WO2021081980A1 - 一种着色水性涂料组合物及其制备方法 - Google Patents

一种着色水性涂料组合物及其制备方法 Download PDF

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WO2021081980A1
WO2021081980A1 PCT/CN2019/115001 CN2019115001W WO2021081980A1 WO 2021081980 A1 WO2021081980 A1 WO 2021081980A1 CN 2019115001 W CN2019115001 W CN 2019115001W WO 2021081980 A1 WO2021081980 A1 WO 2021081980A1
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formulation
resin emulsion
water
coating composition
formula
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PCT/CN2019/115001
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English (en)
French (fr)
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朱晨润
张丽
卢志峰
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泰州清润环保科技有限公司
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Publication of WO2021081980A1 publication Critical patent/WO2021081980A1/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
    • 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
    • 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
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the invention relates to the field of coatings, in particular to a colored coating composition and a preparation method thereof.
  • the present invention provides a colored coating composition comprising the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Formulation B includes polyisocyanate, organic solvent and color pigments.
  • X is a hydrolyzable group
  • X is selected from alkoxy, alkanoyloxy and halogen
  • the alkoxy is selected from methoxy, ethoxy and isopropoxy
  • the alkane The acyloxy group is selected from formyloxy and acetoxy, and the halogen is selected from chlorine and bromine;
  • m and n are positive integers, m is 2-5, and n is 3-25.
  • the amount of the silane represented by formula (I) is in the range of 1-10 parts by mass.
  • the mass ratio of low molecular weight alcohol solvent to water is (1-49): (51-99); low molecular weight alcohol solvent is selected from methanol, ethanol, propanol, isopropanol, n-butyl Alcohol, isobutanol, ethylene glycol, propylene glycol, butylene glycol.
  • the organic solvent is selected from one or more of alcohol ethers, ketones or ester organic solvents.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment in formulation B is (20-30): (40-50): (20-60).
  • the resin emulsion is selected from acrylic resin emulsion, polyurethane resin emulsion, epoxy resin emulsion, and alkyd resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of (70-80): (20-30).
  • the colored water-based coating composition of the present invention is suitable for various metal surfaces, such as stainless steel, iron, aluminum, copper, zinc and other metal surfaces. Generally, these metals are materials used to manufacture automobiles, and therefore, the colored water-based coating composition of the present invention is particularly suitable for automobile surface coating.
  • the colored water-based coating composition of the present invention is usually coated on the surface of the primer in advance, and then the clear coating composition is coated and dried together.
  • silane is added, which has a hydrolyzable group X, so that in-situ hydrolysis in the coating film can obtain nano-silica particles, thereby increasing the strength of the coating film.
  • silane is X 3 Si-(CH 2 )m-(OR)n-NH-C(COOH)-CH 2 -S.
  • polyoxyalkylene group -(OR)n- which can suppress the low leveling that is easily generated during the re-film formation of water-based coatings, thereby ensuring that the coating film has excellent smooth surface and resistance to grit impact .
  • the above silane structure also has a cysteine group, namely -NH-C(COOH)-CH 2 -SH.
  • the sulfhydryl group in the cysteine group formed in the coating film will form disulfide bonds after being oxidized in the air, making the coating film layer cross-linked and dense, further improving the three-dimensional structure of the coating film, and improving the mechanical properties of the coating film.
  • the adhesion of the coating film on the surface of the substrate provides a guarantee for the excellent resistance to grit impact of the coating film.
  • a colored water-based coating composition including the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Solution B including polyisocyanate, organic solvent and color pigment
  • X is a hydrolyzable group, X is an ethoxy group; m is 3 and n is 12.
  • the amount of the silane represented by the formula (I) is in the range of 3 parts by mass.
  • the mass ratio of the low-molecular-weight alcohol solvent to water is 20:80; the low-molecular-weight alcohol solvent is ethanol.
  • the organic solvent is an alcohol ether organic solvent.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment is 25:45:40.
  • the resin emulsion is an acrylic resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of 75:25.
  • a colored water-based coating composition including the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Solution B including polyisocyanate, organic solvent and color pigment
  • X is a hydrolyzable group, X is a formyloxy group; m is 5 and n is 22.
  • the amount of the silane represented by the formula (I) is in the range of 10 parts by mass.
  • the mass ratio of the low-molecular-weight alcohol solvent to water is 10:90; the low-molecular-weight alcohol solvent is ethylene glycol.
  • the organic solvent is a ketone organic solvent.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment is 20:50:50.
  • the resin emulsion is a polyurethane resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of 80:20.
  • a colored water-based coating composition including the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Solution B including polyisocyanate, organic solvent and color pigment
  • X is a hydrolyzable group, X is chlorine; m is 2 and n is 6.
  • the amount of the silane represented by the formula (I) is in the range of 1 part by mass.
  • the mass ratio of the low-molecular-weight alcohol solvent to water is 30:70; the low-molecular-weight alcohol solvent is propanol.
  • the organic solvent is an ester organic solvent.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment is 30:45:45.
  • the resin emulsion is selected from acrylic resin emulsion, polyurethane resin emulsion, epoxy resin emulsion, and alkyd resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of 70:30.
  • a colored water-based coating composition including the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Solution B including polyisocyanate, organic solvent and color pigment
  • X is a hydrolyzable group
  • X is an isopropoxy group
  • m is 4, and n is 16.
  • the amount of the silane represented by the formula (I) is in the range of 6 parts by mass.
  • the mass ratio of the low-molecular-weight alcohol solvent to water is 5:95; the low-molecular-weight alcohol solvent is ethanol.
  • the organic solvent is alcohol ethers.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment is 20:50:30.
  • the resin emulsion is an epoxy resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of 70:30.
  • a colored water-based coating composition including the following two formulations:
  • Formulation A includes resin emulsion, silane represented by formula (I), water, and low-molecular-weight alcohol solvent;
  • Solution B including polyisocyanate, organic solvent and color pigment
  • X is a hydrolyzable group, X is an ethoxy group; m is 3 and n is 20.
  • the amount of the silane represented by the formula (I) is in the range of 2 parts by mass.
  • the mass ratio of the low-molecular-weight alcohol solvent to water is 18:82; the low-molecular-weight alcohol solvent is propanol.
  • the organic solvent is a ketone organic solvent.
  • the mass ratio of polyisocyanate, organic solvent, and color pigment is 30:40:30.
  • the resin emulsion is an alkyd resin emulsion.
  • the colored aqueous coating composition of the present invention can be obtained by mixing the formulation A and the formulation B in a volume ratio of 75:25.
  • Example 1 Compared with Example 1, the silane represented by formula (I) in the formulation A is omitted, and the rest is the same.
  • Performance tests were performed on the colored water-based coating compositions of Examples 1-5 and Comparative Examples.
  • the transparent coating film layer on the surface was omitted, specifically the surface brightness and the coating film in the decorative effect.
  • the squeeze hardness in the impact resistance of sand was tested, and the corresponding results are shown in the table below. Among them, the squeeze hardness is expressed by the Martens hardness value, and the unit is N/mm 2 .
  • Example 1 Example 2
  • Example 3 Example 4
  • Comparison Surface brightness 95 95 95 95 95 95 95 95 95 Squeeze hardness 22.2 22.9 21.9 23.3 22.6 6.7

