CN103013324B - Self-repair type ultraviolet-cured paint - Google Patents
Self-repair type ultraviolet-cured paint Download PDFInfo
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- CN103013324B CN103013324B CN201210562296.7A CN201210562296A CN103013324B CN 103013324 B CN103013324 B CN 103013324B CN 201210562296 A CN201210562296 A CN 201210562296A CN 103013324 B CN103013324 B CN 103013324B
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Abstract
The invention provides a kind of self-repair type ultraviolet-cured paint, comprise weight part be the polyester polyurethane acrylate oligopolymer of 5 ~ 15, the vinylformic acid upgrading of 8 ~ 18 containing solvent-borne type oligopolymer, 5 ~ 15 high official can urethane acrylate oligomer, 4 ~ 10 high functional acrylate monomers, 0.2 ~ 0.5 adhesion promoter, the light trigger of 0.3 ~ 0.5, the thinner of 40 ~ 80 and 0.2 ~ 0.5 auxiliary agent.Solve prior art medium ultraviolet photo-curing paint and do not have self-reparing capability, poor stability, snappiness is poor, and resistance to bending performance is low, the technical problem of rub resistance ability.
Description
Technical field
The present invention relates to paint field, especially, relate to a kind of self-repair type ultraviolet-cured paint.
Background technology
Ultraviolet-curing paint, compared with traditional coating, has curing speed fast, saves the advantage such as the energy, good, the applicable automatic production of paint film property, is thus widely used in the fields such as mobile phone, makeup, computer.For making the surface of paint film not affect the attractive in appearance of product because of scuffing, prior art generally adopts to be increased hardness of paint film and strengthens coating surface slickness to improve the resistance to marring of paint film.Although the method can improve the scratch resistance of paint film to a certain extent, significantly can reduce the snappiness of paint film, cause the resistance to bending of paint film and resistance to Steel Wool degradation, not there is self-healing properties; Meanwhile, add the cross-linking density of paint film owing to improving hardness, therefore the internal stress of solidified coating significantly increases, and easily causes paint film coating to affect use properties to the attachment bad stability of base material.
Summary of the invention
The object of the invention is to provide a kind of self-repair type ultraviolet-cured paint, and do not have self-reparing capability, poor stability to solve prior art medium ultraviolet photo-curing paint, snappiness is poor, and resistance to bending performance is low, the technical problem of rub resistance ability.
For achieving the above object, according to an aspect of the present invention, provide a kind of self-repair type ultraviolet-cured paint, comprise weight part be the polyester polyurethane acrylate oligopolymer of 5 ~ 15, the vinylformic acid upgrading of 8 ~ 18 containing solvent-borne type oligopolymer, 5 ~ 15 high official can urethane acrylate oligomer, 4 ~ 10 high functional acrylate monomers, 0.2 ~ 0.5 adhesion promoter, the light trigger of 0.3 ~ 0.5, the thinner of 40 ~ 80 and 0.2 ~ 0.5 auxiliary agent.
Further, polyester polyurethane acrylate oligopolymer is 8 ~ 12 weight parts.
Further, vinylformic acid upgrading is 10 ~ 15 weight parts containing solvent-borne type oligopolymer.
Further, high official can urethane acrylate oligomer be 8 ~ 12 weight parts.
Further, adhesion promoter is silane coupling agent and phosphate modified acrylate monomer.
Further, high functional acrylate monomers is 6 ~ 8 weight parts.
Further, high functional acrylate monomers is 3 functionality or 4 functionality acrylate monomers.
Further, comprise weight part be the polyester polyurethane acrylate oligopolymer of 8, the vinylformic acid upgrading of 11 containing solvent-borne type oligopolymer, 8 high official can urethane acrylate oligomer, 6 high functional acrylate monomers, 0.3 adhesion promoter, the light trigger of 0.4, the thinner of 80 and 0.4 auxiliary agent.
