CN102391743A - Aqueous primer used for bicycles - Google Patents
Aqueous primer used for bicycles Download PDFInfo
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Abstract
本发明涉及一种自行车用水性底漆，它是由水性环氧丙烯酸树脂25～45，固化剂树脂2～10，中和剂二甲基乙醇胺1～3，复合防锈颜料2～10，着色颜料和填料5～20，消泡剂0.1～0.5，流平剂0.1～0.5，去离子水20～40，各组分含量之和为100，以上均为重量份百分比；其水性环氧丙烯酸树脂中环氧树脂在树脂总重量中占10～40％；固化剂树脂是由质量比为1∶5～5∶1的水性封闭型聚氨酯固化剂树脂和氨基固化剂树脂组成，其水性封闭型固化剂在130℃时解封并固化，氨基固化剂树脂为甲醇或丁醇醚化三聚氰胺甲醛树脂；复合防锈颜料由改性磷酸锌、氧化锌和离子交换型防锈颜料组成。特别适合自行车等结构的防锈、防腐蚀。The invention relates to a water-based primer for bicycles, which is composed of 25-45 water-based epoxy acrylic resins, 2-10 curing agent resins, 1-3 neutralizing agents dimethyl ethanolamine, 2-10 composite antirust pigments, and colored Pigment and filler 5-20, defoamer 0.1-0.5, leveling agent 0.1-0.5, deionized water 20-40, the sum of the contents of each component is 100, and the above are percentages by weight; its water-based epoxy acrylic resin The epoxy resin accounts for 10-40% of the total weight of the resin; the curing agent resin is composed of a water-based closed polyurethane curing agent resin and an amino curing agent resin with a mass ratio of 1:5-5:1. The curing agent is unblocked and cured at 130°C. The amino curing agent resin is methanol or butanol etherified melamine formaldehyde resin; the composite antirust pigment is composed of modified zinc phosphate, zinc oxide and ion exchange antirust pigment. It is especially suitable for anti-rust and anti-corrosion of structures such as bicycles.
Description
Technical field
The present invention relates to a kind of bicycle use aqueous priming paint, be specially adapted to isostructural antirust, the protection against corrosion of bike.
Background technology
The application of bike is similar with other vehicular traffic applications, generally all adopt priming paint, in be coated with and the finish paint system.At the domestic solvent-based system that generally adopts of bicycle trade, the discharging of a large amount of organic volatile compounds not only destroys environment at present, and the harm people are healthy, also wastes the resource and the energy simultaneously.Under these circumstances, bike manufacturing concern requires exploitation bicycle use aqueous coating system with the replacement solvent based coating in order to respond the national industrial policies developing direction.But the coating process of existing bike is different from general vehicular traffic; Requirement is filmed at 135 ± 3 ℃; Toast 10～15 minutes completely solidified dryings, and the salt tolerant rerum natura of filming, anti-boiling water cooking will reach specified requirement, and the amino system of current water soluble acrylic acid is to be main film-forming resin with water-borne acrylic resin; Aminoresin is curing agent resin; Because the erosion resistance of water-borne acrylic resin can not satisfy bike coating to etch-proof requirement,, solidify the back film performance and be difficult to reach protection against corrosion and antirust requirement though the aminoresin price is low; In addition, the electrophoresis system that adopted of general vehicular traffic priming paint is not suitable for the processing requirement of bike application.Develop a kind of compliance with environmental protection requirements for this reason, can satisfy the requirement of bike coating process, have the priming paint of performances such as excellent antirust, protection against corrosion and anti-boiling water simultaneously, seem particularly necessary to satisfy the growing demand of bicycle trade.
Summary of the invention
The objective of the invention is: a kind of suitable bike baking condition is provided, antirust, protection against corrosion and resistance to boiling water can improve and the bicycle use aqueous priming paint of compliance with environmental protection requirements.
