WO2022007425A1 - 环保水性涂层及其制备方法 - Google Patents

环保水性涂层及其制备方法 Download PDF

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WO2022007425A1
WO2022007425A1 PCT/CN2021/080108 CN2021080108W WO2022007425A1 WO 2022007425 A1 WO2022007425 A1 WO 2022007425A1 CN 2021080108 W CN2021080108 W CN 2021080108W WO 2022007425 A1 WO2022007425 A1 WO 2022007425A1
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water
wetting agent
weight
agent
based coating
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PCT/CN2021/080108
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English (en)
French (fr)
Inventor
潘省予
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上海德粼水性油墨有限公司
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Publication of WO2022007425A1 publication Critical patent/WO2022007425A1/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
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/47—Levelling agents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of water-based coatings, in particular to an environment-friendly water-based coating.
  • the main components of water-based coatings are acrylic emulsions or acrylic resins.
  • a large amount of emulsifier must be used, and the acrylic resins or acrylic emulsions must be neutralized with an aqueous solution of organic amines or ammonia water to generate carboxylate dissolved in water.
  • the pH value must be kept above 8.5, so they all contain ammonia water, organic amines, etc. to maintain weak alkalinity and have a certain odor.
  • the current water-based coatings also need to add some organic solvents in the actual use process, such as ethanol, isopropanol and other low-boiling organic solvents to help drying, if the printing speed is above 100 m/min, the general organic solvent addition amount It will be more than 25%, or even more than 50%.
  • organic solvents such as ethanol, isopropanol and other low-boiling organic solvents
  • the invention provides an aqueous coating, which does not use low-boiling organic solvents such as ethanol and isopropanol, does not use an emulsifier, does not contain a large amount of ammonia water or organic amines, and belongs to an environmentally friendly aqueous coating.
  • An environment-friendly water-based coating the components of which are 30.0-45.0 parts by weight of water-based acrylic monodisperse resin and 20.0-40.0 parts by weight of water-based styrene-acrylic resin as main connecting materials, and 0.3-1.0 parts by weight of rheology aid and 0.5 -1.5 parts by weight of wetting agent A, 0.1-0.5 parts by weight of wetting agent B, and no low-boiling organic solvent, wherein the rheology assistant is an associative polyether polyurethane, and the wetting agent A It is an ethoxy-modified acetylene glycol base material wetting agent, and the wetting agent B is a polyether-modified organic silicon wetting agent.
  • the adduct of the associative polyether polyurethane polyether and diisocyanate contains hydrophobic end groups.
  • the present invention also provides a kind of environment-friendly water-based coating, which comprises the following main components by weight:
  • the rheological aid is associative polyether polyurethane
  • the wetting agent A is an ethoxy-modified acetylenic glycol base material wetting agent
  • the wetting agent B is a polyether-modified silicone Wetting agent
  • the environmentally friendly water-based coating does not contain low-boiling organic solvents.
  • the adduct of the associative polyether polyurethane polyether and diisocyanate contains hydrophobic end groups.
  • the present invention also provides a method for preparing the above-mentioned environmentally friendly water-based coating, which includes the following steps: adding two kinds of connecting materials in a formula amount in a container, turning on stirring, then adding the remaining required additives in turn, and using a high-speed Dispersion process, the dispersion is uniform, and the environment-friendly water-based coating is prepared.
  • the environmental protection water-based coating of the present invention does not need to use an emulsifier in the manufacturing process, has good water solubility, and does not need to adjust the pH value by adding ammonia water, organic amines, etc.
  • the environmental protection of the product reduces the use of amines and emulsifiers.
  • the environmental protection water-based coating of the present invention has the functionality of traditional products, and the coating completely uses water as the dispersion medium, and can be diluted with water to the required viscosity during use, and can ensure good drying performance.
  • the coating In the high-speed printing process of more than 200 m/min, it is not necessary to add fast-drying low-boiling organic solvents such as ethanol to improve the dryness of the product and ensure the environmental friendliness of the product; the actual coating amount is traditional under the same physical properties. 60--70% of water-based coating.
  • the viscosity of the acrylic monodispersion is much lower than that of the acrylic emulsion, the viscosity of the finished water-based coating is too low, and a flat ink film cannot be formed whether it is gravure, flexo or roller coating.
  • the present invention makes the acrylic monodispersion have suitable viscosity and rheological behavior by selecting a specific rheology aid (associative polyether polyurethane), and by selecting a suitable combination of wetting agents (polyether modified silicone moisturizing agent) Wetting agent and ethoxy-modified acetylenic glycol wetting agent), so that the product can adapt to different substrates such as paper, gold and silver cardboard, has good printability, and can meet the requirements of gravure, flexo and offset printing. Optical machine and other different printing methods.
  • a range represented by "one value to another value” is a general representation that avoids listing all the values in the range in the specification. Therefore, the recitation of a specific numerical range includes any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were expressly written in the specification. same range.
