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WO2015058679A1 - Aqueous bicomponent acrylic acid-polyurethane resin and preparation method therefor - Google Patents

Aqueous bicomponent acrylic acid-polyurethane resin and preparation method therefor Download PDF

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Publication number
WO2015058679A1
WO2015058679A1 PCT/CN2014/089100 CN2014089100W WO2015058679A1 WO 2015058679 A1 WO2015058679 A1 WO 2015058679A1 CN 2014089100 W CN2014089100 W CN 2014089100W WO 2015058679 A1 WO2015058679 A1 WO 2015058679A1
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hours
component
composition
temperature
methacrylate
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PCT/CN2014/089100
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French (fr)
Chinese (zh)
Inventor
马成龙
秦文
王英
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北京金汇利应用化工制品有限公司
廊坊金汇利工业涂料有限公司
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Publication of WO2015058679A1 publication Critical patent/WO2015058679A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6237—Polymers of esters containing glycidyl groups of alpha-beta ethylenically unsaturated carboxylic acids; reaction products 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

Definitions

  • the present invention relates to an aqueous two-component acrylic-urethane resin which is curable at room temperature.
  • the invention also relates to a process for the preparation of the resin.
  • the two-component polyurethane system has excellent mechanical properties (high hardness of coating film, strong adhesion, high abrasion resistance, etc.), good chemical resistance, weather resistance and low-temperature film forming properties, and is widely used in industrial protection, wood furniture and Automotive finishing and other aspects.
  • VOCs volatile organic compounds
  • the water-based two-component polyurethane coating is a new environmentally friendly coating system that combines the high-performance coating of solvent-based two-component polyurethane with the low VOC emissions of waterborne coatings.
  • Current products consist primarily of hydroxyl-containing aqueous polyols and isocyanate-containing curing agents.
  • the advantages of the aqueous two-component polyurethane system are relatively high, because the curing agent used contains isocyanate groups, some defects are also obvious, and its application is severely limited, such as: short activation period, mixed isocyanate and The hydroxyl group and water also react at room temperature, which causes the system to fail, loses the crosslinking ability of the coating film, and affects the performance.
  • the isocyanate is more likely to react with water during the curing process, and the gas CO 2 is generated. If the thickness of the coating film is large, the CO 2 generated during the drying and solidification process cannot be smoothly discharged, or the discharge is slow, and it will form on the coating film. Bubbles or pinholes that severely affect performance and appearance. According to the investigation, the coating film of the aqueous two-component polyurethane coating on industrial production is generally difficult to reach 80 ⁇ m or more, and attention should be paid to the moisture in the environment.
  • the technical problem to be solved by the present invention is to provide an aqueous two-component acrylic-polyurethane resin and a preparation method thereof.
  • an aqueous two-component acrylic-polyurethane resin prepared by mixing A composition and B composition;
  • the A composition consists of the following components:
  • the B composition consists of the following components:
  • the weight ratio of the A composition to the B composition is 4 to 7:1.
  • the molecular weight modifier is selected from one of isooctyl 3-mercaptopropionate, n-dodecyl mercaptan or t-dodecyl mercaptan. a mixture of one or more of the constituents.
  • the acidic neutralizing agent is an organic acid.
  • the organic acid is selected from the group consisting of one or more of formic acid, acetic acid or lactic acid.
  • the preparation method of the aqueous two-component acrylic-polyurethane resin as described above includes the following steps:
  • component A Preparation of component A: adding n-butanol, glycidyl methacrylate, hydroquinone and/or p-hydroxyanisole to the reactor, heating to 50 ° C, adding monoethanolamine and / or n-butylamine, After 1 to 2 hours, the mixture is kept at 48-52 ° C for 2 hours; the temperature is raised to 70-75 ° C, and the temperature is kept for 3 to 4 hours. The material is discharged with methyl methacrylate and/or isobornyl methacrylate.
  • component B Preparation of component B: adding butanone and/or ethyl acetate, glycidyl hexahydrophthalate and/or glycidyl tetrahydrophthalate to the reactor, heating to 40 ° C under stirring, starting Add monoethanolamine and / or n-butylamine dropwise, the temperature is 40 ⁇ 43 ° C, 1 ⁇ 1.5 hours after the completion of the drop; after the completion of the drop to 50 ⁇ 53 ° C, 2 hours of heat preservation; 70 ⁇ 75 ° C, 3 ⁇ 4 hours of heat preservation Cool down to 40 ° C, IPDI and/or HDI diluted with propylene glycol methyl ether acetate was added dropwise, and the mixture was dropped in 2 to 3 hours.
  • the temperature was kept at 39 to 42 ° C for 2 hours; the temperature was raised to 45 to 49 ° C, and the temperature was maintained for 3 hours; °C, keep warm for 3 hours, measure the NCO content, then measure the NCO value every hour, until the NCO value ⁇ 0.5 reaction is complete; remove some solvent by vacuum, add neutralizer, ethylene glycol monobutyl ether and / or ethylene glycol, Water, adjust the pH to 6 ⁇ 6.5, cooling filter output is the B component.
  • the A composition and the B composition are mixed as formulated.
  • the invention has the beneficial effects that the water-based acrylic resin is prepared as an A component by copolymerizing a modified functional monomer capable of crosslinking the amine group at a low temperature with a common acrylate monomer, and the urethane group can be combined with A.
  • the resin which is cross-linked and cured under low temperature conditions is a B component, which together constitutes an aqueous two-component acrylic-polyurethane resin system, and the obtained coating is flashed for 15 minutes, baked at 80 ° C for 30 minutes, and after cooling, measured Basic performance, film thickness up to 150 microns above the surface of the coating is normal without blistering, pinholes.
