WO2018041128A1 - 一种水性氨基烤漆及其制备方法 - Google Patents

一种水性氨基烤漆及其制备方法 Download PDF

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WO2018041128A1
WO2018041128A1 PCT/CN2017/099629 CN2017099629W WO2018041128A1 WO 2018041128 A1 WO2018041128 A1 WO 2018041128A1 CN 2017099629 W CN2017099629 W CN 2017099629W WO 2018041128 A1 WO2018041128 A1 WO 2018041128A1
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Prior art keywords
aqueous
epoxy resin
polyester resin
agent
baking varnish
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PCT/CN2017/099629
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English (en)
French (fr)
Inventor
胡中源
董立志
程璐
郑齐
祁艳东
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河北晨阳工贸集团有限公司
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Priority to US16/329,438 priority Critical patent/US20190218417A1/en
Publication of WO2018041128A1 publication Critical patent/WO2018041128A1/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
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid groups
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
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    • C08K5/00—Use of organic ingredients
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    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
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    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
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    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/45—Anti-settling agents
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    • 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
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80—Processes for incorporating ingredients
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    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1472—Fatty acids
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
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Definitions

  • the present invention relates to the field of coating compositions.
  • coatings generally use organic solvents as raw materials. Such coatings not only cause a large amount of organic solvent emissions, but also endanger the health of operators, and pose a major hidden danger to environmental safety.
  • the technical problem to be solved by the present invention is to provide an aqueous amino baking varnish and a preparation method thereof, the water-based amino baking varnish is water-friendly, has good stability, high hardness, can be multi-coated, has strong adhesion, fast drying, and protects It has strong lightness, excellent aging resistance, good water resistance, convenient construction, low cost, non-combustible, non-explosive, pollution-free, and low-temperature storage. It also has the characteristics of convenient and quick construction, smooth and smooth paint film and good hand feeling.
  • the technical solution adopted by the present invention is: an aqueous amino baking varnish
  • the aqueous amino baking varnish is made by the following raw material ratio, calculated as: 25-40% of water-based poly Ester resin, 4-5% aqueous epoxy resin, 7-10% aqueous amino resin, 25-35% deionized water, 1. 5-2.5% pH adjuster, 0.3-0.5 ⁇ 3 ⁇ 4 wetting Agent, 0.2-0.6% antifoaming agent, 0.5-1% dispersant, 1-5% cosolvent, 10-20% pigment filler, 2-5% nano alumina, 0.3-0.5% silicon Lithium magnesium hydride, 0.3-0.5% thickener, 0.5-0.8% leveling agent; uniformly prepared by mixing and stirring.
  • the aqueous polyester resin is obtained by copolymerizing an aqueous branched polyester resin and a glycidyl tert-carbonate, and the aqueous polyester resin has an acid value of 40 to 50 mgKOH/g.
  • the preparation method of the aqueous polyester resin is: an aqueous branched polyester resin having an acid value of 50-60 mgKOH/g, adding glycidyl tert-carbonate, and copolymerizing at 120-150 ° C, The acid value to the end point was 40-50 mgKOH/g, and an aqueous polyester resin was obtained.
  • the aqueous epoxy resin is polymerized from a low iodine value fatty acid and an epoxy resin to form a fatty acid-modified epoxy resin having a secondary hydroxyl group, and has an acid value of ⁇ 5 mgKOH/g.
  • the preparation method of the aqueous epoxy resin is: low iodine value fatty acid and epoxy resin in 100-
  • the low iodine value fatty acid and the epoxy resin are polymerized at 120 ° C; the mass ratio of the epoxy resin to the low iodine fatty acid is 2-2.5: 1, and the iodine value of the low iodine fatty acid is ⁇ 70 g /100g.
  • the wetting agent is a polyether modified silicone wetting agent
  • the defoaming agent is a polyether modified siloxane copolymer defoamer containing fumed silica
  • the dispersing agent is a polyether a phosphate ester anionic compound
  • the co-solvent is one or two of dipropylene glycol methyl ether and ethylene glycol monobutyl ether
  • the thickener is a nonionic associative polyurethane thickener, an acrylic acid and an acrylate copolymer Two of the alkali-swellable thickeners
  • the leveling agent is a high molecular weight polydimethylsiloxane emulsion.
  • a method for preparing an aqueous amino baking varnish comprising the steps of:
  • the preparation method of the aqueous amino baking varnish comprises the following steps:
  • the aqueous amino baking varnish of the present invention can be widely applied to tricycles, bicycles, electric vehicles, motorcycles, small electric vehicles, and the like.
  • the aqueous amino baking paint product of the invention has the advantages of water-saving environmental protection, good stability, high hardness, multi-pass coating, strong adhesion, fast drying, strong gloss retention, excellent aging resistance, good water resistance, construction Convenient, low cost, non-combustible, non-explosive, pollution-free, low-temperature storage does not deteriorate. It also has the characteristics of convenient and quick construction, smooth and smooth paint film and good hand feeling.
