CN101974132A - Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid - Google Patents
Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid Download PDFInfo
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- CN101974132A CN101974132A CN 201010517713 CN201010517713A CN101974132A CN 101974132 A CN101974132 A CN 101974132A CN 201010517713 CN201010517713 CN 201010517713 CN 201010517713 A CN201010517713 A CN 201010517713A CN 101974132 A CN101974132 A CN 101974132A
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Abstract
The invention discloses a modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid. The modified acrylic resin is formed by esterification and copolymerization of 5 to 10 percent of unsaturated fatty acid, 2 to 6 percent of polyalcohol, 3 to 7 percent of diacid or diacid anhydride, 10 to 50 percent of styrene, 40 to 80 percent of acrylic ester monomer and 0.8 to 3 percent of initiator in percentage by mass. The normal temperature quick-drying automobile paint has the characteristics of thermoplastic acrylic resin paint such as quick drying and good weather resistance, has good fullness and easy construction, is suitable for coating automobiles with high decorative performance, and also can be used for coating household appliances, machinery and the like. Because of high solid and low VOC emission, the automobile paint meets nowadays environment-friendly requirements.
Description
Technical field
The invention belongs to paint field, be specifically related to a kind of acrylic resin modified, acrylic resin modified preparation method and based on this acrylic resin modified high fullness ratio, high solid normal temperature quick-drying automobile finish.
Background technology
Acrylic resin paint is protected light, tint retention can be good, can keep the gloss and the color and luster of original paint film for a long time, fast light, good weatherability; The outdoor exposure weather resistance is strong, and the ultraviolet resistance irradiation is difficult for decomposing or flavescence; The acrylic resin varnish color and luster is very shallow, and fabulous transparency is arranged; Corrosion-resistant, the contamination and the corrosive nature of chemical such as acid-and base-resisting preferably, salt, grease, washing composition are arranged.Advantages such as domestic technique reaches its maturity simultaneously, raw material (Acrylic Acid Monomer) is in liberal supply are more and more accepted by the user, so its quantity increase is more and more, and kind is more and more complete, and the application and construction technology is also ripe gradually.Became development one of coating variety the most rapidly in recent years.
But acrylic resin paint also exist the paint film fullness ratio not good, to temperature sensitive, snappiness is poor, solid part is low, to shortcoming such as the pigment wetting dispersiveness is not good, all weakness cause its suitability not strong.
Use alkyd modified vinylformic acid, both kept acrylic resin paint and protected light, protect characteristics such as look, corrosion resistance and good, make the acrylic resin modified characteristics such as the Synolac fullness ratio is good, easy construction that have again, and cost is lower, and outstanding cost performance is arranged.
The method of alkyd modified acrylic resin has cold spelling, acrylic polymer esterification process, copolymerization method.Cold spelling is exactly to mix at normal temperatures with Synolac for preparing and acrylic resin to get final product, because molecular weight, polarity all differ greatly between Synolac and the acrylic resin, so consistency is bad, this method causes that gloss of film is poor, fullness ratio is bad, so substantially need not.The acrylic polymer esterification process is owing to be first acrylic acid synthesizing prepolymer, utilize carboxyl on the acrylic polymer molecule and polyvalent alcohol esterification and make acrylic resin modified, but this method still is shortcomings such as Synolac, acrylic polymer esterification are incomplete owing to molecular backbone chain, shortcomings such as the paint film erosion resistance of preparation is bad, gloss difference.Thereby acrylic resin modified copolymerization method preparation commonly used.
Chinese patent 200510123053.3A is disclosed to carry out modification with Vinyl toluene to Synolac separately, but because a large amount of easy xanthochromia of Vinyl toluene, weathering resistance is bad, therefore can't use out of doors, has limited application greatly.Chinese patent 200580017013.9,200810152804.8 disclosed acrylic acid modified alkyd resins all because acrylic acid content low (13-20%), still based on Synolac, are protected light, are protected look, corrosion resistance nature is suitable with Synolac.Therefore still need to improve.A kind of interpenetrating(polymer)networks acrylic resin is disclosed in Chinese patent 200710022329.8 and " interpenetrating(polymer)networks acrylic resin synthetic and to the influence of film performance " article, but it is only synthetic in its polyester polyol by a kind of oleic acid of ricinolic acid, because the ricinolic acid degree of unsaturation is very low, cause most acrylic monomer can't be grafted on the polyester polyol, substantially can't realize the IPN modification, and the present invention adopts several oleic acid compound, guarantee percentage of grafting, realize real IPN modification, so excellent performance, especially water-fast, weathering resistance performance of the present invention is much better than the disclosed performance of its article.
