CN102993422A - Epoxy modified saturated polyester resin for undercoat of coil coating and undercoat of coil coating - Google Patents
Epoxy modified saturated polyester resin for undercoat of coil coating and undercoat of coil coating Download PDFInfo
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Abstract
本发明公开一种卷材涂料底漆用环氧改性饱和聚酯树脂及卷材涂料底漆，按重量份计环氧改性饱和聚酯树脂包含以下组分：甲基丙二醇50~80份、环氧树脂609 100~140份、间苯二甲酸110~150份、己二酸110~150份、新戊二醇105~145份、有机锡0.1~0.6份、二甲苯20~40份、S-150#溶剂油380~500份、丙二醇甲醚30~60份。本发明制备的环氧改性饱和聚酯树脂应用于卷材涂料底漆，使卷材涂料底漆不但对金属具有很强的粘接力和防腐蚀性能，同时也有很高的加工性，在较好的表面硬度和耐候性下又具有极佳的变形性，综合性能有显著提高，成本降低。The invention discloses an epoxy-modified saturated polyester resin for a coil coating primer and a coil coating primer. The epoxy-modified saturated polyester resin comprises the following components in parts by weight: 50-80 parts of methyl propylene glycol , epoxy resin 609 100~140 parts, isophthalic acid 110~150 parts, adipic acid 110~150 parts, neopentyl glycol 105~145 parts, organotin 0.1~0.6 parts, xylene 20~40 parts, S-150# solvent oil 380~500 parts, propylene glycol methyl ether 30~60 parts. The epoxy-modified saturated polyester resin prepared by the present invention is applied to the coil coating primer, so that the coil coating primer not only has strong adhesion and anti-corrosion performance to metal, but also has high processability. With good surface hardness and weather resistance, it has excellent deformability, the overall performance is significantly improved, and the cost is reduced.
Description
技术领域 technical field
本发明属于化工领域，具体涉及一种卷材涂料底漆用环氧改性饱和聚酯树脂及卷材涂料底漆。The invention belongs to the field of chemical industry, and in particular relates to an epoxy-modified saturated polyester resin for a coil coating primer and a coil coating primer.
背景技术 Background technique
随着技术的不断成熟，卷材涂料发展速度很快，现在市场上卷材涂料主要有聚酯树脂卷材涂料、丙烯酸树脂卷材涂料、环氧树脂底漆涂料等组成。聚酯树脂组成的卷材涂料有很高的加工性，在较好的表面硬度下又具有极佳的变形性。丙烯酸树脂卷材涂料硬度、耐候性很好，加工性能一般。环氧树脂漆对金属具有很强的粘接力和防腐蚀性能，而变形性和耐候性方面比较薄弱。市场上卷材涂料比较常见的就是冷拼树脂，希望利用树脂性能的互补来提高产品的性能，多了一道工序，比较麻烦不说，而且还有两个树脂混溶性的要求，混溶性不好还不能冷拼。性能提高不多达不到理想的目的和最佳的效果。由于冷拼树脂对提高涂料的性能效果不是很好，而对于卷材底漆来说是起到承上启下的作用，粘接力、防腐性、加工性能都很重要。针对这一性能要求，需要开发一只包含饱和聚酯树脂和环氧树脂综合性能的树脂。从而来满足卷材涂料底漆涂料的要求。With the continuous maturity of technology, coil coatings are developing rapidly. Now coil coatings on the market mainly include polyester resin coil coatings, acrylic resin coil coatings, and epoxy resin primer coatings. Coil coatings composed of polyester resins have high processability and excellent deformability with good surface hardness. Acrylic resin coil coating has good hardness and weather resistance, and the processability is average. Epoxy paint has strong adhesion and corrosion resistance to metals, but is weak in deformation and weather resistance. The most common coil coatings on the market are cold blend resins. We hope to use the complementary properties of the resins to improve the performance of the product. There is one more process, which is more troublesome. There are also two requirements for resin compatibility, which is not good. Still can't fight coldly. The performance improvement is not less than the ideal purpose and the best effect. Because the cold-splicing resin is not very effective in improving the performance of the coating, but it plays a connecting role for the coil primer, and the adhesion, corrosion resistance, and processing performance are all important. In response to this performance requirement, it is necessary to develop a resin that contains the comprehensive properties of saturated polyester resin and epoxy resin. In order to meet the requirements of coil coating primer coating.