  • the aqueous amino baking varnish of the invention adopts an aqueous polyester resin to make the lacquer film have high hardness, high gloss and high fullness, and has good storage stability and water resistance, and the inside of the molecule
  • the tertiary carbon structure can effectively shield the hydrolysis of the esterification point in the molecular structure of the branched polyester, improve the storage stability and water resistance of the product, and improve the storage stability and water resistance of the product;
  • the modification of the molecular structure of the aqueous polyester resin is easy to hydrolyze and the stability is not good.
  • the aqueous amino baking varnish of the invention adopts a water-based epoxy resin, and the polyester resin is circumvented by low iodine value fatty acid modification under the premise that the epoxy resin improves the adhesion to the substrate and the flexibility of the paint film.
  • Epoxy resin mixed spells due to compatibility problems caused by the decrease in gloss and fullness, ensuring the apparent effect of the paint film; the addition of low iodine value fatty acids in the molecular structure also effectively improves the hydrophobicity of the paint film.
  • the aqueous amino baking varnish of the invention is combined with a nano-scale filler-nano-alumina ( ⁇ - ⁇ 1 2 0 3 ;), which is filled in the paint film, and has obvious toughness, scratch resistance and impact resistance to the paint film. It is improved, and its particle size is nanometer. It can be added to the topcoat without affecting the gloss and fullness of the paint film. It is suitable for the waterborne topcoat coating system with large impact probability of stone body such as car body.
  • the aqueous amino baking varnish of the invention adopts a method of compounding an aqueous polyester resin and an aqueous epoxy resin, and improves the coating on the substrate under the apparent demand of high gloss, high fullness and high hardness of the user. Attachment Force, water resistance and storage stability, water-resistant 240h paint film without abnormalities.
  • the aqueous amino baking varnish of the invention is used in combination with lithium magnesium silicate and a thickener to solve the problem of poor stability of the water-based paint, and there is no abnormality in the heat storage at 50 ° C for more than 30 days.
  • An aqueous amino baking varnish is made by the following raw material ratio, calculated as: 25% aqueous polyester resin, 5% aqueous epoxy resin, 9% aqueous amino resin 35% deionized water, 2% pH adjuster, 0.3% wetting agent, 0.4% antifoam, 0.5% dispersant, 2% cosolvent, 17.1% pigment and filler, 2% Nano-alumina, 0.5% lithium magnesium silicate, 0.4% thickener, 0.8% leveling agent.
  • the preparation method of the aqueous polyester resin is: an aqueous branched polyester resin having an acid value of 50 mgKOH/g, adding glycidyl tert-carbonate, copolymerization modification at 120 ° C for 0.5 h, to an acid value of 40 mg KOH at the end point. /g, an aqueous polyester resin is obtained.
  • the mass ratio of the aqueous branched polyester resin to the glycidyl tert-carbonate was 8.5:1.
  • the preparation method of the aqueous epoxy resin is as follows: a low iodine value fatty acid and an epoxy resin are polymerized at 120 ° C for 2 h to an end point acid value of 5 mg KOH / g to form a fatty acid-modified epoxy resin having a secondary hydroxyl group.
  • the mass ratio of epoxy resin to low iodine fatty acid is 2.2: 1, and the iodine value of low iodine fatty acid is ⁇ 70g/100g.
  • the wetting agent is a polyether modified silicone wetting agent;
  • the defoaming agent is a polyether modified siloxane copolymer defoamer containing fumed silica;
  • the dispersing agent is a polyether phosphate system Anionic compound; cosolvent is dipropylene glycol methyl ether; thickener is nonionic association type polyurethane thickener, alkali swellable thickener of acrylic acid and acrylate copolymer (nonionic in thickener)
  • the weight ratio of the associative polyurethane thickener to the alkali swellable thickener of the acrylic acid and acrylate copolymer is 2:1);
  • the leveling agent is a high molecular weight polydimethylsiloxane emulsion.
  • a method for preparing an aqueous amino baking varnish comprising the steps of:
  • the aqueous polyester resin, deionized water, pH adjuster, wetting agent, antifoaming agent are sequentially added to the paint mixing tank, and stirred at 800-1000 rpm;
  • An aqueous amino baking varnish is made by the following raw material ratio, calculated as: 30% aqueous polyester resin, 4% aqueous epoxy resin, 7% aqueous amino resin 28.8 ⁇ 3 ⁇ 4 deionized water, 1.5% pH adjuster, 0.4% wetting agent, 0.2% defoamer, 0.7% dispersion ij, 1% cosolvent, 20% pigment and filler, 5 % nano-alumina, 0.4% lithium magnesium silicate, 0.3% thickener, 0.7% leveling agent.