  • Example 1 an aqueous two-component acrylic-polyurethane resin is prepared by mixing an A composition and a B composition;
  • the A composition consists of the following components:
  • N-butanol 50g Monoethanolamine 61g; Quinol 0.05g; Glycidyl methacrylate 140g; Methyl methacrylate 65g; Butyl acrylate 65g; Hydroxyethyl acrylate 10g;
  • Azobisisobutyronitrile 6g Ethylene glycol monobutyl ether 80g; Molecular weight regulator (tert-dodecyl mercaptan) 4g; dimethylformamide 24g; Acid neutralizer (formic acid) 13.6g; water 600g;
  • the B composition consists of the following components:
  • Butanone 40g Propylene glycol methyl ether acetate 10g; Butylamine 22.8g; Glycidyl hexahydrophthalate 200g; IPDI 34.6g; Ethylene glycol monobutyl ether 20g; Acid neutralizer (formic acid) 14.4g; water 10g;
  • component A Preparation of component A: adding n-butanol, glycidyl methacrylate and hydroquinone in a 500 ml reactor, heating to 50 ° C, adding monoethanolamine dropwise, dropping in 1 to 2 hours, keeping at 50 ° C for 2 hours; The temperature was raised to 70 ° C, and the temperature was kept for 3 hours.
  • component B Preparation of component B: adding methyl ethyl ketone, hexahydrophthalic acid glycidyl ester in a 500 ml flask, heating to 40 ° C under stirring, starting to add n-butylamine dropwise, the temperature is 40 ° C, 1 hour drop; After heating to 50 ° C, heat for 2 hours; temperature 70 ⁇ 75 ° C, heat for 3 hours; cooling to 40 ° C, began to add IPDI diluted with propylene glycol methyl ether acetate, 2 to 3 hours after the completion of the drop, after the drop 39 ⁇ Incubate at 42 ° C for 2 hours; heat to 45 ° C, heat for 3 hours; heat to 60 ⁇ 64 ° C, heat for 3 hours, measure NCO content, then measure the NCO value every hour, until the NCO value ⁇ 0.5 reaction is complete (after 3 hours, The NCO value is 0.42); a part of the solvent is removed by vacuum, a neutralizing agent, ethylene glyco
  • the A composition and the B composition were mixed in a weight ratio of 4:1, water was added to adjust the viscosity, and sprayed.
  • Example 2 the aqueous two-component acrylic-polyurethane resin is prepared by mixing the A composition and the B composition;
  • the A composition consists of the following components:
  • the B composition consists of the following components:
  • component A 15 g of propylene glycol methyl ether, n-butanol, glycidyl methacrylate and p-hydroxyanisole were added to a 500 ml reactor, heated to 50 ° C, and monoethanolamine was added dropwise, and the mixture was dripped in 1-2 hours. Incubate at 50 ° C for 2 hours; heat up to 70 ° C, keep warm for 3 hours, discharge.
  • component B Preparation of component B: adding butanone, ethyl acetate, glycidyl hexahydrophthalate, glycidyl tetrahydrophthalate in a 500 ml flask, heating to 40 ° C under stirring, and starting to add n-butyl Amine, temperature is 40 ° C, 2 hours drop; after the completion of the drop, the temperature is raised to 50 ° C, heat preservation for 3 hours; temperature 70 ⁇ 72 ° C, heat preservation for 2 hours; temperature drop to 40 ° C, began to drip diluted with propylene glycol methyl ether acetate IPDI, 2 to 3 hours after the completion of the drop, after the completion of the drop of 39 ⁇ 42 ° C for 2 hours; warmed to 45 ° C, heat for 3 hours; warmed to 60 ° C, heat for 3 hours, measured NCO content, then measured NCO value every hour, To the NCO value ⁇ 0.5 reaction is complete (after 3 hours, the NCO value is 0.
  • the A composition and the B composition were mixed in a weight ratio of 6:1, water was added to adjust the viscosity, and sprayed.
  • Example 3 the aqueous two-component acrylic-polyurethane resin is prepared by mixing the A composition and the B composition;
  • the A composition consists of the following components:
  • the B composition consists of the following components:
  • Butanone 40g Propylene glycol methyl ether acetate 8g; Butylamine 22.8g; Glycidyl tetrahydrophthalate 200g; HDI 26.2g; Ethylene glycol 15g; Acid neutralizer (lactic acid) 14.4g; water 10g;
  • component A Add 50g of ethylene glycol monobutyl ether, glycidyl methacrylate and hydroquinone in a 500ml reactor, heat to 50 ° C, add monoethanolamine dropwise, 1-2 hours drop, 50 ° C Insulation for 2 hours; heating to 70 ° C, holding for 3 hours, discharging.