发明内容 Contents of the invention
本发明的目的在于提供一种卷材涂料底漆用环氧改性饱和聚酯树脂。The object of the present invention is to provide an epoxy-modified saturated polyester resin for coil coating primer.
本发明的另一目的在于提供一种卷材涂料底漆。Another object of the present invention is to provide a coil coating primer.
本发明的目的可以通过以下技术方案实现：The purpose of the present invention can be achieved through the following technical solutions:
一种卷材涂料底漆用环氧改性饱和聚酯树脂，按重量份计包含以下组分：甲基丙二醇50~80份、环氧树脂609 100~140份、间苯二甲酸110~150份、己二酸110~150份、新戊二醇105~145份、有机锡0.1~0.6份、二甲苯20~40份、S-150#溶剂油380~500份、丙二醇甲醚30~60份。An epoxy-modified saturated polyester resin for a coil coating primer, comprising the following components in parts by weight: 50-80 parts of methyl propylene glycol, 100-140 parts of epoxy resin 609, and 110-150 parts of isophthalic acid 110~150 parts of adipic acid, 105~145 parts of neopentyl glycol, 0.1~0.6 parts of organotin, 20~40 parts of xylene, 380~500 parts of S-150# solvent oil, 30~60 parts of propylene glycol methyl ether share.
优选的，上述卷材涂料底漆用环氧改性饱和聚酯树脂各组分的含量为：甲基丙二醇60~70份、环氧树脂609 110~130份、间苯二甲酸120~140份、己二酸120~140份、新戊二醇115~135份、有机锡0.1~0.5份、二甲苯25~35份、S-150#溶剂油 400~480份、丙二醇甲醚40~50份。Preferably, the content of each component of the epoxy-modified saturated polyester resin for the above-mentioned coil coating primer is: 60-70 parts of methyl propylene glycol, 110-130 parts of epoxy resin 609, 120-140 parts of isophthalic acid , 120~140 parts of adipic acid, 115~135 parts of neopentyl glycol, 0.1~0.5 parts of organotin, 25~35 parts of xylene, 400~480 parts of S-150# solvent oil, 40~50 parts of propylene glycol methyl ether .
所述的有机锡优选为单丁基氧化锡、二丁基氧化锡或二丁基二月桂酸锡。The organotin is preferably monobutyltin oxide, dibutyltin oxide or dibutyltin dilaurate.
上述的卷材涂料底漆用环氧改性饱和聚酯树脂，其制备方法为：按比例将甲基丙二醇、环氧树脂609、间苯二甲酸、己二酸、新戊二醇和有机锡投入反应釜，升温至120~140℃，开动搅拌，在145~155℃反应1~3小时，缓慢升温至170~190℃，维持0.5~3小时后，继续升温至190~210℃连续酯化反应至树脂透明，降温至180℃或180℃以下，加二甲苯，升温至二甲苯回流，回流反应至树脂酸值≤5 mgKOH，降温180℃或180℃以下，按比例加入S-150#溶剂油和丙二醇甲醚兑稀，搅拌均匀，过滤，放料，包装。The above-mentioned epoxy-modified saturated polyester resin for coil coating primer is prepared by adding methyl propylene glycol, epoxy resin 609, isophthalic acid, adipic acid, neopentyl glycol and organotin in proportion Reactor, heat up to 120~140°C, start stirring, react at 145~155°C for 1~3 hours, slowly heat up to 170~190°C, keep it for 0.5~3 hours, continue to heat up to 190~210°C for continuous esterification reaction Until the resin is transparent, cool down to 180°C or below, add xylene, heat up to xylene reflux, reflux until the acid value of the resin is ≤5 mgKOH, cool down to 180°C or below 180°C, add S-150# solvent oil in proportion Dilute with propylene glycol methyl ether, stir evenly, filter, discharge, and pack.