  • the invention provides an environment-friendly water-based coating, the components of which use 30.0-45.0 parts by weight of water-based acrylic monodisperse resin and 20.0-40.0 parts by weight of water-based styrene-acrylic resin as main connecting materials, and add 0.3-1.0 parts by weight of rheology Auxiliary and 0.5-1.5 parts by weight of wetting agent A, 0.1-0.5 parts by weight of wetting agent B, and do not contain low-boiling organic solvents, wherein the rheological auxiliary is an associative polyether polyurethane, and the The wetting agent A is an ethoxy-modified acetylenic glycol base material wetting agent, and the wetting agent B is a polyether-modified organic silicon wetting agent.
  • the associative polyether polyurethane is an adduct of a polyether and a diisocyanate, and contains hydrophobic end groups.
  • the present invention adopts acrylic monodispersion (also called water-based acrylic monodispersed resin) as the main resin, and does not need to use emulsifier in the manufacturing process.
  • Butyl ester is polymerized by the action of initiator in pure water system.
  • the resin has narrow molecular weight distribution and excellent quick-drying performance.
  • the pH of the resin after synthesis is about 7.0, and it has excellent water solubility.
  • the diluent is completely deionized water, and ammonia organic amine is not used to adjust the pH value.
  • the speed can reach 250 m/min
  • low-boiling organic solvents such as alcohol isopropyl alcohol to aid drying.
  • the viscosity of the acrylic monodispersion is much lower than that of the acrylic emulsion, resulting in the low viscosity of the finished water-based coating, and it is impossible to form a smooth ink film whether it is gravure, flexo or roller coating.
  • the invention makes the acrylic monodispersion have suitable viscosity and rheological behavior by selecting a specific rheological additive (associative polyether polyurethane). The requirements of high, medium and low shear viscosity, the influence of pseudoplastic fluid characteristics on the mixed system of water-based coatings, coating leveling, fluidity of mixed systems, etc.
  • Low shear, medium shear and high shear viscosity can be provided in the mixed system, but among them, the rheological additive that provides low shear performance not only increases the viscosity of the system, but also makes the system have strong pseudoplastic fluid characteristics. It has strong viscosity in state and low viscosity when agitated, so it is not suitable for high-speed printing application scenarios of the present invention, and the product has poor leveling; high shear rheological additives provide thickening properties with Newtonian fluid characteristics, Make the product have suitable viscosity and have good flow.
  • the associative polyether polyurethane selected in the present invention is a high-shear rheology aid, which not only has excellent thickening properties, but also has good compatibility with the dispersion used. If the rheology aid is compatible with the dispersion Poor performance will affect the gloss of the product, and the product will have a water separation phenomenon after storage.
  • the present invention selects a rheological additive with suitable thickening and good compatibility through theoretical analysis and a large number of tests.
  • the present invention also selects a suitable combination of wetting agents, specifically polyether-modified silicone wetting agents and ethoxy-modified acetylenic glycol wetting agents, modified silicone wetting agents.
  • the agent can reduce the static surface tension of the system very well, so that the product has good wetting performance on substrates with low surface tension, such as gold and silver cardboard or cellophane, but when printing at high speed, only use modified silicone to wet Wetting agents cannot control the dynamic surface tension very well, resulting in poor wetting.
  • the selection of ethoxy-modified acetylenic diol wetting agents can well control the dynamic surface tension during high-speed printing, so that the product has excellent printing suitability. sex.
  • the combination of the above two wetting agents makes the water-based coating formula product suitable for different substrates such as paper, gold and silver cardboard, and has good printability, which can meet the requirements of gravure printing, flexo printing, offset printing varnishing machines, etc. printing method.
  • the selection of the rheological agent and the wetting agent needs to be determined by appropriate design experiments on the basis of the research principle, and any existing one cannot be arbitrarily selected.
  • a rheological agent or wetting agent, improper selection of the above reagents will cause compatibility and stability problems in the water-based coating mixing system, and problems such as loss of gloss, water separation or post-thickening will occur, which will affect the performance of the product and make the product unable to meet the standard. .
  • the above-mentioned environmentally friendly water-based coating of the present invention can be added with functional additives according to customer requirements to provide products that meet various requirements for wear resistance, water resistance, gloss and the like.
  • the environment-friendly water-based coating generally also includes 10.0-15.0 parts by weight of water.
  • the environmental protection water-based coating preferably further comprises 0.2-1.0 parts by weight of a defoamer, which can be DOWSIL 65, a water-based polyether-modified silicone defoamer produced by BYK or Taoxi Company.
  • a defoamer which can be DOWSIL 65, a water-based polyether-modified silicone defoamer produced by BYK or Taoxi Company.
  • the environmentally friendly water-based coating preferably further includes 3.0-8.0 parts by weight of an anti-wear agent, which can be an oxidized polyethylene wax emulsion, such as Onkel 842N, Onkel MD-2000, BASF WAX35, and the like.
  • an anti-wear agent which can be an oxidized polyethylene wax emulsion, such as Onkel 842N, Onkel MD-2000, BASF WAX35, and the like.
  • the environment-friendly water-based coating preferably further includes 0.1-1.0 parts by weight of a slip agent, and the slip agent can be a polyether-modified silicone slip agent DOWSIL 51 or TEGO 410 provided by Digao or Taoxi Company.
  • a slip agent can be a polyether-modified silicone slip agent DOWSIL 51 or TEGO 410 provided by Digao or Taoxi Company.