The technical scheme that realizes the object of the invention is: a kind of bicycle use aqueous priming paint is characterized in that be made up of following component, in weight part per-cent, each amounts of components is following:
Water-based epoxy acrylic resin 25～45, curing agent resin 2～10, neutralizing agent dimethylethanolamine 1～3; Composite antirust pigment 2～10, tinting pigment and filler 5～20, skimmer 0.1～0.5; Flow agent 0.1～0.5, deionized water 20～40, each component concentration sum is 100%;
Said water-based epoxy acrylic resin is the vinyl resin of epoxy resin modification, and its vinyl resin acid value is 50～200mgKOH/g, and the epoxy equivalent (weight) of epoxy resin is 500～1500g/mol, and epoxy resin accounts for 10～40% in total resin weight;
Said curing agent resin is that 1: 5～5: 1 watersoluble closed type polyurethane curing agent resin and amino curing agent resin formed by mass ratio; Wherein watersoluble closed type curing agent resin is deblocking and curing in the time of 130 ℃, and the amino curing agent resin is methylated melamine formaldehyde resin or butyl alcohol etherified melamine-formaldehyde resin;
Said composite antirust pigment is made up of modified zinc phosphate, zinc oxide and Ion exchange anticorrosive pigment.
In the above-mentioned bicycle use aqueous priming paint; Said water-based epoxy acrylic resin is that the use epoxy equivalent (weight) is 500～1500g/mol; In total resin weight, account for 10～40% epoxy resin with solvent heating for dissolving and part amination, carrying out acid value that radical polymerization forms with vinylformic acid, Propylene glycol monoacrylate, Bing Xisuandingzhi and styrene monomer then is that the vinyl resin of 50～200mgKOH/g heats and carries out catalytic esterification and make.
In the above-mentioned bicycle use aqueous priming paint, the watersoluble closed type polyurethane curing agent resin in the said curing agent resin prepares as follows: in reaction vessel, add 100 weight part POLYMETHYLENE POLYPHENYLISOCYANATE in solid ,≤25 weight part solubility promoters and attemperation to 50 ℃; Add the encapsulant 3 of 10～30 weight parts then, insulation reaction is after 2 hours; Be warming up to 60～80 ℃ again, add the hydrophilic composition dimethylol propionic acid of 2～10 weight parts, insulation reaction 4 hours; Be cooled to 50 ℃ then, add in the neutralizing agent dimethylethanolamine of 2～8 weight parts and after, using deionized water to be diluted to solid again is 40 weight %; Filtration, packing promptly make watersoluble closed type polyurethane curing agent resin; Wherein POLYMETHYLENE POLYPHENYLISOCYANATE is hexamethylene diisocyanate biuret or hexamethylene diisocyanate tripolymer.
In the above-mentioned bicycle use aqueous priming paint, said filler is talcum powder and permanent white; Tinting pigment is carbon black and titanium white; Skimmer is Bi Ke chemistry Company products BYK025, and flow agent is Bi Ke chemistry Company products BYK331; De-ionized electrical conductivity of water≤20 μ s/cm.
Technique effect of the present invention is: the bicycle use aqueous priming paint of technical scheme of the present invention has following useful effect: 1. improved anticorrosion ability with water-based epoxy acrylic resin as the main film forming matter of priming paint.Because water-based epoxy acrylic resin is the vinyl resin by appropriate epoxy resin modification, making priming paint be higher than with water-borne acrylic resin performances such as the sticking power of base material and protection against corrosions is the priming paint of main film forming matter; 2. it is composite that solidifying agent uses two kinds of curing agent resins, improved paint film property and be fit to existing bike baking process.When the solidifying priming paint film forming; Two kinds of composite curing agent resins can obtain to have the paint film of tridimensional network with water-based epoxy acrylic resin; Make paint film have proper intensity and toughness; Particularly composite an amount of watersoluble closed type polyurethane curing agent resin has significantly improved the cooking characteristic of anti-boiling water of priming paint paint film; Watersoluble closed type polyurethane curing agent resin of while deblocking in the time of 130 ℃ also solidifies makes priming paint be fit to existing bike baking process, and composite an amount of amino curing agent resin can suitably reduce the cost of whole priming paint; 3. adopt by the composite composite antirust pigment of modified zinc phosphate, zinc oxide and Ion exchange anticorrosive pigment and improved rust-proof effect and environmental protection.Used three kinds of pigment not only can be given full play to the rust-proof effect of each rust-stabilising pigment but also also have synergy each other, and three kinds of pigment all do not contain heavy metal ion, and its feature of environmental protection meets the Rohs standard can satisfy the European market requirement; 4. each component collocation of priming paint of the present invention rationally can better bring into play the effect of each component, and each component synergetic property is good, and then has been guaranteed paint film property.The paint film of priming paint of the present invention is carried out correlated performance detects and show, paint film have excellent protection against corrosion, resistance to boiling water can and excellent weathering resistance and protect light, tint retention (seeing table 4).