  • the preparation method of the aqueous polyester resin is: an aqueous branched polyester resin having an acid value of 60 mgKOH/g, adding glycidyl tert-carbonate, copolymerization modification at 130 ° C for 0.5 h, to an acid value of 50 mg KOH at the end point. /g, an aqueous polyester resin is obtained.
  • the mass ratio of the aqueous branched polyester resin to the glycidyl tert-carbonate was 9:1.
  • the preparation method of the aqueous epoxy resin is as follows: a low iodine value fatty acid and an epoxy resin are polymerized at 100 ° C for 3 h to an end point acid value of 4 mg KOH / g to form a fatty acid-modified epoxy resin having a secondary hydroxyl group.
  • the mass ratio of epoxy resin to low iodine fatty acid is 2.5: 1, and the iodine value of low iodine fatty acid is ⁇ 70g/100g.
  • the wetting agent is a polyether modified silicone wetting agent;
  • the defoaming agent is a polyether modified siloxane copolymer defoamer containing fumed silica;
  • the dispersing agent is a polyether phosphate system Anionic compound;
  • cosolvent is ethylene glycol monobutyl ether;
  • thickener is nonionic association type polyurethane thickener, alkali swellable thickener of acrylic acid and acrylate copolymer (in thickener
  • the weight ratio of the nonionic associative polyurethane thickener to the alkali swellable thickener of the acrylic acid and acrylate copolymer is 2:1);
  • the leveling agent is a high molecular weight polydimethylsiloxane emulsion.
  • An aqueous amino baking varnish is made by the following raw material ratio, calculated as: 35% aqueous polyester resin, 4.5% aqueous epoxy resin, 10% aqueous amino resin , 26 ⁇ 3 ⁇ 4 deionized water, 2.5% pH adjustment, ij, 0.3% wetting agent, 0.5% defoamer, 0.8% dispersion Qi ij, 5% cosolvent, 11% pigment filler, 3% nano alumina, 0.3% lithium magnesium silicate, 0.5% thickener, 0.6% leveling agent.
  • the preparation method of the aqueous polyester resin is: an aqueous branched polyester resin having an acid value of 55 mgKOH/g, adding glycidyl tert-carbonate, copolymerization modification at 140 ° C for 0.5 h, to an acid value of 45 mg KOH at the end point. /g, an aqueous polyester resin is obtained.
  • the mass ratio of the aqueous branched polyester resin to the glycidyl tert-carbonate was 8.8:1.
  • the preparation method of the aqueous epoxy resin is as follows: a low iodine value fatty acid and an epoxy resin are polymerized at 110 ° C for 2.5 h to an end point acid value of 3 mg KOH / g to form a fatty acid-modified epoxy resin having a secondary hydroxyl group.
  • the mass ratio of epoxy resin to low iodine fatty acid is 2: 1, and the iodine value of low iodine fatty acid is ⁇ 70g/100g.
  • the wetting agent is a polyether modified silicone wetting agent;
  • the defoaming agent is a polyether modified siloxane copolymer defoamer containing fumed silica;
  • the dispersing agent is a polyether phosphate system Anionic compound;
  • the co-solvent is two of dipropylene glycol methyl ether and ethylene glycol monobutyl ether (weight ratio of dipropylene glycol methyl ether to ethylene glycol monobutyl ether is 1:1)
  • Thickeners are two types of nonionic associative polyurethane thickeners, alkali swellable thickeners of acrylic acid and acrylate copolymers (nonionic associative polyurethane thickeners with acrylic acid and acrylic acid in thickeners)
  • the weight ratio of the alkali-swelling thickener of the ester copolymer is 2:1; the leveling agent is a high molecular weight polydimethylsiloxane emulsion.
  • the preparation method was the same as in Example 1.
  • An aqueous amino baking varnish is made by the following raw material ratio, calculated as:
  • aqueous polyester resin 40% aqueous polyester resin, 4.9% waterborne epoxy resin, 8% aqueous amino resin, 25% deionized water, 1.5% pH adjuster, 0.5% wetting agent, 0.6% defoamer 1% dispersant, 3% cosolvent, 10% pigment filler, 4% nano alumina, 0.5% lithium magnesium silicate, 0.5% thickener, 0.5% leveling agent.
  • the preparation method of the aqueous polyester resin is: an aqueous branched polyester resin having an acid value of 50 mgKOH/g, adding glycidyl tert-carbonate, copolymerization modification at 150 ° C for 0.5 h, to an acid value of 42 mg KOH at the end point. /g, an aqueous polyester resin is obtained.
  • the mass ratio of the aqueous branched polyester resin to the glycidyl tert-carbonate was 8.7:1.