一种卷材涂料底漆， 按重量百分含量计包含以下组分：上述的环氧改性饱和聚酯树脂50%~75%、颜料8%~16%、填料0.5%~3%、防锈颜料2%~10%、747氨基树脂2%~7%、乙二醇丁醚2%~7%、S-100#溶剂油3%~10%、DBE溶剂1%~5%、 分散剂0.1%~0.6%、N1051 0.1%~0.6%、ADP0.5%~4 %。A coil coating primer, comprising the following components by weight percentage: 50%-75% of the above-mentioned epoxy-modified saturated polyester resin, 8%-16% of pigment, 0.5%-3% of filler, anti-corrosion Rust pigment 2%~10%, 747 amino resin 2%~7%, ethylene glycol butyl ether 2%~7%, S-100# solvent oil 3%~10%, DBE solvent 1%~5%, dispersant 0.1%~0.6%, N1051 0.1%~0.6%, ADP0.5%~4%.
优选的，上述卷材涂料底漆各组分的含量为：上述的环氧改性饱和聚酯树脂55%~70%、颜料10%~14%、填料1%~2%、防锈颜料3%~7%、747氨基树脂3%~6%、乙二醇丁醚3%~6%、S-100#溶剂油4%~8%、DBE溶剂2%~4%、分散剂0.1%~0.4%、N1051 0.1%~0.5%、ADP 1%~3%。Preferably, the content of each component of the above-mentioned coil coating primer is: 55%-70% of the above-mentioned epoxy-modified saturated polyester resin, 10%-14% of pigment, 1%-2% of filler, 3% of anti-rust pigment %~7%, 747 amino resin 3%~6%, butyl glycol ether 3%~6%, S-100# solvent oil 4%~8%, DBE solvent 2%~4%, dispersant 0.1%~ 0.4%, N1051 0.1%~0.5%, ADP 1%~3%.
所述的分散剂优选为BYK-P104或其他与BYK-P104功能相近的分散剂。The dispersant is preferably BYK-P104 or other dispersants with similar functions to BYK-P104.
所述的颜料可根据客户需要进行选择，例如白色油漆可选择钛白粉作为颜料。Described pigment can be selected according to customer's needs, for example white paint can choose titanium dioxide as pigment.
所述的防锈颜料可根据需要进行选择，优选为锶铬黄和锌铬黄中的至少一种。The antirust pigment can be selected according to needs, and is preferably at least one of strontium chrome yellow and zinc chrome yellow.
所述的填料优选为滑石粉。The filler is preferably talcum powder.
N-1051是一种酸是氨基树脂反应催化剂，ADP 是附着力促进剂用于提高漆膜对底材的附着力。N-1051 is an acid that acts as a catalyst for the reaction of amino resins, and ADP is an adhesion promoter used to improve the adhesion of the paint film to the substrate.
本发明技术方案所涉及的原料除特别说明外，均可通过市场购买获得。Unless otherwise specified, the raw materials involved in the technical solution of the present invention can be obtained through market purchase.
本发明的有益效果：Beneficial effects of the present invention:
本发明制备的环氧改性饱和聚酯树脂应用于卷材涂料，使卷材涂料不但对金属具有很强的粘接力和防腐蚀性能，同时也有很高的加工性，在较好的表面硬度和耐候性下又具有极佳的变形性，综合性能有显著提高。The epoxy-modified saturated polyester resin prepared by the present invention is applied to coil coatings, so that the coil coatings not only have strong adhesion and anti-corrosion properties to metals, but also have high processability. It has excellent deformability under the hardness and weather resistance, and the comprehensive performance has been significantly improved.
具体实施方式 Detailed ways
使用原料：Raw materials used:
有机锡：为单丁基氧化锡、二丁基氧化锡或二丁基二月桂酸锡，由南京鼎晨化学科技发展有限公司生产Organotin: Monobutyltin oxide, dibutyltin oxide or dibutyltin dilaurate, produced by Nanjing Dingchen Chemical Technology Development Co., Ltd.