Summary of the invention
The objective of the invention is with traditional technology prepare high fullness ratio, high solid is acrylic resin modified, does not lose simultaneously weathering resistance, the corrosion resistance nature of acrylic resin again.Adopt several oleic acid compound, prepared Synolac with suitable degree of unsaturation, acrylic resin modified with it, guaranteed percentage of grafting, thereby become mem stage unsaturated link(age) crosslinked film forming under the effect of siccative, than unmodified acrylic resin paint better heat resistanceheat resistant after tackiness is arranged.While is owing to acrylic resin modified with the part Synolac, so the high and low VOC discharging of acrylic resin solid part of modification, more meets present environmental requirement.
Another object of the present invention provides a kind of above-mentioned acrylic resin modified preparation method.
A further object of the invention provides a kind of based on above-mentioned acrylic resin modified high fullness ratio, high solid normal temperature quick-drying automobile finish.
Purpose of the present invention can reach by following measure:
A kind of acrylic resin modified, this resin is that 5-10% unsaturated fatty acids, 2-6% polyvalent alcohol, 3-7% diprotic acid or dibasic acid anhydride, 10-50% vinylbenzene, 40-80% acrylic ester monomer and 0.8-3% initiator form through esterification, copolymerization by mass content.The preferred group of each component becomes: 7-10% unsaturated fatty acids, 5-6% polyvalent alcohol, 5-6% diprotic acid or dibasic acid anhydride, 15-30% vinylbenzene, 55-65% acrylic ester monomer and 0.8-1% initiator; Wherein each component sum is 100%.
Wherein unsaturated fatty acids is selected from one or more in linolenic acid, tall oil acid, behenic acid, vegetable seed oleic acid, cocinic acid, ricinolic acid, the dehydrated castor oleic acid.
Polyvalent alcohol is selected from one or more in glycerine, tetramethylolmethane, TriMethylolPropane(TMP), neopentyl glycol, the ethylene glycol.
Diprotic acid or dibasic acid anhydride are selected from one or more in phthalic anhydride, m-phthalic acid, terephthalic acid, the hexanodioic acid.
Acrylic ester monomer is selected from one or more in butyl acrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, vinylformic acid, methacrylic acid, butyl methacrylate, Rocryl 410, the hydroxyethyl methylacrylate.
Initiator is selected from a kind of in Diisopropyl azodicarboxylate, dibenzoyl peroxide, dicumyl peroxide, the peroxidation dimethylbenzoyl.
Acrylic resin modified synthetic through esterification, copolymerization two step process, its preparation method is: earlier unsaturated fatty acids, diprotic acid and polyvalent alcohol are mixed, be warmed up to 160-200 ℃ and carry out the polycondensation esterification, add vinylbenzene, acrylic ester monomer and initiator then, carry out copolyreaction in 110-130 ℃.
Polycondensation esterification to acid number is 10-20mgKOH/g; Copolyreaction to viscosity is 50-200 second (50% solid part is coated with-4 glasss/25 ℃ in dimethylbenzene).The scope of each component among the preparation method as mentioned above.
It is a kind of based on above-mentioned acrylic resin modified high fullness ratio, high solid normal temperature quick-drying automobile finish that the present invention also provides, and its component by following mass content is formed: described acrylic resin modified, the 5-30% pigment of 30-80% claim 1,5-30% xylene solvent and 1-3% auxiliary agent (each component sum is 100%).
Wherein pigment is selected from one or more in titanium dioxide, carbon black, chrome yellow, molybdenum red, ferric oxide series, phthalein mountain valley with clumps of trees and bamboo series, toluidine maroon, talcum powder, lime carbonate, barium sulfate, the silicon-dioxide; Described auxiliary agent is selected from one or more in pigment wetting dispersing agent, flow agent, matting agent, UV stablizer, UV absorption agent, defoamer, anti-sagging agent, anti-settling agent, siccative, the anti.Its preparation method is: acrylic resin modified and needed color stuffing, auxiliary agent, solvent are ground and evenly made.