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

一种着色水性涂料组合物，包含以下两种配液：配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及配液B，包括多异氰酸酯、有机溶剂和色彩颜料。其中，式(I)的具体结构为X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH，其中，X是可水解基团，X选自烷氧基、烷酰氧基和卤素，所述烷氧基选自甲氧基、乙氧基和异丙氧基，所述烷酰氧基选自甲酰氧基和乙酰氧基，所述卤素选自氯和溴；m、n为正整数，m为2-5，n为3-25。通过在水性涂料中添加如式(I)所示的硅烷，可以改善水性涂料膜的抗砂砾冲击性。

Description

一种着色水性涂料组合物及其制备方法 技术领域
本发明涉及涂料领域，具体涉及一种着色涂料组合物及其制备方法。
背景技术
各种颜色靓丽的汽车是通过对汽车金属外壳表面涂覆着色涂料来实现的。目前，最常用的汽车涂装工艺是依次在汽车金属外壳表面涂覆底漆、着色涂料、透明涂料，然后进行共同固化。其中，无论是着色涂料还是透明涂料，通常采用的均是水性涂料。
然而，现有的水性涂料大都以丙烯酸树脂作为成膜主剂，所得到的涂料膜的硬度往往不够，粘附性不足，再汽车行驶过程中，汽车表面的涂料膜容易受到道路上的砂砾的冲击而损伤，即汽车表面涂装的涂料膜的抗砂砾冲击性能不足。
因此，有必要研发一种具有优异的抗砂砾冲击的着色涂料膜。
发明内容
为了解决现有技术中的上述技术问题，本发明人通过大量的研究，发现在水性涂料中添加如式(I)所示的硅烷，可以改善水性涂料膜的抗砂砾冲击性。
X 3Si-(CH2-CR 1R 2-CH2)n-NH-C(COOH)-CH 2-SH  (I)
即，本发明提供了一种着色涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料。
式(I)中，X是可水解基团，X选自烷氧基、烷酰氧基和卤素，所述烷氧基选自甲氧基、乙氧基和异丙氧基，所述烷酰氧基选自甲酰氧基和乙酰氧基，所述卤素选自氯和溴；m、n为正整数，m为2-5，n为3-25。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为1-10质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为(1-49)：(51-99)；低分子醇类溶剂选自甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙二醇、丁二醇。
其中、配液B中，有机溶剂选自醇醚类、酮类或酯类有机溶剂中的一种或多种。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为(20-30)：(40-50)：(20-60)。
其中，所述树脂乳液选自丙烯酸树脂乳液、聚氨酯树脂乳液、环氧树脂乳液、醇酸树脂乳液。
通过将配液A和配液B按照体积比为(70-80)：(20-30)混合即可获得本发明的着色水性涂料组合物。
本发明的着色水性涂料组合物适用于各类金属表面，例如不锈钢、铁、铝、铜、锌等金属表面。通常，这些金属是用于制造汽车的材料，因而，本发明的着色水性涂料组合物特别适用于汽车表面涂装。
对于汽车表面的具体涂装工艺，通常预先将本发明的着色水性涂料组合物涂覆于底漆 表面，然后再涂覆透明涂料组合物，并共同干燥即可。
本发明的着色水性涂料组合物中，添加了硅烷，其具有水解性基团X，使得涂料膜中原位水解得到纳米二氧化硅颗粒，增加涂料膜的强度。
硅烷的结构为X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-S。在该结构中，具有聚氧化烯基团-(OR)n-，可以抑制水性涂料再成膜过程中容易产生的低流平性，从而确保涂料膜具有优异的平滑性表面和抗砂砾冲击性能。
上述硅烷结构中还具有半胱氨酸基团，即-NH-C(COOH)-CH 2-SH。形成于涂料膜中的该半胱氨酸基团中的巯基在空气中氧化后会形成二硫键，使得涂料膜层交联致密，进一步改善涂料膜的三维结构，改善涂料膜的机械性能和涂料膜在基体表面的附着力，为涂料膜优异的抗砂砾冲击性能提供保障。
具体实施方式
下面，将结合具体的实例对本发明进行详细说明。当然，所描述的实施例仅仅是本发明的一部分创造内容，而不是全部。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的情况下所获得的其他实例均落入本发明的保护范围內。
实施例1
一种着色水性涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
式(I)中，X是可水解基团，X为乙氧基；m为3，n为12。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为3质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为20：80；低分子醇类溶剂为乙醇。