Embodiment
Below in conjunction with embodiment the present invention is done further specific descriptions, but be not limited to this.
Unless otherwise indicated raw materials used among the embodiment, be coating and use commercially available industrial goods, the raw material consumption is weight part.
Embodiment 1 preparation water-based epoxy acrylic resin
Water-based epoxy acrylic resin is that the use epoxy equivalent (weight) is 500～1500g/mol; In total resin weight, account for 10～40% epoxy resin with solvent heating for dissolving and part amination; Carrying out acid value that radical polymerization forms with vinylformic acid, Propylene glycol monoacrylate, Bing Xisuandingzhi and styrene monomer then is that the vinyl resin of 50～200mgKOH/g heats and carries out catalytic esterification and make, and concrete operations are following:
1. the preparation of vinyl resin
244 weight part butyl glycol ethers and 90 weight part propylene glycol monomethyl ethers are joined in the 1000ml four-hole boiling flask that TM, whipping appts and condensing works are housed, start to stir and be warming up to 115 ℃ of temperature of reaction, with the Lucidol stirring and dissolving of the vinylbenzene of 92.7 parts by weight of acrylic hydroxypropyl acrylates, 51.3 parts by weight of acrylic, 186 parts by weight of acrylic butyl esters, 155 weight parts and 12 weight parts evenly after; Slowly be added drop-wise in the above-mentioned four-hole boiling flask then; About 4h of dropping time after dropwising, keeps 0.5h for 115 ℃ in temperature of reaction; Drip the mixture of 3 weight part Oxybenzene formyls and 75 weight part butyl glycol ethers again; About 1h of dropping time, at last at 115 ℃ of insulation reaction 2h of temperature of reaction, the cooling stopped reaction; Promptly make the vinyl resin that acid value is 80mgKOH/g, subsequent use;
2. the preparation of water-based epoxy acrylic resin
The epoxy E-12 resin of 100 weight parts (is accounted for 30% of whole weight resin; Its epoxy equivalent (weight) is 714～1111g/mol) to join in the 1000ml four-hole boiling flask that TM, whipping appts and condensing works are housed with the butyl glycol ether of 50 weight parts; Start stirring and be warming up to 120 ℃ of dissolvings of temperature of reaction evenly, carry out the part amination in 120 ℃ of mixtures that drip the butyl glycol ether of 6.6 weight part diethylolamine and 37.2 weight parts down, 1h drips; Insulation reaction 2h again; Add the 1. vinyl resin of middle preparation of 415 weight parts and the esterifying catalyst dimethylethanolamine of 20 weight parts then, in 120 ℃ of reactions 3 hours, the cooling stopped reaction; Promptly get water-based epoxy acrylic resin, its solid is 55 weight %.
Embodiment 2 watersoluble closed type polyurethane curing agent resin A of preparation and B
(1) concrete prescription is seen table 1.
Table 1
Annotate: N75 is the hexamethylene diisocyanate biuret product that Beyer Co., Ltd produces; N3390 is the hexamethylene diisocyanate tripolymer product that Beyer Co., Ltd produces.
(2) concrete preparation method
Press table 1 prescription, in reaction vessel, add POLYMETHYLENE POLYPHENYLISOCYANATE, solubility promoter and attemperation to 50 ℃; Add the encapsulant 3 then, insulation reaction is after 2 hours; Be warming up to 60～80 ℃ again, add hydrophilic composition dimethylol propionic acid, insulation reaction 4 hours; Be cooled to 50 ℃ then, add in the neutralizing agent dimethylethanolamine and after, using deionized water to be diluted to solid again is 40 weight %; Filtration, packing promptly make watersoluble closed type polyurethane curing agent resin A and B respectively, and wherein the NCO content of A is 11.7 weight % (in solid); The NCO content of B is 12.7 weight % (in solid).