  • the environment-friendly water-based coating preferably further comprises not more than 0.5 parts by weight of an anti-adhesive agent, and the anti-adhesive agent can be DOESIL 23N, an epoxy-modified silicone rubber anti-adhesive agent provided by Taoxi Company.
  • the environment-friendly water-based coating preferably further comprises 0.1-0.2 parts by weight of an antifungal agent.
  • the mildew inhibitor can be a heterocyclic compound such as MB-11 provided by Hemings Specialty Chemicals.
  • the environment-friendly water-based coating preferably further comprises 0.2-0.5 parts by weight of an amine neutralizer.
  • the amine neutralizer can be a low-odor glycol amine product, such as DeuAdd MA-95 provided by Hemings Special Chemicals.
  • the present invention also provides an environmentally friendly water-based coating, which comprises the following main components in parts by weight:
  • the rheological aid is associative polyether polyurethane
  • the wetting agent A is an ethoxy-modified acetylenic glycol base material wetting agent
  • the wetting agent B is a polyether-modified silicone Wetting agent
  • the environmentally friendly water-based coating does not contain low-boiling organic solvents.
  • the associative polyether polyurethane is an adduct of a polyether and a diisocyanate, and contains hydrophobic end groups.
  • the main water-based acrylic monodisperse resin of the above-mentioned environmental protection water-based coating of the present invention completely uses water as the dispersing medium.
  • the basic monomers methacrylic acid, methyl methacrylate and butyl acrylate are used in the pure water system. It is polymerized by the action of the initiator, directly synthesized and stored in the pure water system, instead of being emulsified and dispersed in the later stage or dissolved and swelled in water by the use of hydrophilic groups. It has good water solubility and does not need to increase the pH value of the dispersion. To increase the water solubility, make the product neutral, ensure the environmental protection of the product, and reduce the use of amines and emulsifiers.
  • the water-based styrene-acrylic resin used in the present invention does not contain an emulsifier, thereby ensuring the environmental protection performance of the product.
  • the water-based acrylic monodisperse resin is one of the main connecting materials of the water-based coating of the present invention, and it is a nano-pure water-based polyacrylic acid monodisperse resin.
  • the water group dissolves and swells in water, which reduces the impact of the use of emulsifiers on the environment and ensures the environmental protection of the product.
  • the water-based styrene-acrylic resin is one of the main connecting materials of the water-based coating of the present invention, and is synthesized by using water, ethylene glycol amine and solid styrene-acrylic resin, without using an emulsifier in the synthesis, and using water as a medium to maintain the environmental friendliness of the product, And has good gloss, transparency, printing adaptability, excellent water solubility.
  • the water-based resin used in the water-based coating of the present invention has good water solubility, the viscosity in water is low, and cannot meet the viscosity required for printing by the printing machine. Therefore, the present invention adopts an environmentally friendly water-based resin with zero VOC, no organic tin and APEO.
  • Rheology additives such as associative polyether polyurethane rheology additives, adjust waterborne coating products to suitable application viscosity, coating leveling, mixing system fluidity, and compatibility.
  • the above defoamer is a water-based polyether-modified silicone defoamer that does not contain organic tin and APEO, and is used to suppress the bubbles that appear in the production and use of the product.
  • the above wetting agent A is an efficient wetting agent based on acetylene glycol modification, such as ethoxylated acetylene glycol base material wetting agent, which can greatly reduce static and dynamic surface tension, and has good wetting agent and high-speed printing performance.
  • the above wetting agent B is a polyether modified silicone wetting agent, which makes the product have good wetting agent leveling.
  • wetting agent A and wetting agent B makes the water-based coating suitable for both substrates with low surface tension and high-speed printing.
  • the above-mentioned anti-wear agent is selected from oxidized polyethylene wax emulsion, which can endow the product with good anti-friction performance.
  • the above slip agent is a polyether-modified silicone slip agent, which provides the product with good slip properties, scratch resistance and anti-blocking properties.
  • the above-mentioned anti-sticking agent is an epoxy-modified silicone rubber anti-sticking agent, which can endow the product with excellent anti-sticking and abrasion resistance.
  • antifungal agents and amine neutralizers provide antifungal properties and pH stability of the product, respectively.
  • the preparation of the above-mentioned environmental protection water-based coating can be carried out by the following method: adding the connecting material of the formula amount in the container, starting the stirring, then adding the required auxiliary agents in turn, using a high-speed dispersion process, and dispersing evenly to prepare the pure water of the present invention. coating.
  • the coating In addition to the functionality of traditional products, because the coating completely uses water as the dispersion medium, it can be completely diluted with water to the required viscosity during use, and can ensure good drying performance. During the high-speed printing process, there is no need to add fast-drying organic solvents such as ethanol to improve the dryness of the product.
  • the actual coating amount is 60--70% of the traditional water-based coating under the same physical properties, which ensures the environmental friendliness of the product.
  • wetting agent B Polyether modified silicone wetting agent 0.2
  • the pure water-based coating is prepared by adding two kinds of connecting materials in the formula amount in the container, starting the stirring, and then adding the required additives in turn, using a high-speed dispersing process, and dispersing evenly.
