound; the number average molecular weight of the inorganic pigment dispersant is 1800; the linear phenolic resin is The linear structure has a number average molecular weight of 600.
  • the anti-sticking agent is composed of mineral spirits, modified polysiloxane and sorbitan fatty acid ester; the composition of the solvent oil, modified polysiloxane and sorbitan fatty acid ester in the anti-sticking agent is The fractions are 26wt%, 35wt%, and 39wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1:2.
  • a low-VOC high-brightness and wear-resistant water-based environmentally friendly ink calculated by mass percentage, including the following components: water-soluble resin 35%, dispersant 15%, anti-sticking agent 7.5%, anti-scratch agent 6.5%, pigment 15%, PH
  • the adjusting agent is 1% and water is 20%;
  • the pH adjusting agent includes a mixture of a potassium hydroxide aqueous solution and a sodium pyrophosphate aqueous solution, and the mixing ratio of the mixture of the potassium hydroxide aqueous solution and the sodium pyrophosphate aqueous solution is 2:7.
  • the water-soluble resin also includes a colloidal dispersion; the colloidal dispersion includes a thickener, a coupling agent and a defoamer; the thickener accounts for 50% of the mass ratio of the colloidal dispersion, and the The mass ratio of the coupling agent to the colloidal dispersion is 40%, and the mass ratio of the defoamer to the colloidal dispersion is 10%.
  • the dispersant is composed of 28.0 parts by weight of methyl methacrylate, 2.2 parts of dimethylformamide, 3.2 parts of isocyanate, 27.0 parts of vinyl acetate, 1.8 parts of catalyst, 8.0 parts of aldehyde and ketone resin, and acetic acid. 50.0 parts of ethyl ester.
  • the catalyst is a mixture of dibutyltin dilaurate and benzoyl peroxide, and the mixing ratio is 1:1.
  • the dispersant of the present invention can uniformly disperse the compound and make the pigment adhere firmly on the substrate.
  • the above dispersant is made by the following steps:
  • Connecting material preparation According to the formula ratio, add the weighed aldehyde and ketone resin to the above mixture III, stir evenly to prepare the dispersant.
  • the pigment is an inorganic pigment; the inorganic pigment dispersant is a sulfonate formed by the reaction of a linear phenolic resin and a sultone compound; the number average molecular weight of the inorganic pigment dispersant is 1800; the linear phenolic resin is The linear structure has a number average molecular weight of 600.
  • the anti-sticking agent is composed of mineral spirits, modified polysiloxane and sorbitan fatty acid ester; the composition of the solvent oil, modified polysiloxane and sorbitan fatty acid ester in the anti-sticking agent is The fractions are 20wt%, 30wt%, and 50wt%.
  • the anti-scratch agent includes polyvinyl fluoride wax and silicone; the mixing ratio of the polyvinyl fluoride wax and silicone is 1:3.
  • the prepared material not only guarantees a suitable pH range, but also has better tinting strength, and the properties of dryness, fluidity, and adhesion fastness are better than those of ordinary materials, and the surface tension Smaller, much smaller than the surface tension of water, can better make the ink adhere to the substrate to achieve printing.