  • the preparation method of the aqueous epoxy resin is as follows: a low iodine value fatty acid and an epoxy resin are polymerized at 120 ° C for 3 h to an acid value of 2 mg KOH / g at the end point to form a fatty acid-modified epoxy resin having a secondary hydroxyl group.
  • Epoxy resin and low iodine The mass ratio of the fatty acids is 2.4: 1, and the iodine value of the low iodine fatty acid is ⁇ 70 g/100 g.
  • the wetting agent is a polyether modified silicone wetting agent;
  • the defoaming agent is a polyether modified siloxane copolymer defoamer containing fumed silica;
  • the dispersing agent is a polyether phosphate system Anionic compound; cosolvent is dipropylene glycol methyl ether; thickener is nonionic association type polyurethane thickener, alkali swellable thickener of acrylic acid and acrylate copolymer (nonionic in thickener)
  • the weight ratio of the associative polyurethane thickener to the alkali swellable thickener of the acrylic acid and acrylate copolymer is 2:1);
  • the leveling agent is a high molecular weight polydimethylsiloxane emulsion.
  • Adhesion ⁇ 1 cross-cut test lmm
  • the water-based amino baking paint product of the invention has the advantages of water-saving, good stability, high hardness, multi-coating, strong adhesion, fast drying, strong gloss retention, excellent aging resistance, good water resistance, convenient construction and cost. Low, non-combustible, non-explosive, pollution-free, low-temperature storage does not deteriorate. It also has the characteristics of convenient and quick construction, smooth and smooth paint film and good hand feeling.

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Abstract

一种水性氨基烤漆，按重量百分比含量由以下原材料经混合搅拌均匀制成：25-40％的水性聚酯树脂、4-5％的水性环氧树脂、7-10％的水性氨基树脂、25-35％的去离子水、1.5-2.5％的pH调节剂、0.3-0.5％的润湿剂、0.2-0.6％的消泡剂、0.5-1％的分散剂、1-5％的助溶剂、10-20％的颜填料、2-5％的纳米氧化铝、0.3-0.5％的硅酸镁锂、0.3-0.5％的增稠剂、0.5-0.8％的流平剂。

Description

说明书 发明名称：一种水性氨基烤漆及其制备方法 技术领域
[0001] 本发明涉及涂料组合物技术领域落。
背景技术
[0002] 日益发展的现代涂料行业， 对环境保护要求越来越高。 减少有机溶剂的排放， 既保护环境， 又降低成本， 对操作人员的健康安全也更有保障。