  • component B Preparation of component B: adding butanone, glycidyl tetrahydrophthalate in a 500 ml flask, heating to 40 ° C under stirring, starting to add n-butylamine dropwise, the temperature is 40 ° C, 1 hour dripping; After heating to 50 ° C, heat for 2 hours; temperature 70 ⁇ 75 ° C, heat for 3 hours; cooling to 40 ° C, began to add dropwise diluted with propylene glycol methyl ether acetate HDI, 2 ⁇ 3 hours after the completion of the drop, after the drop 39 ⁇ Incubate at 42 ° C for 2 hours; heat up to 45 ° C, keep warm for 3 hours; heat up to 60 ° C, keep warm for 3 hours, measure NCO content, then measure NCO value every hour, until NCO value ⁇ 0.5 reaction is complete (3 hours later, NCO value It is 0.36); 30 g of solvent is removed by vacuum at 60 ° C, neutralizer, ethylene glycol and water are added to adjust
  • the A composition and the B composition were mixed in a weight ratio of 7:1, water was added to adjust the viscosity, and sprayed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The present invention relates to an aqueous bicomponent acrylic acid-polyurethane resin and a preparation method therefor, comprising, component A: butanol; monoethanolamine and/or butylamine; hydroquinone and/or hydroxyanisole; glycidyl methacrylate; methyl methacrylate and/or isobornyl methacrylate; butyl acrylate and/or butyl methacrylate and/or acrylate laurate ester; hydroxyethyl acrylate; azobisisobutyronitrile; 2-butoxyethanol and/or propylene glycol ether; a molecular weight regulator; dimethylformamide; an acid neutralizer; water; and component B: butanone and/or ethyl acetate; propylene glycol methyl ether acetate; ethanolamine and/or butylamine; hexahydrophthalic acid glycidyl ester and/or tetrahydrophthalic glycidyl ester; IPDI and/or HDI; ethylene glycol monobutyl ether and/or ethylene glycol; an acid neutralizer; water. The weight ratio between component A and component B is 4-7:1. The coating prepared with the resin of the present invention can have a thickness reaching 150 micrometers and above, and has no foam or pinhole.

Description

一种水性双组分丙烯酸-聚氨酯树脂及其制备方法Aqueous two-component acrylic-polyurethane resin and preparation method thereof 技术领域Technical field
本发明涉及一种水性双组分丙烯酸-聚氨酯树脂，该树脂能够在常温固化。本发明还涉及该树脂的制备方法。The present invention relates to an aqueous two-component acrylic-urethane resin which is curable at room temperature. The invention also relates to a process for the preparation of the resin.
背景技术Background technique
双组分聚氨酯体系具有优良的机械性能(涂膜硬度高、附着力强、耐磨性高等)，良好的耐化学品性、耐候性和低温成膜性能，广泛应用于工业防护、木器家具和汽车涂饰等方面。随着各国环保法规的健全和人们环保意识的增强，传统溶剂型双组分聚氨酯中的挥发性有机化合物(VOC)的排放量受到愈来愈严格的限制。而水性双组分聚氨酯涂料则是将溶剂型双组分聚氨酯的高性能涂料和水性涂料的低VOC排放相结合的产物，是一种新的环境友好型型涂料体系。目前的产品主要由含羟基的水性多元醇和含异氰酸酯基的固化剂组成。The two-component polyurethane system has excellent mechanical properties (high hardness of coating film, strong adhesion, high abrasion resistance, etc.), good chemical resistance, weather resistance and low-temperature film forming properties, and is widely used in industrial protection, wood furniture and Automotive finishing and other aspects. With the improvement of environmental regulations in various countries and the increasing awareness of environmental protection, the emission of volatile organic compounds (VOCs) in traditional solvent-based two-component polyurethanes is increasingly restricted. The water-based two-component polyurethane coating is a new environmentally friendly coating system that combines the high-performance coating of solvent-based two-component polyurethane with the low VOC emissions of waterborne coatings. Current products consist primarily of hydroxyl-containing aqueous polyols and isocyanate-containing curing agents.
虽然水性双组分聚氨酯体系的优点比较多，但因为使用的固化剂含有异氰酸酯基团，其存在的一些缺陷也比较明显，也严重限制了它的应用，如：活化期短，混合后异氰酸酯与羟基、水在室温下也会发生反应，而使体系失效，丧失涂膜的交联能力，影响性能。还有异氰酸酯固化过程中与水也比较容易发生反应，产生气体CO2，如果涂膜厚度较大，干燥固化过程中产生的CO2无法顺利排出，或排出较慢，就会在涂膜上形成气泡或针孔，严重影响性能和外观。据调查工业生产上的水性双组分聚氨酯涂料的涂膜一般很难达到80μm以上，还要注意环境中的水分。 Although the advantages of the aqueous two-component polyurethane system are relatively high, because the curing agent used contains isocyanate groups, some defects are also obvious, and its application is severely limited, such as: short activation period, mixed isocyanate and The hydroxyl group and water also react at room temperature, which causes the system to fail, loses the crosslinking ability of the coating film, and affects the performance. In addition, the isocyanate is more likely to react with water during the curing process, and the gas CO 2 is generated. If the thickness of the coating film is large, the CO 2 generated during the drying and solidification process cannot be smoothly discharged, or the discharge is slow, and it will form on the coating film. Bubbles or pinholes that severely affect performance and appearance. According to the investigation, the coating film of the aqueous two-component polyurethane coating on industrial production is generally difficult to reach 80 μm or more, and attention should be paid to the moisture in the environment.
发明内容Summary of the invention
本发明所要解决的技术问题是提供一种水性双组分丙烯酸-聚氨酯树脂及其制备方法。The technical problem to be solved by the present invention is to provide an aqueous two-component acrylic-polyurethane resin and a preparation method thereof.
本发明解决上述技术问题的技术方案如下：一种水性双组分丙烯酸-聚氨酯树脂，由A组合物和B组合物混合制得；The technical solution of the present invention to solve the above technical problems is as follows: an aqueous two-component acrylic-polyurethane resin prepared by mixing A composition and B composition;
所述A组合物由以下组分组成：The A composition consists of the following components:
Figure PCTCN2014089100-appb-000001
Figure PCTCN2014089100-appb-000001
所述B组合物由以下组分组成：The B composition consists of the following components:
Figure PCTCN2014089100-appb-000002
Figure PCTCN2014089100-appb-000002
Figure PCTCN2014089100-appb-000003
Figure PCTCN2014089100-appb-000003
混合时，所述A组合物和所述B组合物的重量配比为4～7:1。When mixed, the weight ratio of the A composition to the B composition is 4 to 7:1.