  • the finished product of the pure water-based coating is a stable and uniform colloid without delamination or material precipitation, and it is sealed and protected from light at 5-25 degrees.
  • the shelf life is greater than or equal to 1 year, and a large amount of water can be diluted to maintain its stable and uniform colloidal form.
  • the above water-based coating was printed in a printing factory in Changsha with a gravure printing machine, silver cardboard, and a printing speed of 200 m/min.
  • the performance of the obtained coating completely met the packaging requirements. See Table 1 for details.
  • the solvent residue should be less than 10 mg/m 2 , and the data of the product of this example in Table 1 below are all close to 0, far below the standard. It can be seen that the organic solvent content in the water-based coating product of this embodiment is almost zero.
  • wetting agent B Polyether modified silicone wetting agent 0.2
  • the pure water-based coating is prepared by adding two kinds of connecting materials in the formula amount in the container, starting the stirring, and then adding the required additives in turn, using a high-speed dispersing process, and dispersing evenly.
  • the above-mentioned pure water-based coating product obtained in this example is a stable and uniform colloid after production, without delamination or material precipitation, and is sealed and protected from light. Under the condition of 5-25 degrees, the shelf life is greater than or equal to 1 year, and a large amount of water can be diluted to maintain its stable and uniform colloidal form.
  • the above-mentioned water-based coating was printed in a printing factory in Yanji, with gravure printing machine, high-gloss paper, transfer paper, and printing at a speed of 120 m/min.
  • the performance of the obtained coating completely met the packaging requirements. See Table 2 for details.
  • Table 2 shows YC 171-2014 Standard for cigarette tipping paper, residual solvent content.
  • the solvent residue should be less than 10 mg/m 2 , and the data of the product of this example in Table 1 below are all close to 0, far below the standard. It can be seen that the organic solvent content in the water-based coating product of this embodiment is almost zero.
  • wetting agent B Polyether modified silicone wetting agent 0.3
  • the pure water-based coating is prepared by adding two kinds of connecting materials in the formula amount in the container, starting the stirring, then adding the required additives in turn, and using a high-speed dispersion process to uniformly disperse the coating.