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Abstract

本发明公开了一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂25-50％、分散剂7-23％、防粘剂4.5-10％、抗刮剂4.5-10％、颜料13-19％、PH调节剂1-2％和水20-30％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1～2:2～7。在本发明中，水性油墨的PH得到了精确控制，通过本发明PH调节剂的使用，一般PH控制在8.0-9.5之间，保证油墨具有良好的性能，比如粘度、干燥性和耐磨性。

Description

一种低VOC高亮耐磨水性环保油墨 技术领域
本发明涉及油墨的技术领域，特别是涉及一种低VOC高亮耐磨水性环保油墨。
背景技术
油墨在印刷行业、塑料薄膜、尼龙产品上被大量使用，它主要是由连接料树脂、颜料、溶剂、助剂等成分构成，目前所使用的油墨大部分是溶剂型的油墨，此类油墨会挥发出对人体和环境都有危害的有机溶剂，且有些溶剂的毒性较大，会对人体有较大的伤害，特别是有些直接与人体接触的油墨，要改善油墨的环保性，需要从改变油墨配方着手，采用新型环保材料取代传统有毒有害成分，同时获得令人满意的干燥速度、使用性能以及良好的印刷适应性。目前解决油墨的环保性，主要从两方面下手。一是将溶剂型油墨换成水性油墨。二是改变溶剂型油墨中的易挥发有机溶剂，采用单一，基本无毒的溶剂。虽然水性油墨已广泛应用于铜版纸、白纸板和塑料薄膜的印刷中，但由于其成本问题，许多包装厂家都不愿采用；而且在水墨的印刷中还存在着一些问题，例如水墨很容易干结在网纹辊上，影响传墨的均匀性；水墨很容易起泡沫，影响色密度；水墨的耐水、耐溶剂以及耐磨性比较差等。
发明内容
针对上述不足之处，本发明的目的在于提供一种低VOC高亮耐磨水性环保油墨，能在分散设备上充分研磨、分散均匀，使颜料在承印物上附着牢固，油墨的流动性、粘度、干燥性都提高。
本发明的技术方案概述如下：一种低VOC高亮耐磨水性环保油墨，其创新点在于，按质量百分比计算，包括如下组分：水溶性树脂25-50％、分散剂7-23％、防粘剂4.5-10％、抗刮剂4.5-10％、颜料13-19％、PH调节剂1-2％和水20-30％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1～2:2～7。
在此基础上，所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为43～53％，所述偶联剂占胶态分散体的质量比为20～40％，所述消泡剂占胶态分散体的质量比为7-37％。
在此基础上，所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯14.0～32.0份、二 甲基甲酰胺0.4～3.0份、异氰酸酯0.6～4.0份、醋酸乙烯16.0～32.0份、催化剂0.6～2.5份、醛酮树脂3.0～12.0份、乙酸乙酯40.0～60.0份。
在此基础上，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。
在此基础上，所述分散剂按以下步骤制成：
配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下的催化剂，搅拌，得一混合液Ⅱ；
配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1～1.5h，控制反应温度在72～80℃，滴加完毕后控制反应温度在55～85℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
在此基础上，所述颜料为有机颜料或无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分子量为600。
在此基础上，还包括助剂，所述助剂包含丙烯酸类壳聚合物、丙烯酸类核聚合物和非水溶剂；其中壳聚合物封装丙烯酸类核聚合物，形成核/壳聚合物颗粒和该核/壳聚合物颗粒分散在非水溶剂内；其中90％的丙烯酸类核/壳聚合物颗粒的粒度小于3微米；其中至少50％的丙烯酸类核/壳聚合物颗粒的粒度小于1.5微米。
在此基础上，所述分散剂为有机二环氧化物或聚环氧化物与含有稠合或非稠合芳族酰亚胺基团的伯胺、氨基醇、氨基酸、羟基酸或醇的反应产物。
在此基础上，所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为20～28wt％、30～40wt％以及30～50wt％。
在此基础上，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1～2:3。
本发明的有益效果是：本发明的低VOC高亮耐磨水性环保油墨，水性油墨的PH得 到了精确控制，通过本发明PH调节剂的使用，一般PH控制在8.0-9.5之间，保证油墨具有良好的性能，比如粘度、干燥性和耐磨性。一般的，当PH值高于9.5时，碱性太强，油墨粘度降低过多，导致干燥速度变慢，耐水性能也变差，而当PH值低于8.0时，则碱性太弱，油墨粘度过高，油墨易干燥的同时，会造成脏版、糊版的问题，不利于印刷。
具体实施方式
下面结合实施例对本发明做进一步的详细说明，以令本领域技术人员参照说明书文字能够据以实施。
本案提出一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂25-50％、分散剂7-23％、防粘剂4.5-10％、抗刮剂4.5-10％、颜料13-19％、PH调节剂1-2％和水20-30％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1～2:2～7。在本发明中，水性油墨的PH得到了精确控制，通过本发明PH调节剂的使用，一般PH控制在8.0-9.5之间，保证油墨具有良好的性能，比如粘度、干燥性和耐磨性。一般的，当PH值高于9.5时，碱性太强，油墨粘度降低过多，导致干燥速度变慢，耐水性能也变差，而当PH值低于8.0时，则碱性太弱，油墨粘度过高，油墨易干燥的同时，会造成脏版、糊版的问题，不利于印刷。
作为进一步优选的，在本发明的此实施方式中，所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为43～53％，所述偶联剂占胶态分散体的质量比为20～40％，所述消泡剂占胶态分散体的质量比为7-37％。在本发明中，为了解决因油墨体系里聚合物过少而导致稀释峰的反复出现，导致粘度高峰甚至油墨胶束而影响正常的包装印刷，在本发明中，增加胶态分散体，使油墨粘度回升。