其中、配液B中，有机溶剂为醇醚类有机溶剂。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为25：45：40。
其中，所述树脂乳液为丙烯酸树脂乳液。
通过将配液A和配液B按照体积比为75：25混合即可获得本发明的着色水性涂料组合物。
实施例2
一种着色水性涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
式(I)中，X是可水解基团，X为甲酰氧基；m为5，n为22。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量 为10质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为10：90；低分子醇类溶剂为乙二醇。
其中、配液B中，有机溶剂为酮类有机溶剂。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为20：50：50。
其中，所述树脂乳液为聚氨酯树脂乳液。
通过将配液A和配液B按照体积比为80：20混合即可获得本发明的着色水性涂料组合物。
实施例3
一种着色水性涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
式(I)中，X是可水解基团，X为氯；m为2，n为6。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为1质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为30：70；低分子醇类溶剂为丙醇。
其中、配液B中，有机溶剂为酯类有机溶剂。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为30：45：45。
其中，所述树脂乳液选自丙烯酸树脂乳液、聚氨酯树脂乳液、环氧树脂乳液、醇酸树脂乳液。
通过将配液A和配液B按照体积比为70：30混合即可获得本发明的着色水性涂料组合物。
实施例4
一种着色水性涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
式(I)中，X是可水解基团，X为异丙氧基，m为4，n为16。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为6质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为5：95；低分子醇类溶剂为乙醇。
其中、配液B中，有机溶剂为醇醚类。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为20：50：30。
其中，所述树脂乳液为环氧树脂乳液。
通过将配液A和配液B按照体积比为70：30混合即可获得本发明的着色水性涂料组合物。
实施例5
一种着色水性涂料组合物，包含以下两种配液：
配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
式(I)中，X是可水解基团，X为乙氧基；m为3，n为20。
其中，配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为2质量份的范围。
其中，配液A中，低分子醇类溶剂与水的质量比为18：82；低分子醇类溶剂为丙醇。
其中、配液B中，有机溶剂酮类有机溶剂。
其中、配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为30：40：30。
其中，所述树脂乳液为醇酸树脂乳液。
通过将配液A和配液B按照体积比为75：25混合即可获得本发明的着色水性涂料组合物。
对比例
相较于实施例1，省略掉配液A中的式(I)所示的硅烷，其余相同。
分别对实施例1-5和对比例的着色水性涂料组合物进行性能测试，在进行性能测试的过程中，省略掉表面的透明涂料膜层，具体对其装饰效果中的表面光亮度以及涂料膜的抗砂砾冲击性能中的挤入硬度进行测试，相应的结果如下表所示。其中，挤入硬度以马氏硬度值进行表示，单位为N/mm 2。
实例 实施例1 实施例2 实施例3 实施例4 实施例5 对比例
表面光亮度 95 95 95 95 95 95
挤入硬度 22.2 22.9 21.9 23.3 22.6 6.7
从上表可知，在涂料中添加结构为X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH的硅烷，可以确保水性涂料膜具有优异的抗砂砾冲击性能。
以上是本发明的着色水性涂料组合物。需要指出的是，本发明所记载的内容，本领域普通技术人员在没有做出创造性劳动的情况下所获得的其他实例均涵盖于本发明的保护范围內。