The present invention has following beneficial effect:
Self-repair type ultraviolet-cured paint provided by the invention, after application, gained paint film has cut self-repair function, and adopt copper brush with 2000g heavy burden friction coating surface, the cut selfreparing time is 5 ~ 30 seconds.Under load 1000g condition, hardness reaches 3H, and Steel Wool is wear-resisting reaches more than 600 times, and bend 90 degree without cracking phenomena, RCA wear test reaches more than 1500 times; And it is good to be coated on the substrate surface sticking power such as PC, ABS, PMMA, PC/ABS, stainless steel, magnesium alloy, zinc alloy.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to embodiment, the present invention is further detailed explanation.
Embodiment
Below in conjunction with specification sheets, embodiments of the invention are described in detail, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
The object of the present invention is to provide a kind of self-repair type ultraviolet-cured paint, have in excellent self-reparing capability situation, ensure other use properties stability of paint film.
Self-repair type ultraviolet-cured paint comprise weight part be the polyester polyurethane acrylate oligopolymer of 5 ~ 15, the vinylformic acid upgrading of 8 ~ 18 containing solvent-borne type oligopolymer, 5 ~ 15 high official can urethane acrylate oligomer, 4 ~ 10 high functional acrylate monomers, 0.2 ~ 0.5 adhesion promoter, the light trigger of 0.3 ~ 0.5, the thinner of 40 ~ 80 and 0.2 ~ 0.5 auxiliary agent.
Wherein high official's energy urethane acrylate oligomer is the urethane acrylate oligomer of any functionality in 6 functionality, 9 functionality.Sense mentioned in this article is the functionality of polymkeric substance or reactive monomer, and wherein functionality refers to the number of unsaturated double-bond in acrylate group contained by polymkeric substance or reactive monomer.
Because ultraviolet-cured paint easily produces free radical under the action of uv light, free radical causes the component generation crosslinking curing phenomenon of ultraviolet-cured paint.Polyester polyurethane acrylate oligopolymer is a kind of light-cured resin, and it can adsorb the free radical in ultraviolet-cured paint, and the coating forming new chemical structure is to make up the coating of solidification, thus has self-reparing capability.But polyester polyurethane acrylate is added in ultraviolet-cured paint and will affect the stability of ultraviolet-cured paint, affect the self-reparing capability of PAUR acrylic resin simultaneously.In order to improve self-reparing capability and the stability of ultraviolet-cured paint, ensure hardness and the toughness of ultraviolet-cured paint simultaneously, with the addition of vinylformic acid upgrading in ultraviolet-cured paint of the present invention containing solvent-borne type oligopolymer, high official energy urethane acrylate oligomer, high functional acrylate monomers; Wherein high official's energy urethane acrylate oligomer is many containing function functional group number, and chain length is relatively short, has shorter molecular chain in paint film, can strengthen the hardness of paint film.But the high official of short chain can urethane acrylate oligomer easily cause paint film to occur slight crack in the curing process, and vinylformic acid upgrading containing solvent-borne type oligopolymer due to its functional group few, molecular chain length, flexility is more excellent, the one-tenth membrane stress that high official's energy urethane acrylate oligomer that can cushion high rigidity in the curing process produces, prevents from bursting apart during solidification.In addition, vinylformic acid upgrading adds containing solvent-borne type oligopolymer, makes ultraviolet-cured paint have outstanding sticking power on plastic cement and metal base.High functional acrylate monomers can fully be dissolved and letdown resin class material, regulates paint film system viscosity, increases paint film levelling property; Can also photocuring reaction be participated in simultaneously, and then the cross-linking density of adjustment paint film when solidifying, strengthen the wear-resisting and resistance to marring of paint film.
The present invention by the vinylformic acid upgrading of the polyester polyurethane acrylate oligopolymer of 5 ~ 15 weight parts, 8 ~ 18 weight parts containing solvent-borne type oligopolymer, 5 ~ 15 weight parts high official can urethane acrylate oligomer, the high functional acrylate monomers of 4 ~ 10 weight parts, the adhesion promoter of 0.2 ~ 0.5 weight part, the light trigger of 0.3 ~ 0.5 weight part, the thinner of 40 ~ 80 weight parts and 0.2 ~ 0.5 weight part auxiliary agent.The interphase interaction of each material, makes ultraviolet-cured paint take into account self-reparing capability and stability, and simultaneously the performance of the hardness of ultraviolet-cured paint, sticking power, rub resistance power significantly improves.If the content of polyester polyurethane acrylate oligopolymer is too low, then the self-reparing capability of ultraviolet-cured paint reduces, and the stability of ultraviolet-cured paint is deteriorated.If acrylic acid modified too low containing solvent-borne type oligomer, then the snappiness step-down of ultraviolet-cured paint, easily there is slight crack in paint film.The amount of certain added monomer is also influential to paint film property; When certain interpolation monomer is too much, paint film fragility increases impact resistance and declines; And if monomer addition is less, then wear-resisting the and scratch resistance capability of paint film is lower.