Embodiment 3 preparation bicycle use aqueous priming paints
(1) prescription bicycle use aqueous priming paint is made up of following component, and in weight part per-cent, each amounts of components is following:
Water-based epoxy acrylic resin 25～45, curing agent resin 2～10, neutralizing agent dimethylethanolamine 1～3; Composite antirust pigment 2～10, tinting pigment and filler 5～20, skimmer 0.1～0.5; Flow agent 0.1～0.5; Deionized water 20～40, each component concentration sum is 100%, concrete prescription is seen table 2.
Table 2
Annotate: R717 is an Ineos company product amino resin;
BYK025 is the skimmer product of Bi Ke chemical company;
BYK331 is the flow agent product of Bi Ke chemical company;
Titanium white 902 is the rutile type product of E.I.Du Pont Company;
The PU carbon black is the carbon black product of Degussa company;
ZMP is the modified zinc phosphate rust-stabilising pigment product of Heubach GmbH;
Ion exchange anticorrosive pigment is commercially available calcium exchange silica pigment;
The products C TW-6018 of the also available CNOOC Changzhou Paint & Coatings Industry Research Institute of water-based epoxy acrylic resin in the table 2 replacement, its epoxy equivalent (weight) is 800g/mol, epoxy resin accounts for 30% in total resin weight;
(2) specifically prepare the technology of priming paint
1. in Scattered Kettle; Add water-based epoxy acrylic resin, curing agent resin, neutralizing agent, skimmer and the flow agent of table 2 formula ratio, dispersing speed is controlled at 400～500 rev/mins of scopes, stir made it to mix in 10 minutes after; The deionized water that adds table 2 part formula ratio; Dispersing speed increases to 500～700 rev/mins, stirs 15 minutes, and material becomes the oyster white homogeneous dispersion to the Scattered Kettle;
2. the oyster white homogeneous dispersion that 1. step is made shifts out half amount from Scattered Kettle; Preserve in addition, in Scattered Kettle, add pigment, filler, the composite antirust pigment of table 2 formula ratio then, the control dispersing speed is at 500～800 rev/mins; Stirred 15 minutes; Improve dispersing speed to 1000 rev/min then, stirred 20 minutes, make finely dispersed slurry;
3. the slurry that 2. step is made moves into sand mill and grinds, and the sand mill flow control was carried out sand milling at 4～4.5 hours/ton, made one ground slurry fineness reach 45 microns, and two road ground slurry fineness reach 20 microns, promptly meet index request;
4. the grinding disposed slurry that 3. step is made; Move in the Scattered Kettle, half amount oyster white homogeneous dispersion that 2. step is shifted out adds in Scattered Kettle and carries out paint again, and this moment, dispersing speed was controlled at 700～800 rev/mins; Stir after 15 minutes; Filter with 80～200 mesh filter screens, packing promptly makes bicycle use aqueous priming paint 1#.
Embodiment 4～6 preparation bicycle use aqueous priming paint 2#～4#
(1) prescription is seen table 3
Table 3
Annotate: each raw material is identical with table 2;
The products C TW-6018 of the also available CNOOC Changzhou Paint & Coatings Industry Research Institute of water-based epoxy acrylic resin in the table 3 replacement, its epoxy equivalent (weight) is 800g/mol, epoxy resin accounts for 30% in total resin weight;
(2) specifically prepare the technology of priming paint
Press the table 3 except that prescription, all the other technologies by embodiment 3 make bicycle use aqueous priming paint 2#～4# respectively.
Comparative example 1 aqueous priming paint
For the ease of comparing, the aqueous priming paint 1# of aqueous priming paint prescription and embodiment 3 is basic identical, and difference is: curing agent resin is only used 75 weight part R717 aminoresin; The technology of preparation aqueous priming paint is identical with embodiment 3, makes comparative example 1 aqueous priming paint.