  • the above-mentioned pure water-based coating product obtained in this example is a stable and uniform colloid after production, without delamination or material precipitation, and is sealed and protected from light. Under the condition of 5-25 degrees, the shelf life is greater than or equal to 1 year, and it can still maintain its stable and uniform colloidal form when diluted with a large amount of water.
  • the above-mentioned water-based coating was printed in a printing factory in Wenzhou, on a gravure printing machine, on high-gloss paper, and printed at a speed of 140 m/min.
  • the performance of the obtained coating completely met the packaging requirements. See Table 3 for details.
  • Table 3 shows YC 171-2014 Standard for cigarette tipping paper, solvent residue.
  • the solvent residue should be less than 10 mg/m 2
  • the data of the product of this example in Table 1 below are all close to 0, far below the standard. It can be seen that the water-based coating product of this embodiment is an environmentally friendly product that does not contain organic solvents.
  • the detection value below the limit of quantification was regarded as a detection error.
  • This table 3 shows that the organic solvent content of the product of this example is almost zero.

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Abstract

本发明公开了一种环保水性涂层及其制备方法，所述水性涂层组分以30.0-45.0重量份水性丙烯酸单分散树脂及20.0-40.0重量份水性苯丙树脂作为主要连接料，并添加0.3-1.0重量份的流变助剂及0.5-1.5重量份的润湿剂A、0.1-0.5重量份的润湿剂B，并不含低沸点有机溶剂，其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂。本发明的环保水性涂层在制造过程中无需使用乳化剂，具有良好的水溶性，不需通过添加氨水、有机胺等调节pH值来增加水溶性，使产品保持中性，保证了产品的环保性，减少了胺及乳化剂的使用。

Description

环保水性涂层及其制备方法 技术领域
本发明涉及水性涂层技术领域，特别涉及一种环保的水性涂层。
背景技术
目前水性涂层的主要组分是丙烯酸乳液或者丙烯酸树脂，乳液在制造过程中必须使用大量乳化剂，而且丙烯酸树脂或丙烯酸乳液必须使用有机胺或者氨水的水溶液进行中和，生成溶解于水的羧酸盐，来实现树脂乳液的水溶性，所以pH值必须保持8.5以上，因此均含有氨水、有机胺等保持弱碱性，有一定的异味。
此外，目前的水性涂层在实际使用过程中还需要添加部分有机溶剂，比如乙醇、异丙醇等低沸点有机溶剂来帮助干燥，如果在100米/分钟以上的印刷速度时一般有机溶剂添加量会超过25％，甚至超过50％。
发明内容
本发明提供一种水性涂层，不使用乙醇、异丙醇等低沸点有机溶剂，不使用乳化剂，不含有大量氨水或有机胺，属于环保的水性涂层。
本发明的技术方案如下：
一种环保水性涂层，其组分以30.0-45.0重量份水性丙烯酸单分散树脂及20.0-40.0重量份水性苯丙树脂作为主要连接料，并添加0.3-1.0重量份的流变助剂及0.5-1.5重量份的润湿剂A、0.1-0.5重量份的润湿剂B，并不含低沸点有机溶剂，其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂。其中，所述缔合型聚醚聚氨酯聚醚和二异氰酸酯的加合物，并含疏水端基。
基于同样的发明构思，本发明还提供一种环保水性涂层，其包括以下重 量份的主要组分：
(1)水性丙烯酸单分散树脂30.0-45.0，作为主要连接料之一，
(2)水性苯丙树脂20.0-40.0，作为主要连接料之一，
(3)水10.0-15.0，
(4)流变助剂0.3-1.0，
(5)消泡剂0.2-1.0，
(6)润湿剂A 0.5-1.5，
(7)润湿剂B 0.1-0.5，
(8)耐磨剂3.0-8.0，