Further, polyester polyurethane acrylate oligopolymer is preferably 8 ~ 12 weight parts, when the content of polyester polyurethane acrylate is 8 ~ 12 weight part, ultraviolet-cured paint can ensure good cut selfreparing effect, simultaneously not only can ensure certain hardness but also be unlikely to lose due to much higher hard the toughness of paint film, and institute becomes the properties optimum of ultraviolet-cured paint.
Further, vinylformic acid upgrading is preferably 10 ~ 15 weight parts containing solvent-borne type oligopolymer.When the content that vinylformic acid upgrading contains solvent-borne type oligopolymer is 10 ~ 15 weight part, the toughness of ultraviolet-cured paint is strong, can resistance to 90 ° of bendings.
Further, high official urethane acrylate oligomer can be preferably 8 ~ 12 weight parts, and hardness and the wear resisting property of its ultraviolet-cured paint are strong.
Further, high functional acrylate monomers is preferably 6 ~ 8 weight parts, and the impact resistance of its ultraviolet-cured paint, wear resisting property is strong.
Further, 3 functionality that high functional acrylate monomers is preferably or 4 functionality acrylate monomers, the self-healing properties of its ultraviolet-cured paint, wear resisting property, toughness are all best.
Further, adhesion promoter is silane coupling agent and phosphate modified acrylate monomer, can ensure that hard coat can secure anchorage base material when cure shrinkage, stable curing coating to the sticking power of base material, thus makes paint film sticking power while having high rigidity also guaranteed.
Further, self-repair type ultraviolet-cured paint comprise weight part be the polyester polyurethane acrylate oligopolymer of 8, the vinylformic acid upgrading of 11 containing solvent-borne type oligopolymer, 8 high official can urethane acrylate oligomer, 6 high functional acrylate monomers, 0.3 adhesion promoter, the light trigger of 0.4, the thinner of 80 and 0.4 auxiliary agent, its wear resisting property, crocking resistance, resistance to bending performance, self-healing properties, hardness are all best.
Embodiment
The invention provides ultraviolet light polymerization selfreparing paint, required solidification energy is 600 ~ 1000mJ/cm
2, specifically can be provided by ultraviolet lamp.Various types of resins is known conventional resin herein, and the high functional acrylate monomers adopted in embodiment is herein dipentaerythritol acrylate.
In following examples, having the elastic polyester polyurethane acrylate oligopolymer of vulcanite, is UV-SH100 and UV-SH200 purchased from Japanese combination.
Vinylformic acid upgrading containing solvent-borne type oligopolymer be purchased from Changxing, Taiwan chemistry 6071 and 6076.
High official's energy urethane acrylate oligomer is the CN9013 of purchased from American Sartomer, the 6145-100 of Changxing, Taiwan chemistry.
High functional acrylate monomers is EM231 and EM241 purchased from Changxing, Taiwan chemistry.
In light trigger Alpha-hydroxy cyclohexyl benzophenone model be Irgacure 184 purchased from Ciba company of Switzerland, TMDPO model is that Darocur TPO is purchased from Ciba company of Switzerland.
In auxiliary agent, defoamer for poly-methyl alkyl siloxane solution model be BYK 077, flow agent be polyether-modified Dimethicone Copolyol build number is BYK333, all purchased from German BYK company.Auxiliary agent can improve coating performance and the use properties of ultraviolet light polymerization selfreparing paint.
The A-171 of silane coupling agent purchased from American union carbide corporation in adhesion promoter, phosphate modified acrylate monomer is the CD9050 of purchased from American Sartomer.The reasonably combined of this two classes adhesion promoter can strengthen the sticking power of paint film on multiple material effectively.