Comparative example 2 aqueous priming paints
For the ease of comparing; The aqueous priming paint prescription is basic identical with the aqueous priming paint 1# of embodiment 3; Difference is: the water-based epoxy acrylic resin (embodiment 1 system) that replaces embodiment 3 with the water-borne acrylic resin (the Jiangsu three wooden EA3842 of company type water-borne acrylic resins) of 420 weight parts; The technology of preparation aqueous priming paint is identical with embodiment 3, makes comparative example 2 aqueous priming paints.
Comparative example 3 aqueous priming paints
For the ease of relatively, the aqueous priming paint 1# of aqueous priming paint prescription and embodiment 3 is basic identical, and difference is: the composite antirust pigment of being made up of three kinds of pigment with a kind of aluminium triphosphate (APW-2 of Guangxi Chemical Inst. type product) replacement embodiment 3 of 70 weight parts; The technology of preparation aqueous priming paint is identical with embodiment 3, makes comparative example 3 aqueous priming paints.
The performance of embodiment 7 test bicycle use aqueous priming paints
Detect and use model: plate size 10cm * 5cm, the surface sprays the aqueous priming paint of aqueous priming paint 1#～4# and comparative example 1～3 respectively after oil removing, polishing, first surface drying 20min, in 135 ℃ of baking 15min, build is 25 ± 2 μ m again.
By coatings industry concerned countries standard above-mentioned model is carried out the detection of correlated performance, detected result is listed in table 4 and table 5.
Table 4
Table 5
Annotate: the water resistant test in table 4 and table 5 test item (anti-boiling water boiled 1 hour, and each item performance is constant), ' each item performance ' wherein is meant the sticking power after the anti-boiling water boiling of paint film, the foaming situation of coating surface.
Can find out the bicycle use aqueous priming paint 1#～4# of embodiment of the invention preparation, the shock-resistant 50cm that all reaches of its paint film from the detected result of table 4 and table 5; Snappiness and sticking power reach 1 grade; Pencil hardness is 2H, and salt fog resistance can reach 240h, satisfies the RoHS standard of European Union;
Can find out that with comparative example 1 contrast the present invention adopts the priming paint of composite curing agent resin preparation, the anti-boiling water of its paint film boils especially good, and 1 hour paint film each item of boiling water boiling performance is constant;
Can find out that with comparative example 2 contrasts the present invention adopts water-based epoxy acrylic resin to make the priming paint of film-forming resin preparation, the salt spray resistance of its paint film improves;
Can find out that with comparative example 3 contrasts the present invention adopts the priming paint of the composite antirust pigment prepared of being made up of three kinds of pigment, the salt spray resistance of its paint film is superior to only using a kind of traditional aluminium triphosphate, has obviously improved the rust-proof effect of system.
Each the component collocation of the aqueous priming paint of technical scheme of the present invention is reasonable, and each component synergetic property is good, therefore, has the weathering resistance of excellent protection against corrosion, resistance to boiling water ability and excellence and protects light, tint retention, is particularly suitable for isostructural antirust, the protection against corrosion of bike.
Claims (4)
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| CN104087129A (en) * | 2014-07-27 | 2014-10-08 | 广西梧州龙鱼漆业有限公司 | Primer composition for bicycles |
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| CN105602402A (en) * | 2016-01-09 | 2016-05-25 | 安徽万诚达新型材料有限公司 | Waterborne epoxy sealing paint and preparation method thereof |
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Address after: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee after: China National Offshore Oil Corporation Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Patentee after: CNOOC Changzhou EP Coating Co., Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC Changzhou Paint & Coatings Industry Research Institute Patentee before: CNOOC Energy Development Co., Ltd. Patentee before: CNOOC Changzhou EP Coating Co., Ltd. |
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Effective date of registration: 20161228 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee after: CNOOC Energy Technology Co., Ltd. Patentee after: CNOOC Changzhou Environmental Protection Paint Co.,Ltd. Address before: 100010 Dongcheng District, Chaoyangmen, North Street, No. 4705, No. 25, box office, Beijing Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE CO., LTD. Patentee before: CNOOC Energy Technology Co., Ltd. Patentee before: CNOOC Changzhou Environmental Protection Paint Co.,Ltd. |