(9)滑爽剂0.1-1.0，
(10)抗粘剂0.0-0.5，
(11)防霉剂0.1-0.2，
(12)胺中和剂0.2-0.5；
其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂，并且所述环保水性涂层不含低沸点有机溶剂。其中，所述缔合型聚醚聚氨酯聚醚和二异氰酸酯的加合物，并含疏水端基。
基于同样的发明构思，本发明还提供上述的环保水性涂层的制备方法，包括如下步骤：在容器内添加配方量的两种连接料，开启搅拌，再依次添加其余所需助剂，使用高速分散工艺，分散均匀，制备得所述环保水性涂层。
与现有技术相比，本发明的有益效果如下：
第一、本发明的环保水性涂层在制造过程中无需使用乳化剂，具有良好的水溶性，不需通过添加氨水、有机胺等调节pH值来增加水溶性，使产品保持中性，保证了产品的环保性，减少了胺及乳化剂的使用。
第二、本发明的环保水性涂层具有传统产品的功能性，并且该涂层完全以水为分散介质，使用时可以完全以水进行稀释到所需粘度，并能保证良好 的干燥性能，在200米/分钟以上的高速印刷过程中不需要添加快干性的低沸点有机溶剂如乙醇等提高产品的干燥性，保证产品的环境友好性；在保证相同的物理性能下实际涂布量为传统水性涂层的60--70％。
第三、由于丙烯酸单分散体的粘度远远低于丙烯酸乳液，造成了做出的水性涂层成品粘度过低，无论是凹印、柔印或者辊筒涂布均无法形成平整的墨膜，因此本发明通过选择特定的流变助剂(缔合型聚醚聚氨酯)使丙烯酸单分散体具有合适粘度及流变行为，并通过选择合适的润湿剂的组合(聚醚改性有机硅润湿剂及乙氧基改性炔二醇类润湿剂)，使产品能适应不同的纸张、金银卡纸等基材，具有良好的印刷适性，能满足凹印、柔印、胶印上光机等不同的印刷方式。
当然，实施本发明的任一产品并不一定需要同时达到以上所述的所有优点。
具体实施方式
在本文中，由「一数值至另一数值」表示的范围，是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此，某一特定数值范围的记载，涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围，如同在说明书中明文写出该任意数值和该较小数值范围一样。
本发明提供一种环保的水性涂层，其组分以30.0-45.0重量份水性丙烯酸单分散树脂及20.0-40.0重量份水性苯丙树脂作为主要连接料，并添加0.3-1.0重量份的流变助剂及0.5-1.5重量份的润湿剂A、0.1-0.5重量份的润湿剂B，并不含低沸点有机溶剂，其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂。所述缔合型聚醚聚氨酯聚醚和二异氰酸酯的加合物，并含疏水端基。
本发明采用丙烯酸单分散体(也称水性丙烯酸单分散树脂)作为主体树脂，在制造过程中无需使用乳化剂，该树脂在合成时，所用基础单体甲基丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯在纯水体系中通过引发剂的作用聚合而 成，该树脂具有较窄的分子量分布，具有优异的快干性能。该树脂合成后的pH在7.0左右，并且具有优异的水溶性，稀释剂完全采用去离子水，不采用氨水有机胺调节pH值，在实际高速印刷过程中(速度可达到250米/分钟)也无需添加酒精异丙醇等低沸点有机溶剂帮助干燥。
但是，丙烯酸单分散体的粘度远远低于丙烯酸乳液，造成了做出的水性涂层成品粘度过低，无论是凹印、柔印或者辊筒涂布均无法形成平整的墨膜，因此本发明通过选择特定的流变助剂(缔合型聚醚聚氨酯)使丙烯酸单分散体具有合适粘度及流变行为，特别地，本发明在选择流变助剂时综合考虑了水性涂层混合体系剪切粘度高中低的要求、假塑性流体特征对水性涂层混合体系的影响、涂层流平性、混合体系流动性等多个方面，具体地，不同种类的流变助剂在水性涂层混合体系中可提供低剪切、中剪切和高剪切粘度，但其中，提供低剪切性能的流变助剂不仅提高体系的粘度，还使体系具有强的假塑性流体特性，在静止状态时有很强的粘度，搅动时粘度很低，因此不适合本发明的高速印刷应用场景，并且产品流平性差；高剪切性的流变助剂提供具有牛顿流体特性的增稠性，使产品具有合适的粘度并具有良好的流动性。本发明选择的缔合型聚醚聚氨酯是高剪切性的流变助剂，不仅具有优异的增稠性，而且与所用分散体的相容性良好，若流变助剂与分散体相容性不好，会影响产品光泽，而且储存后产品会有分水现象，本发明是通过理论分析并结合大量测试选择出具有合适增稠性和良好相容性的流变助剂。
与其他组分匹配的，本发明还选择了合适的润湿剂组合，具体是聚醚改性有机硅润湿剂及乙氧基改性炔二醇类润湿剂，改性有机硅润湿剂能很好的降低体系静态表面张力，使产品在表面张力较低的基材上具有良好的润湿性能，如金银卡纸或玻璃纸，但在高速印刷时，仅用改性有机硅润湿剂不能很好的控制动态表面张力，出现润湿不良现象，选择搭配乙氧基改性炔二醇类润湿剂能很好控制高速印刷时的动态表面张力，使产品具有优异的印刷适性。上述两种润湿剂的组合使水性涂层配方产品能适应不同的纸张、金银卡纸等基材，具有良好的印刷适性，能满足凹印、柔印、胶印上光机等不同的印刷方式。
因本发明所述水性涂层所用分散体的特殊性，对流变剂及润湿剂的选择需要在研究原理的基础上适当的设计实验来进行最终的确定，不能任意的选择已有的任一种流变剂或润湿剂，上述试剂选择不当水性涂层混合体系会出现相容性及稳定性问题，会出现失光、分水或后增稠等问题，影响产品性能，使产品不能达标。
本发明的上述环保水性涂层可以按照客户要求添加功能性助剂，提供满足各种耐磨性、耐水性、光泽度等等需求的产品。
所述的环保水性涂层通常还包括10.0-15.0重量份的水。
所述的环保水性涂层优选还包括0.2-1.0重量份的消泡剂，所述消泡剂可以为毕克或陶熙公司生产的水性聚醚改性有机硅消泡剂DOWSIL 65。
所述的环保水性涂层优选还包括3.0-8.0重量份的耐磨剂，所述耐磨剂可以为氧化聚乙烯蜡乳液，例如翁开尔842N，翁开尔MD-2000，巴斯夫WAX35等。