[0003] 目前， 涂料一般采用有机溶剂为原料， 这种涂料不仅会造成大量的有机溶剂排 放造成污染， 还会危害操作者的健康， 为环境安全问题埋下了重大隐患。
技术问题
[0004] 本发明要解决的技术问题是提供一种水性氨基烤漆及其制备方法， 该水性氨基 烤漆水性环保、 稳定性好、 硬度高、 可多道涂装、 附着力强、 干燥快、 保光性 强、 耐老化性优异、 耐水性好， 施工方便， 成本低， 不燃、 不爆、 无公害、 低 温贮存不变质。 还具有施工方便快捷、 漆膜平整光滑、 手感俱佳等特点。
问题的解决方案
技术解决方案
[0005] 为解决上述技术问题， 本发明所采取的技术方案是： 一种水性氨基烤漆， 水性 氨基烤漆是由以下原材料配比制成的， 按重量百分比计算为： 25-40%的水性聚 酯树脂、 4-5%的水性环氧树脂、 7-10%的水性氨基树脂、 25-35%的去离子水、 1. 5-2.5%的 pH调节剂、 0.3-0.5<¾的润湿剂、 0.2-0.6%的消泡剂、 0.5-1%的分散剂、 1 -5%的助溶剂、 10-20%的颜填料、 2-5%的纳米氧化铝、 0.3-0.5%的硅酸镁锂、 0.3 -0.5%的增稠剂、 0.5-0.8%的流平剂； 经混合搅拌均匀制成的。
[0006] 优选的， 水性聚酯树脂由水性支链型聚酯树脂与叔碳酸缩水甘油酯共聚而成， 水性聚酯树脂酸值为 40-50mgKOH/g。
[0007] 进一步优选的， 水性聚酯树脂的制备方法为： 酸值 50-60mgKOH/g的水性支链 型聚酯树脂， 加入叔碳酸缩水甘油酯， 在 120-150°C进行共聚改性， 至终点酸值 为 40-50mgKOH/g， 得到水性聚酯树脂。 [0008] 更进一步优选的， 水性支链型聚酯树脂与叔碳酸缩水甘油酯的质量比为 8.5-9: 1 =
[0009] 优选的， 水性环氧树脂由低碘值脂肪酸与环氧树脂聚合， 形成带有仲羟基的脂 肪酸改性环氧树脂， 酸值≤5mgKOH/g。
[0010] 进一步优选的， 水性环氧树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 100-
120°C下聚合， 至终点酸值≤5mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂
[0011] 更进一步优选的， 低碘值脂肪酸与环氧树脂在 120°C下聚合； 环氧树脂与低碘 值脂肪酸的质量比为 2-2.5: 1， 低碘值脂肪酸的碘值≤70g/100g。
[0012] 优选的， 润湿剂为聚醚改性聚硅氧烷润湿剂； 消泡剂为含气相二氧化硅的聚醚 改性硅氧烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为 二丙二醇甲醚和乙二醇单丁醚中的一种或两种； 增稠剂为非离子缔合型聚氨酯 增稠剂、 丙烯酸和丙烯酸酯共聚物的碱溶胀型增稠剂中的两种； 流平剂为高分 子量聚二甲基硅氧烷乳液。
[0013] 水性氨基烤漆的制备方法， 包括以下步骤：
[0014] (1) 按配比， 将水性聚酯树脂、 去离子水、 pH调节剂、 润湿剂、 消泡剂加入 调漆缸中， 搅拌；
[0015] (2) 加入分散剂、 颜填料、 硅酸镁锂、 纳米氧化铝， 搅拌；
[0016] (3) 加入助溶剂， 搅拌；
[0017] (4) 将水性氨基树脂、 水性环氧树脂、 流平剂、 消泡剂加入， 搅拌， 测初始 粘度， 根据初始粘度， 加入增稠剂进行增稠至 25°C、 斯托默粘度计 80-90KU, 得 到水性氨基烤漆。
[0018] 优选的， 水性氨基烤漆的制备方法， 包括以下步骤：
[0019] (1) 按配比， 依次将水性聚酯树脂、 去离子水、 pH调节剂、 润湿剂、 消泡剂 加入调漆缸中， 以 800-1000rpm的速度搅拌；
[0020] (2) 加入分散剂、 颜填料、 硅酸镁锂、 纳米氧化铝， 以 1000-1200rpm的速度 搅拌 20分钟， 研磨细度≤15 ！^
[0021] (3) 加入助溶剂， 以 1000-1200rpm的速度搅拌 10分钟； [0022] (4) 依次将水性氨基树脂、 水性环氧树脂、 流平剂、 消泡剂加入， 以 600-800r pm的速度搅拌， 测初始粘度， 根据初始粘度， 加入增稠剂进行增稠至 25°C、 斯 托默粘度计 80-90KU, 得到水性氨基烤漆。
[0023] 本发明水性氨基烤漆可广泛应用于三轮车、 自行车、 电动车、 摩托车、 小型电 动汽车等。
发明的有益效果
有益效果
[0024] 采用上述技术方案所产生的有益效果在于：
[0025] (1) 本发明水性氨基烤漆产品水性环保、 稳定性好、 硬度高、 可多道涂装、 附着力强、 干燥快、 保光性强、 耐老化性优异、 耐水性好， 施工方便， 成本低 ， 不燃、 不爆、 无公害、 低温贮存不变质。 还具有施工方便快捷、 漆膜平整光 滑、 手感俱佳等特点。