作为进一步优选的，在本发明的此实施方式中，所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯14.0～32.0份、二甲基甲酰胺0.4～3.0份、异氰酸酯0.6～4.0份、醋酸乙烯16.0～32.0份、催化剂0.6～2.5份、醛酮树脂3.0～12.0份、乙酸乙酯40.0～60.0份。进一步的，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。本发明的分散剂，能够使得化合物分散均匀，并且使颜料在承印物上附着牢固。
作为进一步优选的，在本发明的此实施方式中，所述分散剂按以下步骤制成：
配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下 的催化剂，搅拌，得一混合液Ⅱ；
配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1～1.5h，控制反应温度在72～80℃，滴加完毕后控制反应温度在55～85℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
作为进一步优选的，在本发明的此实施方式中，所述颜料为有机颜料或无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分子量为600。
在本发明的另一实施方式中，还包括助剂，所述助剂包含丙烯酸类壳聚合物、丙烯酸类核聚合物和非水溶剂；其中壳聚合物封装丙烯酸类核聚合物，形成核/壳聚合物颗粒和该核/壳聚合物颗粒分散在非水溶剂内；其中90％的丙烯酸类核/壳聚合物颗粒的粒度小于3微米；其中至少50％的丙烯酸类核/壳聚合物颗粒的粒度小于1.5微米。
在本发明的另一实施方式中，作为替代的，本发明的分散剂还可以为有机二环氧化物或聚环氧化物与含有稠合或非稠合芳族酰亚胺基团的伯胺、氨基醇、氨基酸、羟基酸或醇的反应产物。
作为进一步优选的，在本发明的此实施方式中，所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为20～28wt％、30～40wt％以及30～50wt％。此外，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1～2:3。
下面列出的具体实施例：
实施例1：
一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂25％、分散剂7％、防粘剂4.5％、抗刮剂4.5％、颜料19％、PH调节剂1％和水20％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1:2。
所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为43％，所述偶联剂占胶态分散体的质量比为20％，所述消泡剂占胶态分散体的质量比为37％。
所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯14.0份、二甲基甲酰胺0.4份、异氰酸酯0.6份、醋酸乙烯16.0份、催化剂0.6份、醛酮树脂3.0份、乙酸乙酯40.0份。进一步的，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。
上述分散剂按以下步骤制成：
配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下的催化剂，搅拌，得一混合液Ⅱ；
配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1h，控制反应温度在72℃，滴加完毕后控制反应温度在55℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
所述颜料为无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分子量为600。
所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为22wt％、30wt％以及48wt％。此外，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1～2。
实施例2
一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂50％、分散剂7％、防粘剂4.5％、抗刮剂4.5％、颜料13％、PH调节剂2％和水20％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1:7。
所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为53％，所述偶联剂占胶态分散体的质量比为40％，所述消泡剂占胶态分散体的质量比为7％。
所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯32.0份、二甲基甲酰胺3.0份、异氰酸酯4.0份、醋酸乙烯32.0份、催化剂2.5份、醛酮树脂12.0份、乙酸乙酯60.0份。 进一步的，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。
上述分散剂按以下步骤制成：
配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下的催化剂，搅拌，得一混合液Ⅱ；
配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1.5h，控制反应温度在80℃，滴加完毕后控制反应温度在85℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
所述颜料为有机颜料。
所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为28wt％、40wt％以及32wt％。此外，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1～3。
在本实施例中，还包括助剂，所述助剂包含丙烯酸类壳聚合物、丙烯酸类核聚合物和非水溶剂；其中壳聚合物封装丙烯酸类核聚合物，形成核/壳聚合物颗粒和该核/壳聚合物颗粒分散在非水溶剂内；其中90％的丙烯酸类核/壳聚合物颗粒的粒度小于3微米；其中至少50％的丙烯酸类核/壳聚合物颗粒的粒度小于1.5微米。
实施例3
一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂25％、分散剂11％、防粘剂10％、抗刮剂10％、颜料13％、PH调节剂1％和水30％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1:1。
所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为45％，所述偶联剂占胶态分散体的质量比为30％，所述消泡剂占胶态分散体的质量比为25％。
作为替代的，本实施方式的分散剂还可以为有机二环氧化物或聚环氧化物与含有稠合或非稠合芳族酰亚胺基团的伯胺、氨基醇、氨基酸、羟基酸或醇的反应产物。
所述颜料为无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分子量为600。