进一步，如上所述的水性双组分丙烯酸-聚氨酯树脂中，所述分子量调节剂选自3-巯基丙酸异辛酯、正十二烷基硫醇或叔十二烷基硫醇中的一种或多种组成的混合物。Further, in the aqueous two-component acrylic-urethane resin as described above, the molecular weight modifier is selected from one of isooctyl 3-mercaptopropionate, n-dodecyl mercaptan or t-dodecyl mercaptan. a mixture of one or more of the constituents.
如上所述的水性双组分丙烯酸-聚氨酯树脂中，所述酸性中和剂为有机酸。In the aqueous two-component acrylic-polyurethane resin as described above, the acidic neutralizing agent is an organic acid.
优选地，所述有机酸选自甲酸、乙酸或乳酸中的一种或多种组成的混合物。Preferably, the organic acid is selected from the group consisting of one or more of formic acid, acetic acid or lactic acid.
如上所述水性双组分丙烯酸-聚氨酯树脂的制备方法，包括以下步骤：The preparation method of the aqueous two-component acrylic-polyurethane resin as described above includes the following steps:
A组分制备：在反应器中加入正丁醇、甲基丙烯酸缩水甘油酯、对苯二酚和/或对羟基苯甲醚，加热至50℃，滴加单乙醇胺和/或正丁胺，1～2小时滴完，48～52℃保温2小时；升温至70～75℃，保温3～4小时，出料，并与甲基丙烯酸甲酯和/或甲基丙烯酸异冰片酯，丙烯酸丁酯和/或甲基丙烯酸丁酯和/或丙烯酸月桂酸酯，丙烯酸羟乙酯，分子量调节剂，偶氮二异丁腈，二甲基甲酰胺配制成混合液；在另一反应器中加入乙二醇单丁醚和/或丙二醇甲醚，加热至110℃～115℃，开始滴加混合液，3～4小时滴完，保温2～3小时；补加引发剂，保温1～2小时，降温至90～100℃，抽真空除部分溶剂，加入中和剂，水，调PH为6～7，冷却过滤出料即为A组分；Preparation of component A: adding n-butanol, glycidyl methacrylate, hydroquinone and/or p-hydroxyanisole to the reactor, heating to 50 ° C, adding monoethanolamine and / or n-butylamine, After 1 to 2 hours, the mixture is kept at 48-52 ° C for 2 hours; the temperature is raised to 70-75 ° C, and the temperature is kept for 3 to 4 hours. The material is discharged with methyl methacrylate and/or isobornyl methacrylate. Ester and / or butyl methacrylate and / or acrylic acid laurate, hydroxyethyl acrylate, molecular weight regulator, azobisisobutyronitrile, dimethylformamide formulated as a mixture; added in another reactor Ethylene glycol monobutyl ether and / or propylene glycol methyl ether, heated to 110 ° C ~ 115 ° C, began to add the mixed solution, 3 ~ 4 hours after the completion of the dropwise addition, heat preservation for 2 to 3 hours; additional initiator, heat preservation for 1 to 2 hours , cooling to 90 ~ 100 ° C, vacuuming part of the solvent, adding neutralizer, water, adjusting the pH to 6 ~ 7, cooling filter output is the A component;
B组分制备：在反应器中加入丁酮和/或乙酸乙酯，六氢邻苯二甲酸缩水甘油酯和/或四氢邻苯二甲酸缩水甘油酯，搅拌条件下加热至40℃，开始滴加单乙醇胺和/或正丁胺，温度为40～43℃，1～1.5小时滴完；滴完后升温至50～53℃，保温2小时；升温70～75℃，保温3～4小时；降温至40℃， 开始滴加用丙二醇甲醚醋酸酯稀释的IPDI和/或HDI，2～3小时滴完，滴完后39～42℃保温2小时；升温至45～49℃，保温3小时；升温60～64℃，保温3小时，测NCO含量，以后每小时测一次NCO值，至NCO值<0.5反应完全；抽真空除去部分溶剂，加入中和剂，乙二醇单丁醚和/或乙二醇，水，调PH为6～6.5，冷却过滤出料即为B组分。Preparation of component B: adding butanone and/or ethyl acetate, glycidyl hexahydrophthalate and/or glycidyl tetrahydrophthalate to the reactor, heating to 40 ° C under stirring, starting Add monoethanolamine and / or n-butylamine dropwise, the temperature is 40 ~ 43 ° C, 1 ~ 1.5 hours after the completion of the drop; after the completion of the drop to 50 ~ 53 ° C, 2 hours of heat preservation; 70 ~ 75 ° C, 3 ~ 4 hours of heat preservation Cool down to 40 ° C, IPDI and/or HDI diluted with propylene glycol methyl ether acetate was added dropwise, and the mixture was dropped in 2 to 3 hours. After the completion of the dropping, the temperature was kept at 39 to 42 ° C for 2 hours; the temperature was raised to 45 to 49 ° C, and the temperature was maintained for 3 hours; °C, keep warm for 3 hours, measure the NCO content, then measure the NCO value every hour, until the NCO value <0.5 reaction is complete; remove some solvent by vacuum, add neutralizer, ethylene glycol monobutyl ether and / or ethylene glycol, Water, adjust the pH to 6 ~ 6.5, cooling filter output is the B component.
将所述A组合物和所述B组合物按配方混合。The A composition and the B composition are mixed as formulated.