Adopt the automobile finish of acrylic resin modified preparation of the present invention to have advantages such as high fullness ratio, high solid, normal temperature quick-drying, it has not only inherited thermoplastic acrylic resin lacquer normal temperature quick-drying, characteristics that weather resistance is good, and good, the easy construction of fullness ratio, especially be fit to the application of the automobile of high-decoration energy, also can be used for applications such as household electrical appliances, machinery.Because the high and low VOC discharging of solid part more meets present environmental requirement.
Embodiment
Embodiment 1: drop into 6% behenic acid in stainless steel cauldron, 2% tall oil acid, 5% phthalic anhydride, 5% tetramethylolmethane, start stirring, be warming up to 160 ℃, be incubated after 1 hour, be warming up to 200 ℃ of insulations again after 4 hours, sampling detecting acid number treats that acid number is to 8-12mgKOH/g, be cooled to 120 ℃, add dimethylbenzene, after stirring, begin to drip at 120 ± 5 ℃, 40% butyl methacrylate, 20% Propylene glycol monoacrylate, 1% methacrylic acid, 20% vinylbenzene, 1% benzoyl peroxide, the viscosimetric of taking a sample after 4 hours, treating viscosity, qualified (50% solid part is in dimethylbenzene second for 50-200, be coated with-4 glasss/25 ℃), filter and package.Concrete parameter sees Table one.
Embodiment 2: drop into 5% linolenic acid, 1% behenic acid, 2% ricinolic acid, 5% phthalic anhydride, 6% TriMethylolPropane(TMP) in stainless steel cauldron, operating procedure and controlling index are with embodiment 1, after reaching requirement, begin to drip 40% butyl acrylate, 19% Propylene glycol monoacrylate, 1% methacrylic acid, 20% vinylbenzene, 1% benzoyl peroxide, operating procedure and controlling index are with embodiment 1.Concrete parameter sees Table one.
Embodiment 3: drop into 7% tall oil acid, 3% dehydrated castor oleic acid, 5% m-phthalic acid, 5% tetramethylolmethane in stainless steel cauldron, operating procedure and controlling index are with embodiment 1, after reaching requirement, begin to drip 40% butyl methacrylate, 20% Propylene glycol monoacrylate, 1% methacrylic acid, 18% vinylbenzene, 1% benzoyl peroxide, operating procedure and controlling index are with embodiment 1.Concrete parameter sees Table one.
The acrylic resin modified index of table one the present invention
| Sequence number | Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 1 | Limpid and transparency | Limpid, transparent | Limpid, transparent | Limpid, transparent |
| 2 | Color and luster (Fe-Co method), number | 5 | 9 | 5 |
| 3 | Viscosity (being coated with-4/25 ℃), s | 70 | 98 | 76 |
| 4 | Acid number, mgKOH/g | 10.7 | 11.1 | 10.5 |
| 5 | Non-volatile part, % | 61.6 | 59.8 | 60.3 |
| 6 | Fineness, μ m | 10 | 10 | 10 |
Embodiment 4 with make among 70% embodiment 1 acrylic resin modified and 24% titanium dioxide, 5.1% xylene solvent mixed grinding to fineness less than 20 μ m, add 0.5% siccative, 0.1% anti, 0.3% flow agent, 0.1% defoamer again and mix and make high fullness ratio, the fast dried automobile finish of high solid.Spraying or brush making sheet, self-vulcanizing after 2 days test performance see Table two.
Embodiment 5 with make among 70% embodiment 3 acrylic resin modified and 24% medium chrome yellow medium yellow, 5.1% xylene solvent mixed grinding to fineness less than 20 μ m, add 0.5% siccative, 0.1% anti, 0.3% flow agent, 0.1% defoamer again and mix and make high fullness ratio, the fast dried automobile finish of high solid.Spraying or brush making sheet, self-vulcanizing after 2 days test performance see Table two.
Watch two fast dried automobile finish performance index
Claims (10)
- One kind acrylic resin modified, it is characterized in that this resin is that 5-10% unsaturated fatty acids, 2-6% polyvalent alcohol, 3-7% diprotic acid or dibasic acid anhydride, 10-50% vinylbenzene, 40-80% acrylic ester monomer and 0.8-3% initiator form through esterification, copolymerization by mass content.
- 2. according to claim 1 acrylic resin modified, it is characterized in that described unsaturated fatty acids is selected from one or more in linolenic acid, tall oil acid, behenic acid, vegetable seed oleic acid, cocinic acid, ricinolic acid, the dehydrated castor oleic acid.