所述的环保水性涂层优选还包括0.1-1.0重量份的滑爽剂，所述滑爽剂可以为迪高或陶熙公司提供的聚醚改性有机硅滑爽剂DOWSIL 51或TEGO 410。
所述的环保水性涂层优选还包括不大于0.5重量份的抗粘剂，所述抗粘剂可以为陶熙公司提供的环氧改性硅橡胶类抗粘剂DOESIL 23N。
所述的环保水性涂层优选还包括0.1-0.2重量份的防霉剂。所述防霉剂可以是杂环化合物，如海明斯特殊化学提供的MB-11。
所述的环保水性涂层优选还包括0.2-0.5重量份的胺中和剂。所述胺中和剂可以选择低气味的乙二醇胺类产品，如海名斯特殊化学提供的DeuAdd MA-95。
具体地，本发明还提供一种环保水性涂层，其包括以下重量份的主要组分：
(1)水性丙烯酸单分散树脂30.0-45.0，作为主要连接料之一，
(2)水性苯丙树脂20.0-40.0，作为主要连接料之一，
(3)水10.0-15.0，
(4)流变助剂0.3-1.0，
(5)消泡剂0.2-1.0，
(6)润湿剂A 0.5-1.5，
(7)润湿剂B 0.1-0.5，
(8)耐磨剂3.0-8.0，
(9)滑爽剂0.1-1.0，
(10)抗粘剂0.0-0.5，
(11)防霉剂0.1-0.2，
(12)胺中和剂0.2-0.5；
其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂，并且所述环保水性涂层不含低沸点有机溶剂。所述缔合型聚醚聚氨酯聚醚和二异氰酸酯的加合物，并含疏水端基。
本发明的上述环保水性涂层的主体水性丙烯酸单分散树脂完全以水为分散介质，该树脂在合成时，所用基础单体甲基丙烯酸、甲基丙烯酸甲酯、丙烯酸丁酯在纯水体系中通过引发剂的作用聚合而成，直接合成并保存于纯水体系中，而非后期乳化分散或利用亲水基团溶解溶胀于水中，具有良好的水溶性，不需要通过提高分散体的pH值来增加水溶性，使产品能够保持中性，保证了产品的环保性，减少了胺及乳化剂的使用。
本发明采用的水性苯丙树脂不含有乳化剂，保证了产品的环保性能。
上述各组分中，
水性丙烯酸单分散树脂为本发明水性涂层的主要连接料之一，为纳米纯水性聚丙烯酸单分散树脂，该树脂完全以水为分散介质，在水中合成，而非后期乳化分散或利用亲水基团溶解溶胀于水中，减少了使用乳化剂对环境的影响，保证产品的环保性。
水性苯丙树脂是本发明水性涂层的主要连接料之一，使用水、乙二醇胺及固体苯丙树脂合成，合成中不使用乳化剂，以水为介质，保持产品的环境 友好性，并具有良好的光泽、透明性、印刷适应性、优异的水溶性。
因本发明的水性涂层所用水性树脂都具有良好的水溶性，在水中粘度较低，不能满足印刷机涂布所需的粘度，因此本发明采用零VOC、不含有机锡及APEO的环保水性流变助剂，例如是缔合型聚醚聚氨酯流变助剂，将水性涂层产品调整为合适的应用粘度、涂层流平性、混合体系流动性、相容性。
上述消泡剂为不含有机锡及APEO的水性聚醚改性有机硅消泡剂，用于抑制产品在生产和使用中出现的气泡。
上述润湿剂A采用基于炔二醇改性的高效润湿剂，例如是乙氧基改性炔二醇类基材润湿剂，可大幅降低静态及动态表面张力，具有良好的润湿剂及高速印刷性能。
上述润湿剂B为聚醚改性有机硅润湿剂，使产品具有良好的润湿剂流平性。
润湿剂A与润湿剂B的混合使用，能使该水性涂层同时适用于表面张力较低的基材及高速印刷的情况。
上述耐磨剂选自氧化聚乙烯蜡乳液，能够赋予产品良好的耐摩擦性能。
上述滑爽剂为聚醚改性有机硅滑爽剂，提供产品良好的滑爽性、耐刮性及抗粘连能。
上述抗粘剂为环氧改性硅橡胶类抗粘剂，能够赋予产品优异的抗粘及耐磨性。
上述防霉剂和胺中和剂分别提供产品的防霉性及pH值稳定性。
上述的环保水性涂层的制备，能够通过如下方法进行：在容器内添加配方量的连接料，开启搅拌，再依次添加所需助剂，使用高速分散工艺，分散均匀制备本发明的纯水性涂层。
该产品除具有传统产品的功能性外，因该涂层完全以水为分散介质，使用时可以完全以水进行稀释到所需粘度，并能保证良好的干燥性能，在200米/分钟以上的高速印刷过程中不需要添加快干性的有机溶剂如乙醇等提高产品的干燥性。在保证相同的物理性能下实际涂布量为传统水性涂层的 60--70％，保证了产品的环境友好性。
下面结合具体实施例，进一步阐述本发明。应该理解，这些实施例仅用于说明本发明，而不用于限定本发明的保护范围。在实际应用中技术人员根据本发明做出的改进和调整，仍属于本发明的保护范围。以下实施例中，各组分均为市售。
实施例1
本实施例的一种环保水性涂层，由以下重量份数的主要组分组成：
水性丙烯酸单分散体树脂45
水性苯丙树脂溶液JONCRYL687 29
水15
流变助剂缔合型聚醚聚氨酯0.5
消泡剂DOWSIL 65 0.7
润湿剂A乙氧基改性炔二醇类基材润湿剂0.5
润湿剂B聚醚改性有机硅润湿剂0.2
耐磨剂MD2000 8
滑爽剂TEGO 410 0.3
抗粘剂DOESIL 23N 0.5
防霉剂MB-11 0.1
胺中和剂DeuAdd MA-95 0.2。
通过在容器内添加配方量的两种连接料，开启搅拌，再依次添加所需助剂，使用高速分散工艺，分散均匀制得纯水性涂层。
关于本实施例的纯水性涂层的相容性和稳定性评估结果：纯水性涂层成品生产后为稳定均匀的胶体，无分层或者物质析出，在密闭避光5-25度情况下保质期大于等于1年，大量加入水稀释仍可保持其稳定均匀的胶体形态。
将上述水性涂层在长沙某印刷厂，以凹印机印刷，银卡纸，印刷速度200米/分钟条件印刷，所得涂层性能完全符合包装要求，详见下表1，表1所示 为YC 171-2014烟用接装纸标准，溶剂残留量。按YC 171-2014标准溶剂残留需低于10mg/m 2，下表1中本实施例产品检测的数据皆接近于0，远远低于标准。可见本实施例的水性涂层产品中有机溶剂含量几乎为0。
表1
Figure PCTCN2021080108-appb-000001
实施例2
本实施例的一种环保水性涂层，由以下重量份数的主要组分组成：