Thinner is ethyl acetate, butyl glycol ether, propylene-glycol ethyl ether acetic ester, is commercially available analytical pure.
The preparation method of embodiment 1 ~ 5 self-repair type ultraviolet-cured paint is as follows:
A () is by the preheating 1 ~ 2 hour at 40 ~ 70 DEG C of the higher resin of viscosity in the self-repair type ultraviolet-cured paint composition in embodiment 1 ~ 5, above-mentioned resin is fully dissolved with the thinner of 2/3 volume, wherein 2/3 volume refer to and paint again by ultraviolet light polymerization in after the parts by weight of thinner take, 2/3 of diluent volume, the interpolation of following thinner roughly the same.
B the acrylate monomer weighed in proportion, light trigger, adhesion promoter and auxiliary agent add by (), stir 10 ~ 40 minutes, stirring velocity 400 ~ 1000 revs/min at 40 ~ 70 DEG C.
C the thinner of the auxiliary agent weighed in proportion and 1/3 volume adds by (), stir 10 ~ 30 minutes, obtain product with 400 order filter-cloth filterings under 500 ~ 1200 revs/min.
Embodiment 1 ~ 5 self-repair type ultraviolet-cured paint coated solidified method: be sprayed on base material by ultraviolet light polymerization selfreparing paint obtained for embodiment 1 ~ 5, coating paint thickness is 20 microns, 60 DEG C of infrared lamps irradiate lower levelling 8 minutes, 800mJ/cm2 energy-curable.Ultraviolet light polymerization selfreparing paint obtained in embodiment 1 ~ 5 is sprayed into PC, ABS, PMMA, PC/ABS, metallic substrate surface, and coating process is the same.
The each Composition Weight Parts of embodiment 1 ~ 5 medium ultraviolet photo-curing paint is listed in table 1.
The formula of the ultraviolet-cured paint of table 1 embodiment 1 ~ 5
Comparative example 1
Ultraviolet-cured paint is prepared according to the paint proportioning mentioned in Chinese invention patent CN200780009549.5 embodiment 1 and method.
Comparative example 2
The auxiliary agent composition of the simple function official acrylate monomer of two functional aliphatic's polyurethane acrylic resins of the polyester polyurethane acrylate oligopolymer of 15 weight parts, high official's energy aliphatic polyurethane acrylic resin of 10 weight parts, 5 weight parts, the high functional acrylate monomers of 12 weight parts, 5 weight parts, the adhesion promoter of 0.2 weight part, the light trigger of 0.3 weight part, the thinner of 20 ~ 60 weight parts and 0.5 weight part.
Comparative example 3
The polyester polyurethane acrylate oligopolymer of 2 weight parts, the vinylformic acid upgrading of 25 weight parts containing solvent-borne type oligopolymer, 3 weight parts high official can urethane acrylate oligomer, the high functional acrylate monomers of 15 weight parts, 0.4 weight part adhesion promoter, the light trigger of 0.3 weight part, the thinner of 50 weight parts and 0.3 weight part auxiliary agent.
Comparative example 4
The vinylformic acid upgrading of 25 weight parts containing solvent-borne type oligopolymer, 15 weight parts high official can urethane acrylate oligomer, the high functional acrylate monomers of 10 weight parts, 0.4 weight part adhesion promoter, the light trigger of 0.3 weight part, the thinner of 80 weight parts and 0.3 weight part auxiliary agent.
Comparative example 5
The high official of the polyester polyurethane acrylate oligopolymer of 25 weight parts, 3 weight parts can urethane acrylate oligomer, the high functional acrylate monomers of 15 weight parts, 0.4 weight part adhesion promoter, the light trigger of 0.3 weight part, the thinner of 50 weight parts and 0.3 weight part auxiliary agent.
Embodiment 1 ~ 5 and comparative example 1 ~ 5 are carried out sticking power, selfreparing power, pencil hardness, wear resisting property, resistance to bending performance detect, detected result is listed in table 1.