颜料：钛白粉Pigment: titanium dioxide
填料：滑石粉Filler: Talc powder
防锈颜料：锶铬黄、锌铬黄Anti-rust pigments: strontium chrome yellow, zinc chrome yellow
N-1051：市售，氨基树脂反应催化剂N-1051: commercially available, amino resin reaction catalyst
ADP：台湾德谦公司的附着力促进剂，提高漆膜对底材的附着力ADP: Adhesion promoter of Taiwan Deqian Company, which improves the adhesion of the paint film to the substrate
环氧609：江苏三木公司Epoxy 609: Jiangsu Sanmu Company
747氨基树脂：全甲醚化氨基树脂，美国首诺公司747 amino resin: full methyl etherified amino resin, Solutia Corporation
实施例1 制备环氧改性饱和聚酯树脂Embodiment 1 Preparation of epoxy-modified saturated polyester resin
按重量份计，环氧改性饱和聚酯树脂中各组分的含量为：By weight, the content of each component in the epoxy modified saturated polyester resin is:
配方施工工艺：按比例将甲基丙二醇、环氧树脂609、间苯二甲酸、己二酸、新戊二醇和二丁基二月桂酸锡投入反应釜，升温至130℃，开动搅拌，在150℃反应2小时，缓慢升温至180℃，维持1小时后，继续升温至200℃连续酯化反应至树脂透明，降温至180℃以下，加二甲苯，升温至二甲苯回流（200℃~220℃），回流反应至树脂酸值≤5 mgKOH，降温至180℃以下，按比例加入S-150#和丙二醇甲醚兑稀，搅拌均匀，过滤，放料，包装。Formula construction process: Put methyl propylene glycol, epoxy resin 609, isophthalic acid, adipic acid, neopentyl glycol and dibutyltin dilaurate into the reaction kettle in proportion, raise the temperature to 130°C, start stirring, React at ℃ for 2 hours, slowly raise the temperature to 180℃, keep it for 1 hour, continue to raise the temperature to 200℃ for continuous esterification reaction until the resin is transparent, cool down to below 180℃, add xylene, heat up to xylene reflux (200℃~220℃ ), reflux until the acid value of the resin is ≤5 mgKOH, cool down to below 180°C, add S-150# and propylene glycol methyl ether in proportion to dilute, stir evenly, filter, discharge, and pack.
实施例2 制备环氧改性饱和聚酯树脂Embodiment 2 Preparation of epoxy-modified saturated polyester resin
按重量份计，环氧改性饱和聚酯树脂中各组分的含量为：By weight, the content of each component in the epoxy modified saturated polyester resin is:
配方施工工艺：按比例将甲基丙二醇、环氧树脂609、间苯二甲酸、己二酸、新戊二醇和二丁基氧化锡投入反应釜，升温至135℃，开动搅拌，在148℃反应2小时，缓慢升温至180℃，维持1小时后，继续升温至205℃连续酯化反应至树脂透明，降温至180℃以下，加二甲苯，升温至二甲苯回流，回流反应至树脂酸值≤5 mgKOH，降温至180℃以下，按比例加入S-150#和丙二醇甲醚兑稀，搅拌均匀，过滤，放料，包装。Formula construction process: Put methyl propylene glycol, epoxy resin 609, isophthalic acid, adipic acid, neopentyl glycol and dibutyl tin oxide into the reaction kettle in proportion, raise the temperature to 135°C, start stirring, and react at 148°C For 2 hours, slowly raise the temperature to 180°C, keep it for 1 hour, continue to heat up to 205°C for continuous esterification reaction until the resin is transparent, cool down to below 180°C, add xylene, heat up to xylene reflux, and reflux reaction until the acid value of the resin is ≤ 5 mgKOH, lower the temperature to below 180°C, add S-150# and propylene glycol methyl ether in proportion to dilute, stir evenly, filter, discharge, and pack.