水性丙烯酸单分散体树脂43
水性苯丙树脂溶液JONCRYL687 34
水15
流变助剂缔合型聚醚聚氨酯0.5
消泡剂DOWSIL 65 0.6
润湿剂A乙氧基改性炔二醇类基材润湿剂0.5
润湿剂B聚醚改性有机硅润湿剂0.2
耐磨剂WAX35 5.5
滑爽剂DOWSIL 51 0.2
抗粘剂DOESIL 23N 0.3
防霉剂MB-11 0.1
胺中和剂DeuAdd MA-95 0.2。
通过在容器内添加配方量的两种连接料，开启搅拌，再依次添加所需助剂，使用高速分散工艺，分散均匀制得纯水性涂层。
本实施例的纯水性涂层的相容性和稳定性评估结果：本实施例得到的上述纯水性涂层成品生产后为稳定均匀的胶体，无分层或者物质析出，在密闭避光5-25度情况下保质期大于等于1年，大量加入水稀释仍可保持其稳定均匀的胶体形态。
将上述水性涂层在延吉某印刷厂，凹印机印刷，高光纸，转移纸，速度120米/分钟印刷，所得涂层性能完全符合包装要求，详见下表2，表2所示为YC 171-2014烟用接装纸标准，溶剂残留量。按YC 171-2014标准溶剂残留需低于10mg/m 2，下表1中本实施例产品检测的数据皆接近于0，远远低于标准。可见本实施例的水性涂层产品中有机溶剂含量几乎为0。
表2
Figure PCTCN2021080108-appb-000002
实施例3
本实施例的一种环保水性涂层，由以下重量份数的主要组分组成：
水性丙烯酸单分散体树脂41
水性苯丙树脂溶液JONCRYL687 34.9
水15
流变助剂缔合型聚醚聚氨酯0.7
消泡剂DOWSIL 65 0.8
润湿剂A乙氧基改性炔二醇类基材润湿剂0.5
润湿剂B聚醚改性有机硅润湿剂0.3
耐磨剂WAX35 6
滑爽剂DOWSIL 51 0.3
抗粘剂DOESIL 23N 0.1
防霉剂MB-11 0.2
胺中和剂DeuAdd MA-95 0.2。
通过在容器内添加配方量的两种连接料，开启搅拌，再依次添加所需助 剂，使用高速分散工艺，分散均匀制得纯水性涂层。
本实施例的纯水性涂层的相容性和稳定性评估结果：本实施例得到的上述纯水性涂层成品生产后为稳定均匀的胶体，无分层或者物质析出，在密闭避光5-25度情况下保质期大于等于1年，大量加入水稀释仍可保持其稳定均匀的胶体形态。
将上述水性涂层在温州某印刷厂，凹印机印刷，高光纸，速度140米/分钟印刷，所得涂层性能完全符合包装要求，详见下表3，表3所示为YC 171-2014烟用接装纸标准，溶剂残留量。按YC 171-2014标准溶剂残留需低于10mg/m 2，下表1中本实施例产品检测的数据皆接近于0，远远低于标准。可见本实施例的水性涂层产品为不含有机溶剂的环保产品。
在表3中，空白样是做气象色谱，检测仪器校正数据用，
检测值在定量限以下的认为是检测误差。
该表3表明本实施例的产品有机溶剂含量几乎为0。
表3
Figure PCTCN2021080108-appb-000003
Figure PCTCN2021080108-appb-000004
在本发明及上述实施例的教导下，本领域技术人员很容易预见到，本发明所列举或例举的各原料或其等同替换物、各加工方法或其等同替换物都能实现本发明，以及各原料和加工方法的参数上下限取值、区间值都能实现本发明，在此不一一列举实施例。

Claims (10)

  1. 一种环保水性涂层，其特征在于，其组分以30.0-45.0重量份水性丙烯酸单分散树脂及20.0-40.0重量份水性苯丙树脂作为主要连接料，并添加0.3-1.0重量份的流变助剂及0.5-1.5重量份的润湿剂A、0.1-0.5重量份的润湿剂B，并不含低沸点有机溶剂，其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂。
  2. 如权利要求1所述的环保水性涂层，其特征在于，还包括10.0-15.0重量份的水。
  3. 如权利要求1所述的环保水性涂层，其特征在于，还包括0.2-1.0重量份的消泡剂，所述消泡剂为水性聚醚改性有机硅消泡剂。
  4. 如权利要求1所述的环保水性涂层，其特征在于，还包括3.0-8.0重量份的耐磨剂，所述耐磨剂为氧化聚乙烯蜡乳液。
  5. 如权利要求1所述的环保水性涂层，其特征在于，还包括0.1-1.0重量份的滑爽剂，所述滑爽剂为聚醚改性有机硅滑爽剂。
  6. 如权利要求1所述的环保水性涂层，其特征在于，还包括不大于0.5重量份的抗粘剂，所述抗粘剂为环氧改性硅橡胶类抗粘剂。
  7. 如权利要求1所述的环保水性涂层，其特征在于，还包括0.1-0.2重量份的防霉剂。
  8. 如权利要求1所述的环保水性涂层，其特征在于，还包括0.2-0.5重量份的胺中和剂。
  9. 一种环保水性涂层，其特征在于，包括以下重量份的主要组分：
    (1)水性丙烯酸单分散树脂30.0-45.0，作为主要连接料之一，
    (2)水性苯丙树脂20.0-40.0，作为主要连接料之一，
    (3)水10.0-15.0，
    (4)流变助剂0.3-1.0，
    (5)消泡剂0.2-1.0，
    (6)润湿剂A 0.5-1.5，
    (7)润湿剂B 0.1-0.5，
    (8)耐磨剂3.0-8.0，
    (9)滑爽剂0.1-1.0，
    (10)抗粘剂0.0-0.5，
    (11)防霉剂0.1-0.2，
    (12)胺中和剂0.2-0.5；
    其中所述流变助剂为缔合型聚醚聚氨酯，所述润湿剂A为乙氧基改性炔二醇类基材润湿剂，所述润湿剂B为聚醚改性有机硅润湿剂，并且所述环保水性涂层不含低沸点有机溶剂。
  10. 一种权利要求1-8中任一或者权利要求9所述的环保水性涂层的制备方法，其特征在于，包括如下步骤：在容器内添加配方量的两种连接料，开启搅拌，再依次添加其余所需助剂，使用高速分散工艺，分散均匀，制备得所述环保水性涂层。
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