- 3. according to claim 1 acrylic resin modified, it is characterized in that described polyvalent alcohol is selected from one or more in glycerine, tetramethylolmethane, TriMethylolPropane(TMP), neopentyl glycol, the ethylene glycol.
- 4. according to claim 1 acrylic resin modified, it is characterized in that described diprotic acid or dibasic acid anhydride are selected from one or more in phthalic anhydride, m-phthalic acid, terephthalic acid, the hexanodioic acid.
- 5. according to claim 1 acrylic resin modified, it is characterized in that described acrylic ester monomer is selected from one or more in butyl acrylate, Propylene glycol monoacrylate, Hydroxyethyl acrylate, vinylformic acid, methacrylic acid, butyl methacrylate, Rocryl 410, the hydroxyethyl methylacrylate.
- 6. according to claim 1 acrylic resin modified, it is characterized in that described initiator is selected from a kind of in Diisopropyl azodicarboxylate, dibenzoyl peroxide, dicumyl peroxide, the peroxidation dimethylbenzoyl.
- 7. described acrylic resin modified preparation method of claim 1, it is characterized in that earlier unsaturated fatty acids, diprotic acid and polyvalent alcohol being mixed, be warmed up to 160-200 ℃ and carry out the polycondensation esterification, add vinylbenzene, acrylic ester monomer and initiator then, carry out copolyreaction in 110-130 ℃.
- 8. preparation method according to claim 7 is characterized in that polycondensation esterification to acid number is 10-20mgKOH/g; Copolyreaction to viscosity is 50-200 second (50% solid part is coated with-4 glasss/25 ℃ in dimethylbenzene).
- 9. one kind based on acrylic resin modified high fullness ratio, high solid normal temperature quick-drying automobile finish, it is characterized in that being made up of the component of following mass content: described acrylic resin modified, the 5-30% pigment of 30-80% claim 1,5-30% xylene solvent and 1-3% auxiliary agent.
- 10. according to claim 9 based on acrylic resin modified high fullness ratio, high solid normal temperature quick-drying automobile finish, it is characterized in that described pigment is selected from one or more in titanium dioxide, carbon black, chrome yellow, molybdenum red, ferric oxide series, phthalein mountain valley with clumps of trees and bamboo series, toluidine maroon, talcum powder, lime carbonate, barium sulfate, the silicon-dioxide; Described auxiliary agent is selected from one or more in pigment wetting dispersing agent, flow agent, matting agent, UV stablizer, UV absorption agent, defoamer, anti-sagging agent, anti-settling agent, siccative, the anti.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010517713A CN101974132B (en) | 2010-10-22 | 2010-10-22 | Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid |
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| CN201010517713A CN101974132B (en) | 2010-10-22 | 2010-10-22 | Modified acrylic resin-based normal temperature quick-drying automobile paint with high fullness and high solid |
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| CN101974132B CN101974132B (en) | 2012-10-03 |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181017A (en) * | 2011-04-22 | 2011-09-14 | 常州华科树脂有限公司 | Unsaturated polyester resin for machine-made or hand-pasted plane skylight and preparation method thereof |
| CN102643392A (en) * | 2012-05-21 | 2012-08-22 | 中国科学院新疆理化技术研究所 | Synthesis method of styrene/acrylate-modified quick-drying water-based alkyd resin |
| CN103409016A (en) * | 2013-07-08 | 2013-11-27 | 吴江市物华五金制品有限公司 | High-weatherability paint for steel structure and preparation method of high-weatherability paint |
| CN104073115A (en) * | 2014-06-23 | 2014-10-01 | 无锡市崇安区科技创业服务中心 | Water-soluble acrylic acid paint and preparation method thereof |
| CN105462413A (en) * | 2015-12-28 | 2016-04-06 | 杭州名匠建筑装饰工程有限公司 | High-strength low-covering-thickness high-grade nano finish paint for vehicles and preparation method thereof |