本发明的有益效果是：以可低温交联固化胺基的改性功能单体与普通丙烯酸酯单体共聚制得水性丙烯酸树脂为A组分，以含有氨基甲酸酯基团的可与A组分在低温条件下交联固化的树脂为B组分，共同构成水性双组分丙烯酸-聚氨酯树脂体系，所制得的涂层闪干15分钟，80℃烘烤30分钟，冷却后，测基本性能，膜厚可达150微米以上涂层表面正常无起泡，针孔。The invention has the beneficial effects that the water-based acrylic resin is prepared as an A component by copolymerizing a modified functional monomer capable of crosslinking the amine group at a low temperature with a common acrylate monomer, and the urethane group can be combined with A. The resin which is cross-linked and cured under low temperature conditions is a B component, which together constitutes an aqueous two-component acrylic-polyurethane resin system, and the obtained coating is flashed for 15 minutes, baked at 80 ° C for 30 minutes, and after cooling, measured Basic performance, film thickness up to 150 microns above the surface of the coating is normal without blistering, pinholes.
具体实施方式detailed description
以下结合实施例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。The principles and features of the present invention are described in the following examples, which are intended to be illustrative only and not to limit the scope of the invention.
实施例1Example 1
在实施例1中，水性双组分丙烯酸-聚氨酯树脂由A组合物和B组合物混合制得；In Example 1, an aqueous two-component acrylic-polyurethane resin is prepared by mixing an A composition and a B composition;
所述A组合物由以下组分组成：The A composition consists of the following components:
正丁醇N-butanol 50g；50g;
单乙醇胺Monoethanolamine 61g；61g;
对苯二酚Quinol 0.05g；0.05g;
甲基丙烯酸缩水甘油酯Glycidyl methacrylate 140g；140g;
甲基丙烯酸甲酯Methyl methacrylate 65g；65g;
丙烯酸丁酯Butyl acrylate 65g；65g;
丙烯酸羟乙酯Hydroxyethyl acrylate 10g；10g;
偶氮二异丁腈Azobisisobutyronitrile 6g；6g;
乙二醇单丁醚Ethylene glycol monobutyl ether 80g；80g;
分子量调节剂(叔十二烷基硫醇)Molecular weight regulator (tert-dodecyl mercaptan) 4g；4g;
二甲基甲酰胺dimethylformamide 24g；24g;
酸性中和剂(甲酸)Acid neutralizer (formic acid) 13.6g；13.6g;
水water 600g；600g;
所述B组合物由以下组分组成：The B composition consists of the following components:
丁酮Butanone 40g；40g;
丙二醇甲醚醋酸酯Propylene glycol methyl ether acetate 10g；10g;
正丁胺Butylamine 22.8g；22.8g;
六氢邻苯二甲酸缩水甘油酯Glycidyl hexahydrophthalate 200g；200g;
IPDIIPDI 34.6g；34.6g;
乙二醇单丁醚Ethylene glycol monobutyl ether 20g；20g;
酸性中和剂(甲酸)Acid neutralizer (formic acid) 14.4g；14.4g;
水water 10g；10g;
水性双组分丙烯酸-聚氨酯树脂的制备过程为：The preparation process of the aqueous two-component acrylic-polyurethane resin is:
A组分制备：在500ml反应器中加入正丁醇、甲基丙烯酸缩水甘油酯和对苯二酚，加热至50℃，滴加单乙醇胺，1～2小时滴完，50℃保温2小时；升温至70℃，保温3小时，出料。取出79g与甲基丙烯酸甲酯，丙烯酸丁酯，丙烯酸羟乙酯，分子量调节剂，偶氮二异丁腈，二甲基甲酰胺配制成混合液；在另一1000ml反应器中加入乙二醇单丁醚，加热至110℃，开始滴加混合液，3～4小时滴完，保温2～3小时；降温至100℃，抽真空除部分溶剂，加入中和剂(在本实施例为甲酸)，水，调PH为6～7，冷却过滤出料即为A组合物；Preparation of component A: adding n-butanol, glycidyl methacrylate and hydroquinone in a 500 ml reactor, heating to 50 ° C, adding monoethanolamine dropwise, dropping in 1 to 2 hours, keeping at 50 ° C for 2 hours; The temperature was raised to 70 ° C, and the temperature was kept for 3 hours. Take 79g of methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, molecular weight regulator, azobisisobutyronitrile, dimethylformamide to make a mixture; add ethylene glycol in another 1000ml reactor Monobutyl ether, heated to 110 ° C, began to add the mixture, 3 to 4 hours after the completion of the dropwise addition, heat preservation for 2 to 3 hours; cooling to 100 ° C, vacuum removal of some of the solvent, adding neutralizing agent (in this example formic acid) ), water, adjust the pH to 6 ~ 7, cooling filtered output is the A composition;
B组分制备：在500ml烧瓶中加入丁酮，六氢邻苯二甲酸缩水甘油酯，搅拌条件下加热至40℃，开始滴加正丁胺，温度为40℃，1小时滴完；滴完 后升温至50℃，保温2小时；升温70～75℃，保温3小时；降温至40℃，开始滴加用丙二醇甲醚醋酸酯稀释的IPDI，2～3小时滴完，滴完后39～42℃保温2小时；升温至45℃，保温3小时；升温至60～64℃，保温3小时，测NCO含量，以后每小时测一次NCO值，至NCO值<0.5反应完全(3小时后，NCO值为0.42)；抽真空除去部分溶剂，加入中和剂，乙二醇单丁醚，水，调PH为6～6.5，冷却过滤出料即为B组合物。Preparation of component B: adding methyl ethyl ketone, hexahydrophthalic acid glycidyl ester in a 500 ml flask, heating to 40 ° C under stirring, starting to add n-butylamine dropwise, the temperature is 40 ° C, 1 hour drop; After heating to 50 ° C, heat for 2 hours; temperature 70 ~ 75 ° C, heat for 3 hours; cooling to 40 ° C, began to add IPDI diluted with propylene glycol methyl ether acetate, 2 to 3 hours after the completion of the drop, after the drop 39 ~ Incubate at 42 ° C for 2 hours; heat to 45 ° C, heat for 3 hours; heat to 60 ~ 64 ° C, heat for 3 hours, measure NCO content, then measure the NCO value every hour, until the NCO value <0.5 reaction is complete (after 3 hours, The NCO value is 0.42); a part of the solvent is removed by vacuum, a neutralizing agent, ethylene glycol monobutyl ether, water is added, and the pH is adjusted to 6 to 6.5, and the cooled filtration output is a B composition.