[0026] (2) 本发明水性氨基烤漆采用水性聚酯树脂使漆膜在具有高硬度、 高光泽和 高丰满度的同吋， 又具有很好的储存稳定性和耐水性， 其分子内部的叔碳结构 ， 在提高漆膜丰满度的同吋， 亦可有效屏蔽支链型聚酯分子结构内酯化点的水 解性， 提高产品的储存稳定性和耐水性； 其解决了目前水性氨基涂料在实际应 用中对比溶剂性涂料光泽度、 丰满度较差的问题， 又通过改性手段解决了水性 聚酯树脂其分子结构易水解、 稳定性不佳问题。
[0027] (3) 本发明水性氨基烤漆采用水性环氧树脂， 在环氧树脂提高对基材附着力 、 漆膜柔韧性等前提下， 通过低碘值脂肪酸改性， 规避了聚酯树脂与环氧树脂 混拼因相容性问题造成的光泽度、 丰满度下降， 保证了漆膜的表观效果； 其分 子结构中低碘值脂肪酸的加入， 也有效提高了漆膜的疏水性。
[0028] (4) 本发明水性氨基烤漆配合纳米级填充料一纳米氧化铝 (α-Α1 20 3；)， 其填 充于漆膜中， 对漆膜韧性、 抗刮擦及冲击性有明显提高， 且其粒径为纳米级， 在面漆涂层中加入不影响漆膜光泽度及丰满度， 适用于车体等石砂冲击几率较 大的水性面漆涂料体系。
[0029] (5) 本发明水性氨基烤漆采用水性聚酯树脂和水性环氧树脂复配的方法， 在 满足用户高光泽、 高丰满度、 高硬度等表观需求下， 提高了涂料对基材的附着 力、 耐水性及储存稳定性， 耐水 240h漆膜无异常。
[0030] (6) 本发明水性氨基烤漆选用硅酸镁锂、 增稠剂配合使用， 解决水性漆稳定 性差的问题， 50°C热储存 30天以上无异常现象。
实施该发明的最佳实施例
本发明的最佳实施方式
[0031] 下面结合具体实施方式对本发明作进一步详细的说明。
[0032] 实施例 1
[0033] 一种水性氨基烤漆， 水性氨基烤漆是由以下原材料配比制成的， 按重量百分比 计算为： 25%的水性聚酯树脂、 5%的水性环氧树脂、 9%的水性氨基树脂、 35% 的去离子水、 2%的 pH调节剂、 0.3%的润湿剂、 0.4%的消泡剂、 0.5%的分散剂、 2%的助溶剂、 17.1%的颜填料、 2%的纳米氧化铝、 0.5%的硅酸镁锂、 0.4%的增 稠剂、 0.8%的流平剂。
[0034] 水性聚酯树脂的制备方法为： 酸值 50mgKOH/g的水性支链型聚酯树脂， 加入叔 碳酸缩水甘油酯， 在 120°C进行共聚改性 0.5h， 至终点酸值为 40mgKOH/g， 得到 水性聚酯树脂。 水性支链型聚酯树脂与叔碳酸缩水甘油酯的质量比为 8.5: 1。
[0035] 水性环氧树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 120°C下聚合 2h， 至 终点酸值 5mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂。 环氧树脂与低碘 值脂肪酸的质量比为 2.2: 1， 低碘值脂肪酸的碘值≤70g/100g。
[0036] 润湿剂为聚醚改性聚硅氧烷润湿剂； 消泡剂为含气相二氧化硅的聚醚改性硅氧 烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为二丙二醇 甲醚； 增稠剂为非离子缔合型聚氨酯增稠剂、 丙烯酸和丙烯酸酯共聚物的碱溶 胀型增稠剂中的两种 （增稠剂中非离子缔合型聚氨酯增稠剂与丙烯酸和丙烯酸 酯共聚物的碱溶胀型增稠剂的重量比为 2:1) ； 流平剂为高分子量聚二甲基硅氧 烷乳液。
[0037] 水性氨基烤漆的制备方法， 包括以下步骤：
[0038] (1) 按配比， 依次将水性聚酯树脂、 去离子水、 pH调节剂、 润湿剂、 消泡剂 加入调漆缸中， 以 800-1000rpm的速度搅拌；
[0039] (2) 加入分散剂、 颜填料、 硅酸镁锂、 纳米氧化铝， 以 1000-1200rpm的速度 搅拌 20分钟， 研磨细度≤15 ！^
[0040] (3) 加入助溶剂， 以 1000-1200rpm的速度搅拌 10分钟；
[0041] (4) 依次将水性氨基树脂、 水性环氧树脂、 流平剂、 消泡剂加入， 以 600-SOOr pm的速度搅拌， 测初始粘度， 根据初始粘度， 加入增稠剂进行增稠至 25°C、 斯 托默粘度计 80-90KU, 得到水性氨基烤漆。
[0042] 实施例 2
[0043] 一种水性氨基烤漆， 水性氨基烤漆是由以下原材料配比制成的， 按重量百分比 计算为： 30%的水性聚酯树脂、 4%的水性环氧树脂、 7%的水性氨基树脂、 28.8 <¾的去离子水、 1.5%的 pH调节剂、 0.4%的润湿剂、 0.2%的消泡剂、 0.7%的分散 齐 ij、 1%的助溶剂、 20%的颜填料、 5%的纳米氧化铝、 0.4%的硅酸镁锂、 0.3%的 增稠剂、 0.7%的流平剂。