Claims (7)

  1. 一种着色水性涂料组合物，包含以下两种配液：
    配液A，包括树脂乳液、式(I)所示的硅烷、水、低分子醇类溶剂；以及
    配液B，包括多异氰酸酯、有机溶剂和色彩颜料；
    X 3Si-(CH 2)m-(OR)n-NH-C(COOH)-CH 2-SH  (I)
    式(I)中，X是可水解基团，X选自烷氧基、烷酰氧基和卤素，所述烷氧基选自甲氧基、乙氧基和异丙氧基，所述烷酰氧基选自甲酰氧基和乙酰氧基，所述卤素选自氯和溴；m、n为正整数，m为2-5，n为3-25。
  2. 如权利要求1所述的一种着色水性涂料组合物，其特征在于：配液A中，以树脂乳液的固体含量100质量份计，式(I)所示的硅烷的用量为1-10质量份的范围。
  3. 如权利要求1所述的一种着色水性涂料组合物，其特征在于：配液A中，低分子醇类溶剂与水的质量比为(1-49)：(51-99)；低分子醇类溶剂选自甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙二醇、丁二醇。
  4. 如权利要求1所述的一种着色水性涂料组合物，其特征在于：配液B中，有机溶剂选自醇醚类、酮类或酯类有机溶剂中的一种或多种。
  5. 如权利要求1所述的一种着色水性涂料组合物，其特征在于：配液B中，多异氰酸酯、有机溶剂、色彩颜料的质量比为(20-30)：(40-50)：(20-60)。
  6. 如权利要求1所述的一种着色水性涂料组合物，其特征在于：所述树脂乳液选自丙烯酸树脂乳液、聚氨酯树脂乳液、环氧树脂乳液、醇酸树脂乳液。
  7. 如权利要求1-6任一项所述的一种着色水性涂料组合物，其特征在于：通过将配液A和配液B按照体积比为(70-80)：(20-30)混合即可。
PCT/CN2019/115001 2019-10-28 2019-11-01 一种着色水性涂料组合物及其制备方法 WO2021081980A1 (zh)

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CN111334114A (zh) * 2020-04-29 2020-06-26 青岛盈海涂料科技有限责任公司 涂料添加剂
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