将所述A组合物和所述B组合物按4:1重量比混合，加水调粘度，喷涂施工。The A composition and the B composition were mixed in a weight ratio of 4:1, water was added to adjust the viscosity, and sprayed.
Figure PCTCN2014089100-appb-000004
Figure PCTCN2014089100-appb-000004
实施例2Example 2
在实施例2中，水性双组分丙烯酸-聚氨酯树脂由A组合物和B组合物混合制得；In Example 2, the aqueous two-component acrylic-polyurethane resin is prepared by mixing the A composition and the B composition;
所述A组合物由以下组分组成：
Figure PCTCN2014089100-appb-000005
Figure PCTCN2014089100-appb-000006
The A composition consists of the following components:
Figure PCTCN2014089100-appb-000005
Figure PCTCN2014089100-appb-000006
所述B组合物由以下组分组成：The B composition consists of the following components:
Figure PCTCN2014089100-appb-000007
Figure PCTCN2014089100-appb-000007
水性双组分丙烯酸-聚氨酯树脂的制备过程为：The preparation process of the aqueous two-component acrylic-polyurethane resin is:
A组分制备：在500ml反应器中加入15g丙二醇甲醚，正丁醇、甲基丙烯酸缩水甘油酯和对羟基苯甲醚，加热至50℃，滴加单乙醇胺，1～2小时滴完，50℃保温2小时；升温至70℃，保温3小时，出料。取出82.8g与甲基丙烯酸甲酯，丙烯酸丁酯，丙烯酸月桂酸酯，丙烯酸羟乙酯，分子量调节剂，偶氮二异丁腈，二甲基甲酰胺配制成混合液；在另一1000ml反应器中 加入80g丙二醇甲醚，加热至110℃，开始滴加混合液，3～4小时滴完，保温2～3小时；降温至100℃，抽真空除部分溶剂，加入中和剂(在本实施例为乙酸)，水，调PH为6～7，冷却过滤出料即为A组合物；Preparation of component A: 15 g of propylene glycol methyl ether, n-butanol, glycidyl methacrylate and p-hydroxyanisole were added to a 500 ml reactor, heated to 50 ° C, and monoethanolamine was added dropwise, and the mixture was dripped in 1-2 hours. Incubate at 50 ° C for 2 hours; heat up to 70 ° C, keep warm for 3 hours, discharge. Take 82.8g of methyl methacrylate, butyl acrylate, acrylate laurate, hydroxyethyl acrylate, molecular weight regulator, azobisisobutyronitrile, dimethylformamide to make a mixture; in another 1000ml reaction In the device Add 80g of propylene glycol methyl ether, heat to 110 ° C, start to add the mixture, add 3 to 4 hours, keep warm for 2 to 3 hours; cool down to 100 ° C, vacuum to remove part of the solvent, add neutralizer (in this example) It is acetic acid), water, and the pH is adjusted to 6-7. The cooling and filtering output is the composition A;
B组分制备：在500ml烧瓶中加入丁酮，乙酸乙酯，六氢邻苯二甲酸缩水甘油酯，四氢邻苯二甲酸缩水甘油酯，搅拌条件下加热至40℃，开始滴加正丁胺，温度为40℃，2小时滴完；滴完后升温至50℃，保温3小时；升温70～72℃，保温2小时；降温至40℃，开始滴加用丙二醇甲醚醋酸酯稀释的IPDI，2～3小时滴完，滴完后39～42℃保温2小时；升温至45℃，保温3小时；升温至60℃，保温3小时，测NCO含量，以后每小时测一次NCO值，至NCO值<0.5反应完全(3小时后，NCO值为0.48)；抽真空除去30g溶剂，加入中和剂，乙二醇单丁醚，水，调PH为6～6.5，冷却过滤出料即为B组合物。Preparation of component B: adding butanone, ethyl acetate, glycidyl hexahydrophthalate, glycidyl tetrahydrophthalate in a 500 ml flask, heating to 40 ° C under stirring, and starting to add n-butyl Amine, temperature is 40 ° C, 2 hours drop; after the completion of the drop, the temperature is raised to 50 ° C, heat preservation for 3 hours; temperature 70 ~ 72 ° C, heat preservation for 2 hours; temperature drop to 40 ° C, began to drip diluted with propylene glycol methyl ether acetate IPDI, 2 to 3 hours after the completion of the drop, after the completion of the drop of 39 ~ 42 ° C for 2 hours; warmed to 45 ° C, heat for 3 hours; warmed to 60 ° C, heat for 3 hours, measured NCO content, then measured NCO value every hour, To the NCO value <0.5 reaction is complete (after 3 hours, the NCO value is 0.48); remove 30g of solvent under vacuum, add neutralizer, ethylene glycol monobutyl ether, water, adjust the pH to 6 ~ 6.5, cool the filtered output For the B composition.