[0044] 水性聚酯树脂的制备方法为： 酸值 60mgKOH/g的水性支链型聚酯树脂， 加入叔 碳酸缩水甘油酯， 在 130°C进行共聚改性 0.5h， 至终点酸值为 50mgKOH/g， 得到 水性聚酯树脂。 水性支链型聚酯树脂与叔碳酸缩水甘油酯的质量比为 9: 1。
[0045] 水性环氧树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 100°C下聚合 3h， 至 终点酸值 4mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂。 环氧树脂与低碘 值脂肪酸的质量比为 2.5: 1， 低碘值脂肪酸的碘值≤70g/100g。
[0046] 润湿剂为聚醚改性聚硅氧烷润湿剂； 消泡剂为含气相二氧化硅的聚醚改性硅氧 烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为乙二醇单 丁醚； 增稠剂为非离子缔合型聚氨酯增稠剂、 丙烯酸和丙烯酸酯共聚物的碱溶 胀型增稠剂中的两种 （增稠剂中非离子缔合型聚氨酯增稠剂与丙烯酸和丙烯酸 酯共聚物的碱溶胀型增稠剂的重量比为 2:1) ； 流平剂为高分子量聚二甲基硅氧 烷乳液。
[0047] 制备方法同实施例 1。
[0048] 实施例 3
[0049] 一种水性氨基烤漆， 水性氨基烤漆是由以下原材料配比制成的， 按重量百分比 计算为： 35%的水性聚酯树脂、 4.5%的水性环氧树脂、 10%的水性氨基树脂、 26 <¾的去离子水、 2.5%的 pH调节齐 ij、 0.3%的润湿剂、 0.5%的消泡剂、 0.8%的分散 齐 ij、 5%的助溶剂、 11%的颜填料、 3%的纳米氧化铝、 0.3%的硅酸镁锂、 0.5%的 增稠剂、 0.6%的流平剂。
[0050] 水性聚酯树脂的制备方法为： 酸值 55mgKOH/g的水性支链型聚酯树脂， 加入叔 碳酸缩水甘油酯， 在 140°C进行共聚改性 0.5h， 至终点酸值为 45mgKOH/g， 得到 水性聚酯树脂。 水性支链型聚酯树脂与叔碳酸缩水甘油酯的质量比为 8.8: 1。
[0051] 水性环氧树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 110°C下聚合 2.5h， 至 终点酸值 3mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂。 环氧树脂与低碘 值脂肪酸的质量比为 2: 1， 低碘值脂肪酸的碘值≤70g/100g。
[0052] 润湿剂为聚醚改性聚硅氧烷润湿剂； 消泡剂为含气相二氧化硅的聚醚改性硅氧 烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为二丙二醇 甲醚和乙二醇单丁醚中的两种 （二丙二醇甲醚和乙二醇单丁醚的重量比为 1:1)
； 增稠剂为非离子缔合型聚氨酯增稠剂、 丙烯酸和丙烯酸酯共聚物的碱溶胀型 增稠剂中的两种 （增稠剂中非离子缔合型聚氨酯增稠剂与丙烯酸和丙烯酸酯共 聚物的碱溶胀型增稠剂的重量比为 2:1) ； 流平剂为高分子量聚二甲基硅氧烷乳 液。
[0053] 制备方法同实施例 1。
[0054] 实施例 4
[0055] 一种水性氨基烤漆， 水性氨基烤漆是由以下原材料配比制成的， 按重量百分比 计算为：
40%的水性聚酯树脂、 4.9%的水性环氧树脂、 8%的水性氨基树脂、 25%的去离 子水、 1.5%的 pH调节剂、 0.5%的润湿剂、 0.6%的消泡剂、 1%的分散剂、 3%的 助溶剂、 10%的颜填料、 4%的纳米氧化铝、 0.5%的硅酸镁锂、 0.5%的增稠剂、 0 .5%的流平剂。
[0056] 水性聚酯树脂的制备方法为： 酸值 50mgKOH/g的水性支链型聚酯树脂， 加入叔 碳酸缩水甘油酯， 在 150°C进行共聚改性 0.5h， 至终点酸值为 42mgKOH/g， 得到 水性聚酯树脂。 水性支链型聚酯树脂与叔碳酸缩水甘油酯的质量比为 8.7: 1。
[0057] 水性环氧树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 120°C下聚合 3h， 至 终点酸值 2mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂。 环氧树脂与低碘 值脂肪酸的质量比为 2.4: 1， 低碘值脂肪酸的碘值≤70g/100g。
[0058] 润湿剂为聚醚改性聚硅氧烷润湿剂； 消泡剂为含气相二氧化硅的聚醚改性硅氧 烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为二丙二醇 甲醚； 增稠剂为非离子缔合型聚氨酯增稠剂、 丙烯酸和丙烯酸酯共聚物的碱溶 胀型增稠剂中的两种 （增稠剂中非离子缔合型聚氨酯增稠剂与丙烯酸和丙烯酸 酯共聚物的碱溶胀型增稠剂的重量比为 2: 1) ； 流平剂为高分子量聚二甲基硅氧 烷乳液。