实施例3 制备环氧改性饱和聚酯树脂Embodiment 3 Preparation of epoxy-modified saturated polyester resin
按重量份计，环氧改性饱和聚酯树脂中各组分的含量为：By weight, the content of each component in the epoxy modified saturated polyester resin is:
配方施工工艺：按比例将甲基丙二醇、环氧树脂609、间苯二甲酸、己二酸、新戊二醇和单丁基氧化锡投入反应釜，升温至128℃，开动搅拌，在145℃反应2.5小时，缓慢升温至180℃，维持1小时后，继续升温至205℃连续酯化反应至树脂透明，降温至180℃以下，加二甲苯，升温至二甲苯回流，回流反应至树脂酸值≤5 mgKOH，降温180℃以下，按比例加入S-150#和丙二醇甲醚兑稀，搅拌均匀，过滤，放料，包装。Formula construction process: Put methyl propylene glycol, epoxy resin 609, isophthalic acid, adipic acid, neopentyl glycol and monobutyl tin oxide into the reaction kettle in proportion, raise the temperature to 128°C, start stirring, and react at 145°C After 2.5 hours, slowly raise the temperature to 180°C, keep it for 1 hour, continue to heat up to 205°C for continuous esterification reaction until the resin is transparent, cool down to below 180°C, add xylene, heat up to xylene reflux, and reflux until the acid value of the resin is ≤ 5 mgKOH, lower the temperature below 180°C, add S-150# and propylene glycol methyl ether in proportion to dilute, stir evenly, filter, discharge, and pack.
实施例4 制备卷材涂料底漆Example 4 Preparation of Coil Coating Primer
卷材涂料底漆中各组分的重量百分含量为：实施例1制备的环氧改性饱和聚酯树脂（固含量为50%）62%、钛白粉12%、滑石粉1.5%、锶铬黄3%、锌铬黄2%、747氨基树脂4%、乙二醇丁醚4%、S-100#溶剂油6%、DBE溶剂3%、BYK-P104 0.2%、N1051 0.3%、ADP 2% 。The percentage by weight of each component in the coil coating primer is: 62% of the epoxy-modified saturated polyester resin (solid content is 50%) prepared in Example 1, 12% of titanium dioxide, 1.5% of talcum powder, strontium Chrome yellow 3%, zinc chrome yellow 2%, 747 amino resin 4%, butyl glycol ether 4%, S-100# solvent oil 6%, DBE solvent 3%, BYK-P104 0.2%, N1051 0.3%, ADP 2% .
按比例将各组分搅拌混合均匀。Stir and mix the components in proportion.
实施例5 制备卷材涂料底漆Example 5 Preparation of Coil Coating Primer
卷材涂料底漆中各组分的重量百分含量为：实施例1制备的环氧改性饱和聚酯树脂（固含量为50%）57%、钛白粉13%、滑石粉2%、锶铬黄5%、747氨基树脂5%、乙二醇丁醚5%、S-100#溶剂油7%、DBE溶剂 3.5%、BYK-P104 0.3%、N1051 0.2%、ADP 2%。The percentage by weight of each component in the coil coating primer is: 57% of the epoxy-modified saturated polyester resin (solid content is 50%) prepared in Example 1, 13% of titanium dioxide, 2% of talcum powder, strontium Chrome yellow 5%, 747 amino resin 5%, butyl glycol ether 5%, S-100# solvent oil 7%, DBE solvent 3.5%, BYK-P104 0.3%, N1051 0.2%, ADP 2%.
按比例将各组分搅拌混合均匀。Stir and mix the components in proportion.
实施例6 制备卷材涂料底漆Example 6 Preparation of Coil Coating Primer
卷材涂料底漆中各组分的重量百分含量为：实施例1制备的环氧改性饱和聚酯树脂（固含量为50%）69%、钛白粉11%、滑石粉1.5%、锶铬黄2%、锌铬黄2%、747氨基树脂3%、乙二醇丁醚3%、S-100#溶剂油4%、DBE溶剂 3%、 BYK-P104 0.3%、N1051 0.2%、ADP 1%。The percentage by weight of each component in the coil coating primer is: 69% of epoxy-modified saturated polyester resin (solid content is 50%) prepared in Example 1, 11% of titanium dioxide, 1.5% of talcum powder, strontium Chrome yellow 2%, zinc chrome yellow 2%, 747 amino resin 3%, butyl glycol ether 3%, S-100# solvent oil 4%, DBE solvent 3%, BYK-P104 0.3%, N1051 0.2%, ADP 1%.
按比例将各组分搅拌混合均匀。Stir and mix the components in proportion.