将所述A组合物和所述B组合物按6:1重量比混合，加水调粘度，喷涂施工。The A composition and the B composition were mixed in a weight ratio of 6:1, water was added to adjust the viscosity, and sprayed.
Figure PCTCN2014089100-appb-000008
Figure PCTCN2014089100-appb-000008
实施例3Example 3
在实施例3中，水性双组分丙烯酸-聚氨酯树脂由A组合物和B组合物混合制得； In Example 3, the aqueous two-component acrylic-polyurethane resin is prepared by mixing the A composition and the B composition;
所述A组合物由以下组分组成：The A composition consists of the following components:
Figure PCTCN2014089100-appb-000009
Figure PCTCN2014089100-appb-000009
所述B组合物由以下组分组成：The B composition consists of the following components:
丁酮Butanone 40g；40g;
丙二醇甲醚醋酸酯Propylene glycol methyl ether acetate 8g；8g;
正丁胺Butylamine 22.8g；22.8g;
四氢邻苯二甲酸缩水甘油酯Glycidyl tetrahydrophthalate 200g；200g;
HDIHDI 26.2g；26.2g;
乙二醇Ethylene glycol 15g；15g;
酸性中和剂(乳酸)Acid neutralizer (lactic acid) 14.4g；14.4g;
水water 10g；10g;
水性双组分丙烯酸-聚氨酯树脂的制备过程为： The preparation process of the aqueous two-component acrylic-polyurethane resin is:
A组分制备：在500ml反应器中加入50g乙二醇单丁醚，甲基丙烯酸缩水甘油酯和对苯二酚，加热至50℃，滴加单乙醇胺，1～2小时滴完，50℃保温2小时；升温至70℃，保温3小时，出料。取出79g与甲基丙烯酸甲酯，甲基丙烯酸异冰片酯，丙烯酸丁酯，丙烯酸月桂酸酯，丙烯酸羟乙酯，分子量调节剂，偶氮二异丁腈，二甲基甲酰胺配制成混合液；在另一1000ml反应器中加入60g乙二醇单丁醚，丙二醇甲醚，加热至110℃，开始滴加混合液，3～4小时滴完，保温2,小时；降温至100℃，抽真空除部分溶剂，加入中和剂(在本实施例为乳酸)，水，调PH为6～7，冷却过滤出料即为A组合物；Preparation of component A: Add 50g of ethylene glycol monobutyl ether, glycidyl methacrylate and hydroquinone in a 500ml reactor, heat to 50 ° C, add monoethanolamine dropwise, 1-2 hours drop, 50 ° C Insulation for 2 hours; heating to 70 ° C, holding for 3 hours, discharging. Remove 79g from methyl methacrylate, isobornyl methacrylate, butyl acrylate, acrylate laurate, hydroxyethyl acrylate, molecular weight regulator, azobisisobutyronitrile, dimethylformamide Add 60g of ethylene glycol monobutyl ether, propylene glycol methyl ether to another 1000ml reactor, heat to 110 ° C, start to add the mixture, 3-4 hours, and keep warm for 2 hours; cool down to 100 ° C, pump Vacuum part of the solvent, add neutralizer (lactic acid in this example), water, adjust the pH to 6 ~ 7, the cooling filter output is the A composition;
B组分制备：在500ml烧瓶中加入丁酮，四氢邻苯二甲酸缩水甘油酯，搅拌条件下加热至40℃，开始滴加正丁胺，温度为40℃，1小时滴完；滴完后升温至50℃，保温2小时；升温70～75℃，保温3小时；降温至40℃，开始滴加用丙二醇甲醚醋酸酯稀释的HDI，2～3小时滴完，滴完后39～42℃保温2小时；升温至45℃，保温3小时；升温至60℃，保温3小时，测NCO含量，以后每小时测一次NCO值，至NCO值<0.5反应完全(3小时后，NCO值为0.36)；60℃温度下抽真空除去30g溶剂，加入中和剂，乙二醇，水，调PH为6～6.5，冷却过滤出料即为B组合物。Preparation of component B: adding butanone, glycidyl tetrahydrophthalate in a 500 ml flask, heating to 40 ° C under stirring, starting to add n-butylamine dropwise, the temperature is 40 ° C, 1 hour dripping; After heating to 50 ° C, heat for 2 hours; temperature 70 ~ 75 ° C, heat for 3 hours; cooling to 40 ° C, began to add dropwise diluted with propylene glycol methyl ether acetate HDI, 2 ~ 3 hours after the completion of the drop, after the drop 39 ~ Incubate at 42 ° C for 2 hours; heat up to 45 ° C, keep warm for 3 hours; heat up to 60 ° C, keep warm for 3 hours, measure NCO content, then measure NCO value every hour, until NCO value <0.5 reaction is complete (3 hours later, NCO value It is 0.36); 30 g of solvent is removed by vacuum at 60 ° C, neutralizer, ethylene glycol and water are added to adjust the pH to 6 to 6.5, and the cooled filter output is a B composition.
将所述A组合物和所述B组合物按7:1重量比混合，加水调粘度，喷涂施工。The A composition and the B composition were mixed in a weight ratio of 7:1, water was added to adjust the viscosity, and sprayed.
Figure PCTCN2014089100-appb-000010
Figure PCTCN2014089100-appb-000010
Figure PCTCN2014089100-appb-000011
Figure PCTCN2014089100-appb-000011
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalents, improvements, etc., which are within the spirit and scope of the present invention, should be included in the protection of the present invention. Within the scope.