所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为26wt％、35wt％以及39wt％。此外，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1：2。
实施例4
一种低VOC高亮耐磨水性环保油墨，按质量百分比计算，包括如下组分：水溶性树脂35％、分散剂15％、防粘剂7.5％、抗刮剂6.5％、颜料15％、PH调节剂1％和水20％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例2:7。
所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为50％，所述偶联剂占胶态分散体的质量比为40％，所述消泡剂占胶态分散体的质量比为10％。
所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯28.0份、二甲基甲酰胺2.2份、异氰酸酯3.2份、醋酸乙烯27.0份、催化剂1.8份、醛酮树脂8.0份、乙酸乙酯50.0份。进一步的，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。本发明的分散剂，能够使得化合物分散均匀，并且使颜料在承印物上附着牢固。
上述分散剂按以下步骤制成：
配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下的催化剂，搅拌，得一混合液Ⅱ；
配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1.2h，控制反应温度在76℃，滴加完毕后控制反应温度在70℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
所述颜料为无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生 成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分子量为600。
所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为20wt％、30wt％以及50wt％。此外，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1：3。
下面列出实施例的性能测试结果：
Figure PCTCN2020106977-appb-000001
由上述实例可看出，制得的该料不仅保证具有合适的PH范围，还具有较好的着色力，而且干燥性、流动性、附着牢度等性能均较一般材料好，而且，表面张力较小，远远小于水的表面张力，能够更好的使得油墨附着在承印物上实现印刷。
尽管本发明的实施方案已公开如上，但其并不仅仅限于说明书和实施方式中所列运用，它完全可以被适用于各种适合本发明的领域，对于熟悉本领域的人员而言，可容易地实现另外的修改，因此在不背离权利要求及等同范围所限定的一般概念下，本发明并不限于特定的细节。

Claims (10)

  1. 一种低VOC高亮耐磨水性环保油墨，其特征在于，按质量百分比计算，包括如下组分：水溶性树脂25-50％、分散剂7-23％、防粘剂4.5-10％、抗刮剂4.5-10％、颜料13-19％、PH调节剂1-2％和水20-30％；所述PH调节剂包括氢氧化钾水溶液和焦磷酸钠水溶液的混合物，所述氢氧化钾水溶液和焦磷酸钠水溶液的混合物的混合比例1～2:2～7。
  2. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述水溶性树脂还包括胶态分散体；所述胶态分散体包括增稠剂、偶联剂和消泡剂；所述增稠剂占胶态分散体的质量比为43～53％，所述偶联剂占胶态分散体的质量比为20～40％，所述消泡剂占胶态分散体的质量比为7-37％。
  3. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述分散剂，按重量份计，其组成为：甲基丙烯酸甲酯14.0～32.0份、二甲基甲酰胺0.4～3.0份、异氰酸酯0.6～4.0份、醋酸乙烯16.0～32.0份、催化剂0.6～2.5份、醛酮树脂3.0～12.0份、乙酸乙酯40.0～60.0份。
  4. 根据权利要求3所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述催化剂为二月桂酸二丁基锡和过氧化苯甲酰混合物，所述混合比例为1：1。
  5. 根据权利要求3所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述分散剂按以下步骤制成：
    a、配制混合液Ⅰ：按配方比，将部分催化剂加入配方量的30％乙酸乙酯中并搅拌均匀，得一混合液Ⅰ；
    b、配制混合液Ⅱ：按配方比，依次加入甲基丙烯酸甲酯、二甲基甲酰胺、醋酸乙烯和余下的催化剂，搅拌，得一混合液Ⅱ；
    c、配制混合液Ⅲ：按配方比，称取异氰酸酯加入反应釜中，开启搅拌加温，其搅拌速度为100r/min，升温至105℃时匀速加入混合液Ⅰ，搅拌5min后，开始匀速滴加混合液Ⅱ，滴加时间为1～1.5h，控制反应温度在72～80℃，滴加完毕后控制反应温度在55～85℃，继续反应2.0h；开始降温，并加入配方量余下的乙酸乙酯稀释，得一混合物Ⅲ；
    d、连接料配制：按配方比，将称量好的醛酮树脂加入上述混合物Ⅲ中，搅拌均匀，制得分散剂。
  6. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述颜料为有机颜料或无机颜料；所述无机颜料分散剂为线性酚醛树脂和磺酸内酯类化合物反应生成的磺酸盐；所述无机颜料分散剂的数均分子量为1800；所述线性酚醛树脂为直链结构的，数均分 子量为600。
  7. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，还包括助剂，所述助剂包含丙烯酸类壳聚合物、丙烯酸类核聚合物和非水溶剂；其中壳聚合物封装丙烯酸类核聚合物，形成核/壳聚合物颗粒和该核/壳聚合物颗粒分散在非水溶剂内；其中90％的丙烯酸类核/壳聚合物颗粒的粒度小于3微米；其中至少50％的丙烯酸类核/壳聚合物颗粒的粒度小于1.5微米。
  8. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述分散剂为有机二环氧化物或聚环氧化物与含有稠合或非稠合芳族酰亚胺基团的伯胺、氨基醇、氨基酸、羟基酸或醇的反应产物。
  9. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述防粘剂由溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成；所述防粘剂中溶剂油、改性聚硅氧烷和失水山梨醇脂肪酸酯组成质量分数为20～28wt％、30～40wt％以及30～50wt％。
  10. 根据权利要求1所述的低VOC高亮耐磨水性环保油墨，其特征在于，所述抗刮剂包括聚氟乙烯蜡和有机硅；所述聚氟乙烯蜡和有机硅的混合比例为1～2:3。
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