比较例1Comparative example 1
卷材涂料底漆中各组分的重量百分含量为：固含量为50%的聚酯树脂（HC98352A，无锡市虎皇漆业有限公司）62%、钛白粉12%、滑石粉1.5%、锶铬黄3%、锌铬黄2%、747氨基树脂4%、乙二醇丁醚4%、S-100#溶剂油6%、DBE溶剂 3%、BYK-P104 0.2%、N1051 0.3%、ADP 2% 。The weight percentage of each component in the coil coating primer is: polyester resin (HC98352A, Wuxi Huhuang Paint Co., Ltd.) with a solid content of 50% 62%, titanium dioxide 12%, talcum powder 1.5%, Strontium chrome yellow 3%, zinc chrome yellow 2%, 747 amino resin 4%, ethylene glycol butyl ether 4%, S-100# solvent oil 6%, DBE solvent 3%, BYK-P104 0.2%, N1051 0.3%, ADP 2%.
固含量为50%的聚酯树脂的制备方法为：用质量比为3:1的S-100#溶剂油和乙二醇丁醚的混合溶剂将聚酯树脂调稀至固含量为50%。The preparation method of the polyester resin with a solid content of 50% is as follows: use a mixed solvent of S-100# solvent oil and ethylene glycol butyl ether with a mass ratio of 3:1 to dilute the polyester resin to a solid content of 50%.
按比例将各组分搅拌混合均匀。Stir and mix the components in proportion.
比较例2Comparative example 2
卷材涂料底漆中各组分的重量百分含量为：固含量为50%的环氧树脂（三木 609）62%、钛白粉12%、滑石粉1.5%、锶铬黄3%、锌铬黄2%、747氨基树脂4%、乙二醇丁醚4%、S-100#溶剂油6%、DBE溶剂 3%、BYK-P104 0.2%、N1051 0.3%、ADP 2% 。The weight percentage of each component in the coil coating primer is: 62% epoxy resin (Miki 609) with a solid content of 50%, 12% titanium dioxide, 1.5% talcum powder, 3% strontium chrome yellow, zinc chrome Yellow 2%, 747 amino resin 4%, butyl glycol ether 4%, S-100# solvent oil 6%, DBE solvent 3%, BYK-P104 0.2%, N1051 0.3%, ADP 2%.
固含量为50%的环氧树脂的制备方法为：用质量比为3:1的S-100#溶剂油和环己酮的混合溶剂将环氧树脂调稀至固含量为50%。The preparation method of the epoxy resin with a solid content of 50% is as follows: use a mixed solvent of S-100# solvent oil and cyclohexanone with a mass ratio of 3:1 to dilute the epoxy resin to a solid content of 50%.
按比例将各组分搅拌混合均匀。Stir and mix the components in proportion.
实施例4~6、比较例1和比较例2制备的卷材涂料底漆的性能检测结果见表1The performance detection result of the coil coating primer prepared by embodiment 4～6, comparative example 1 and comparative example 2 is shown in Table 1
表1 实施例4~6、比较例1和比较例2制备的卷材涂料底漆的性能检测结果Table 1 The performance test results of the coil coating primer prepared in Examples 4-6, Comparative Example 1 and Comparative Example 2
结果显示，将本发明制备的环氧改性饱和聚酯树脂应用于卷材涂料底漆，使卷材涂料底漆不但对金属具有很强的粘接力和防腐蚀性能，同时也有很高的加工性，在较好的表面硬度和耐候性下又具有极佳的变形性，综合性能有显著提高，降低成本。The results show that the epoxy-modified saturated polyester resin prepared by the present invention is applied to the coil coating primer, so that the coil coating primer not only has strong adhesion and corrosion resistance to metal, but also has a high Processability, with excellent surface hardness and weather resistance, it has excellent deformability, the overall performance is significantly improved, and the cost is reduced.
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| CN110845710A (en) * | 2019-12-13 | 2020-02-28 | 立邦工业涂料(上海)有限公司 | Epoxy modified polyester resin and preparation method and application thereof |
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| CN116948160A (en) * | 2022-04-16 | 2023-10-27 | 平原温特实业有限公司 | Synthesis method of polyester resin containing epoxy groups |
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