| CN105622908A (en) * | 2014-11-28 | 2016-06-01 | 合众（佛山）化工有限公司 | Preparation method of nano-SiO2 modified alkyd resin |
| CN106084143A (en) * | 2016-06-29 | 2016-11-09 | 潍坊富乐新材料有限公司 | A kind of low VOC Hydroxylated acrylic resin and preparation technology thereof |
| CN109321073A (en) * | 2018-11-06 | 2019-02-12 | 河南恒润昌环保科技有限公司 | A kind of environment-friendly water-based baking enamel and preparation method thereof |
| CN109957298A (en) * | 2019-04-11 | 2019-07-02 | 益帆涂料(无锡)有限公司 | A kind of outer shell of safe deposit box large arch dam wear-resistant paint and its spraying method |
| CN110330596A (en) * | 2019-06-21 | 2019-10-15 | 佛山市顺德区蓝德堡实业有限公司 | A kind of quick-dry type aqueous alkide resin and preparation method thereof |
| CN110951057A (en) * | 2018-09-26 | 2020-04-03 | 万华化学（北京）有限公司 | Preparation method of alkyd resin and prepared resin, preparation method of acrylic acid modified alkyd resin and prepared resin |
| CN110951056A (en) * | 2018-09-26 | 2020-04-03 | 万华化学（北京）有限公司 | Preparation method of alkyd resin and prepared resin, preparation method of acrylic acid modified alkyd resin and prepared resin |
| CN113603833A (en) * | 2021-07-02 | 2021-11-05 | 珠海展辰新材料股份有限公司 | Alkyd-acrylic hybrid emulsion and preparation method thereof |
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| EP1173491A2 (en) * | 1999-04-21 | 2002-01-23 | PPG Industries Lacke GmbH | Polymer |
| CN1355817A (en) * | 1999-04-21 | 2002-06-26 | Ppg工业油漆股份有限公司 | Polymer |
| CN1621430A (en) * | 2004-10-18 | 2005-06-01 | 常州市柏鹤涂料有限公司 | Modified dry oil alkyd resin for protective paint for metal coating on the back of the mirror and the curtain coating paint |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181017A (en) * | 2011-04-22 | 2011-09-14 | 常州华科树脂有限公司 | Unsaturated polyester resin for machine-made or hand-pasted plane skylight and preparation method thereof |
| CN102643392A (en) * | 2012-05-21 | 2012-08-22 | 中国科学院新疆理化技术研究所 | Synthesis method of styrene/acrylate-modified quick-drying water-based alkyd resin |
| CN103409016A (en) * | 2013-07-08 | 2013-11-27 | 吴江市物华五金制品有限公司 | High-weatherability paint for steel structure and preparation method of high-weatherability paint |
| CN104073115A (en) * | 2014-06-23 | 2014-10-01 | 无锡市崇安区科技创业服务中心 | Water-soluble acrylic acid paint and preparation method thereof |
| CN105622908A (en) * | 2014-11-28 | 2016-06-01 | 合众（佛山）化工有限公司 | Preparation method of nano-SiO2 modified alkyd resin |
| CN105462413A (en) * | 2015-12-28 | 2016-04-06 | 杭州名匠建筑装饰工程有限公司 | High-strength low-covering-thickness high-grade nano finish paint for vehicles and preparation method thereof |
| CN106084143A (en) * | 2016-06-29 | 2016-11-09 | 潍坊富乐新材料有限公司 | A kind of low VOC Hydroxylated acrylic resin and preparation technology thereof |
| CN106084143B (en) * | 2016-06-29 | 2019-07-09 | 潍坊富乐新材料有限公司 | A kind of low VOC Hydroxylated acrylic resin and its preparation process |
| CN110951057A (en) * | 2018-09-26 | 2020-04-03 | 万华化学（北京）有限公司 | Preparation method of alkyd resin and prepared resin, preparation method of acrylic acid modified alkyd resin and prepared resin |
| CN110951056A (en) * | 2018-09-26 | 2020-04-03 | 万华化学（北京）有限公司 | Preparation method of alkyd resin and prepared resin, preparation method of acrylic acid modified alkyd resin and prepared resin |
| CN109321073A (en) * | 2018-11-06 | 2019-02-12 | 河南恒润昌环保科技有限公司 | A kind of environment-friendly water-based baking enamel and preparation method thereof |
| CN109957298A (en) * | 2019-04-11 | 2019-07-02 | 益帆涂料(无锡)有限公司 | A kind of outer shell of safe deposit box large arch dam wear-resistant paint and its spraying method |
| CN110330596A (en) * | 2019-06-21 | 2019-10-15 | 佛山市顺德区蓝德堡实业有限公司 | A kind of quick-dry type aqueous alkide resin and preparation method thereof |
| CN113603833A (en) * | 2021-07-02 | 2021-11-05 | 珠海展辰新材料股份有限公司 | Alkyd-acrylic hybrid emulsion and preparation method thereof |
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