[0059] 制备方法同实施例 1。
[0060] 对本发明制作的上述水性氨基烤漆进行检测， 测得的各项技术指标为：
[0061] 硬度 >2H (铅笔硬度测试）
[0062] 光泽 >98 (60°角测试）
[0063] 附着力 ≤1级 （划格测试 lmm)
[0064] 稳定性 >30d (50°C储存）
[0065] 耐水性 >240h
[0066] 冲击性 1级 （100cm) 。
[0067] 本发明水性氨基烤漆产品水性环保、 稳定性好、 硬度高、 可多道涂装、 附着力 强、 干燥快、 保光性强、 耐老化性优异、 耐水性好， 施工方便， 成本低， 不燃 、 不爆、 无公害、 低温贮存不变质。 还具有施工方便快捷、 漆膜平整光滑、 手 感俱佳等特点。

Claims

权利要求书
[权利要求 1] 一种水性氨基烤漆， 其特征在于： 所述水性氨基烤漆是由以下原材料 配比制成的， 按重量百分比计算为：
25-40%的水性聚酯树脂、 4-5%的水性环氧树脂、 7-10%的水性氨基树 脂、 25-35%的去离子水、 1.5-2.5%的 pH调节剂、 0.3-0.5%的润湿剂、 0.2-0.6%的消泡剂、 0.5-1%的分散剂、 1-5%的助溶剂、 10-20%的颜填 料、 2-5%的纳米氧化铝、 0.3-0.5%的硅酸镁锂、 0.3-0.5%的增稠剂、 0 .5-0.8%的流平剂； 经混合搅拌均匀制成的；
所述水性环氧树脂由低碘值脂肪酸与环氧树脂聚合， 形成带有仲羟基 的脂肪酸改性环氧树脂， 酸值≤5mgKOH/g。
[权利要求 2] 根据权利要求 1所述的一种水性氨基烤漆， 其特征在于所述水性聚酯 树脂由水性支链型聚酯树脂与叔碳酸缩水甘油酯共聚而成， 水性聚酯 树脂酸值为 40-50mgKOH/g。
[权利要求 3] 根据权利要求 2所述的一种水性氨基烤漆， 其特征在于所述水性聚酯 树脂的制备方法为： 酸值 50-60mgKOH/g的水性支链型聚酯树脂， 加 入叔碳酸缩水甘油酯， 在 120-150°C进行共聚改性， 至终点酸值为 40-
50mgKOH/g, 得到水性聚酯树脂。
[权利要求 4] 根据权利要求 3所述的一种水性氨基烤漆， 其特征在于： 水性支链型 聚酯树脂与叔碳酸缩水甘油酯的质量比为 8.5-9 : 1。
[权利要求 5] 根据权利要求 1所述的一种水性氨基烤漆， 其特征在于所述水性环氧 树脂的制备方法为： 低碘值脂肪酸与环氧树脂在 100-120°C下聚合， 至终点酸值≤5mgKOH/g， 形成带有仲羟基的脂肪酸改性环氧树脂。
[权利要求 6] 根据权利要求 5所述的一种水性氨基烤漆， 其特征在于： 环氧树脂与 低碘值脂肪酸的质量比为 2-2.5: 1， 低碘值脂肪酸的碘值≤70g/100g。
[权利要求 7] 根据权利要求 1所述的一种水性氨基烤漆， 其特征在于：
所述润湿剂为聚醚改性聚硅氧烷润湿剂；
消泡剂为含气相二氧化硅的聚醚改性硅氧烷共聚物消泡剂； 分散剂为聚醚磷酸酯系的阴离子化合物； 助溶剂为二丙二醇甲醚和乙二醇单丁醚中的一种或两种； 增稠剂为非离子缔合型聚氨酯增稠剂、 丙烯酸和丙烯酸酯共聚物的碱 溶胀型增稠剂中的两种；
流平剂为高分子量聚二甲基硅氧烷乳液。
[权利要求 8] 如权利要求 1-7任一项所述的一种水性氨基烤漆的制备方法， 其特征 在于， 包括以下步骤：
(1) 按配比， 将水性聚酯树脂、 去离子水、 pH调节剂、 润湿剂、 消 泡剂加入调漆缸中， 搅拌；
(2) 加入分散剂、 颜填料、 硅酸镁锂、 纳米氧化铝， 搅拌；
(3) 加入助溶剂， 搅拌；
(4) 将水性氨基树脂、 水性环氧树脂、 流平剂、 消泡剂加入， 搅拌
， 测初始粘度， 根据初始粘度， 加入增稠剂进行增稠至 25°C、 斯托默 粘度计 80-90KU, 得到水性氨基烤漆。
[权利要求 9] 根据权利要求 8所述的一种水性氨基烤漆的制备方法， 其特征在于， 包括以下步骤：
(1) 按配比， 依次将水性聚酯树脂、 去离子水、 pH调节剂、 润湿剂 、 消泡剂加入调漆缸中， 以 800-1000rpm的速度搅拌；
(2) 加入分散剂、 颜填料、 硅酸镁锂、 纳米氧化铝， 以 1000-1200rp m的速度搅拌 20分钟， 研磨细度≤15 ！^
(3) 加入助溶剂， 以 1000-1200rpm的速度搅拌 10分钟；
(4) 依次将水性氨基树脂、 水性环氧树脂、 流平剂、 消泡剂加入， 以 600-800rpm的速度搅拌， 测初始粘度， 根据初始粘度， 加入增稠剂 进行增稠至 25°C、 斯托默粘度计 80-90KU, 得到水性氨基烤漆。
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