Claims (3)

  1. 一种水性双组分丙烯酸-聚氨酯树脂，由A组合物和B组合物混合制得；An aqueous two-component acrylic-polyurethane resin prepared by mixing A composition and B composition;
    所述A组合物由以下组分组成：The A composition consists of the following components:
    Figure PCTCN2014089100-appb-100001
    Figure PCTCN2014089100-appb-100001
    所述B组合物由以下组分组成：The B composition consists of the following components:
    Figure PCTCN2014089100-appb-100002
    Figure PCTCN2014089100-appb-100002
    Figure PCTCN2014089100-appb-100003
    Figure PCTCN2014089100-appb-100003
    混合时，所述A组合物和所述B组合物的重量配比为4～7:1。When mixed, the weight ratio of the A composition to the B composition is 4 to 7:1.
  2. 根据权利要求1所述的水性双组分丙烯酸-聚氨酯树脂，其特征在于，所述分子量调节剂选自3-巯基丙酸异辛酯、正十二烷基硫醇或叔十二烷基硫醇中的一种或多种组成的混合物。The aqueous two-component acrylic-urethane resin according to claim 1, wherein the molecular weight modifier is selected from the group consisting of isooctyl 3-mercaptopropionate, n-dodecyl mercaptan or t-dodecyl sulfide. a mixture of one or more of the alcohols.
  3. 根据权利要求1或2所述水性双组分丙烯酸-聚氨酯树脂的制备方法，所述制备方法包括以下步骤：The method for preparing an aqueous two-component acrylic-urethane resin according to claim 1 or 2, wherein the preparation method comprises the following steps:
    A组分制备：在反应器中加入正丁醇、甲基丙烯酸缩水甘油酯、对苯二酚和/或对羟基苯甲醚，加热至50℃，滴加单乙醇胺和/或正丁胺，1～2小时滴完，48～52℃保温2小时；升温至70～75℃，保温3～4小时，出料，并与甲基丙烯酸甲酯和/或甲基丙烯酸异冰片酯，丙烯酸丁酯和/或甲基丙烯酸丁酯和/或丙烯酸月桂酸酯，丙烯酸羟乙酯，分子量调节剂，偶氮二异丁腈，二甲基甲酰胺配制成混合液；在另一反应器中加入乙二醇单丁醚和/或丙二醇甲醚，加热至110℃～115℃，开始滴加混合液，3～4小时滴完，保温2～3小时；补加引发剂，保温1～2小时，降温至90～100℃，抽真空除部分溶剂，加入中和剂，水，调PH为6～7，冷却过滤出料即为A组分；Preparation of component A: adding n-butanol, glycidyl methacrylate, hydroquinone and/or p-hydroxyanisole to the reactor, heating to 50 ° C, adding monoethanolamine and / or n-butylamine, After 1 to 2 hours, the mixture is kept at 48-52 ° C for 2 hours; the temperature is raised to 70-75 ° C, and the temperature is kept for 3 to 4 hours. The material is discharged with methyl methacrylate and/or isobornyl methacrylate. Ester and / or butyl methacrylate and / or acrylic acid laurate, hydroxyethyl acrylate, molecular weight regulator, azobisisobutyronitrile, dimethylformamide formulated as a mixture; added in another reactor Ethylene glycol monobutyl ether and / or propylene glycol methyl ether, heated to 110 ° C ~ 115 ° C, began to add the mixed solution, 3 ~ 4 hours after the completion of the dropwise addition, heat preservation for 2 to 3 hours; additional initiator, heat preservation for 1 to 2 hours , cooling to 90 ~ 100 ° C, vacuuming part of the solvent, adding neutralizer, water, adjusting the pH to 6 ~ 7, cooling filter output is the A component;
    B组分制备：在反应器中加入丁酮和/或乙酸乙酯，六氢邻苯二甲酸缩水甘油酯和/或四氢邻苯二甲酸缩水甘油酯，搅拌条件下加热至40℃，开始滴加单乙醇胺和/或正丁胺，温度为40～43℃，1～1.5小时滴完；滴完后升温至50～53℃，保温2小时；升温70～75℃，保温3～4小时；降温至40℃，开始滴加用丙二醇甲醚醋酸酯稀释的IPDI和/或HDI，2～3小时滴完，滴完后39～42℃保温2小时；升温至45～49℃，保温3小时；升温60～64℃，保温3小时，测NCO含量，以后每小时测一次NCO值，至NCO值<0.5反应完全；抽真空除去部分溶剂，加入中和剂，乙二醇单丁醚和/或乙二醇，水， 调PH为6～6.5，冷却过滤出料即为B组分；Preparation of component B: adding butanone and/or ethyl acetate, glycidyl hexahydrophthalate and/or glycidyl tetrahydrophthalate to the reactor, heating to 40 ° C under stirring, starting Add monoethanolamine and / or n-butylamine dropwise, the temperature is 40 ~ 43 ° C, 1 ~ 1.5 hours after the completion of the drop; after the completion of the drop to 50 ~ 53 ° C, 2 hours of heat preservation; 70 ~ 75 ° C, 3 ~ 4 hours of heat preservation After cooling to 40 ° C, IPDI and / or HDI diluted with propylene glycol methyl ether acetate was added dropwise, and the mixture was dropped in 2 to 3 hours. After the completion of the dropping, the temperature was kept at 39 to 42 ° C for 2 hours; the temperature was raised to 45 to 49 ° C, and the temperature was maintained. Hour; heat up 60 ~ 64 ° C, heat for 3 hours, measure NCO content, then measure the NCO value every hour, until the NCO value <0.5 reaction is complete; vacuum to remove part of the solvent, add neutralizer, ethylene glycol monobutyl ether and / or ethylene glycol, water, Adjust the pH to 6~6.5, and cool the filtered output as the B component;
    将所述A组合物和所述B组合物按配方混合。 The A composition and the B composition are mixed as formulated.
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