RIM WI-QMR-06-002 standard testing is pressed in the wear-resisting test of each embodiment lacquer painting Steel Wool, namely on the linear wear resistant instrument of Taber 5700 (Taber industry manufactures), adopt 0000# Steel Wool under heavy burden 1000g condition, coating surface is rubbed, speed of circulation is 25 beats/min, and friction length is 2.5 centimetres.
The wear-resisting testing method of RCA is the wear-resisting testing method of conventional RCA, adopts Norman RCA wear-resistant tester, paint film heavy burden 175g.
Resistance to bending performance is by standard GB/T/T12754-1991 test.
Pencil hardness test is tested by standard GB/T/T 6739-2006, heavy burden 1000g; GB9286-1998 standard testing is pressed in sticking power test.
Cut selfreparing testing method: under normal temperature (25 DEG C), carry out backwash 10 times with copper brush (bear a heavy burden heavy 2000g), test solidified coating produces the time of recovery scratched.
The performance test results table of table 3 embodiment 1 ~ 5 and comparative example 1 ~ 5
From the experimental result of table 1, its self-reparing capability of self-repair type ultraviolet-cured paint of embodiment 1 ~ 5, hardness, wear resisting property, resistance to bending performance is apparently higher than comparative example 1 ~ 5, prove to carry out according to the formula of embodiment 1 ~ 5 and formula ratio the self-reparing capability combining the self-repair type ultraviolet-cured paint obtained, hardness, wear resisting property, resistance to bending performance is apparently higher than comparative example 1 ~ 5, if lack polyester polyurethane acrylate oligopolymer or vinylformic acid upgrading containing solvent-borne type oligopolymer, the ability of reviewing one's lessons by oneself of then obtained ultraviolet-cured paint reduces, wear resisting property and resistance to bending performance are deteriorated.Wherein the self-repair type ultraviolet-cured paint performance of embodiment 2 is best, is the optimum embodiment of the present invention.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a self-repair type ultraviolet-cured paint, it is characterized in that, comprise weight part be the polyester polyurethane acrylate oligopolymer of 5 ~ 15, the vinylformic acid upgrading of 8 ~ 18 containing solvent-borne type oligopolymer, 5 ~ 15 high official can urethane acrylate oligomer, 4 ~ 10 high functional acrylate monomers, 0.2 ~ 0.5 adhesion promoter, the light trigger of 0.3 ~ 0.5, the thinner of 40 ~ 80 and 0.2 ~ 0.5 auxiliary agent;
Vinylformic acid upgrading containing solvent-borne type oligopolymer be purchased from Changxing, Taiwan chemistry 6071 and 6076;
Described polyester polyurethane acrylate oligopolymer has self-healing properties;
Described high official's energy urethane acrylate oligomer is the urethane acrylate oligomer of any functionality in 6 functionality, 9 functionality;
Described high functional acrylate monomers is 3 functionality or 4 functionality acrylate monomers.
2. self-repair type ultraviolet-cured paint according to claim 1, is characterized in that, described polyester polyurethane acrylate oligopolymer is 8 ~ 12 weight parts.
3. self-repair type ultraviolet-cured paint according to claim 1, is characterized in that, described vinylformic acid upgrading is 10 ~ 15 weight parts containing solvent-borne type oligopolymer.
4. self-repair type ultraviolet-cured paint according to claim 1, is characterized in that, described high official can urethane acrylate oligomer be 8 ~ 12 weight parts.
5. self-repair type ultraviolet-cured paint according to claim 1, is characterized in that, described adhesion promoter is silane coupling agent and phosphate modified acrylate monomer.
6. self-repair type ultraviolet-cured paint according to claim 1, is characterized in that, described high functional acrylate monomers is 6 ~ 8 weight parts.
7. self-repair type ultraviolet-cured paint according to claim 1, it is characterized in that, comprise weight part be the polyester polyurethane acrylate oligopolymer of 8, the vinylformic acid upgrading of 11 containing solvent-borne type oligopolymer, 8 high official can urethane acrylate oligomer, 6 high functional acrylate monomers, 0.3 adhesion promoter, the light trigger of 0.4, the thinner of 80 and 0.4 auxiliary agent.
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| CN104177885B (en) * | 2014-08-18 | 2017-05-03 | 张家港康得新光电材料有限公司 | Hardening paint and preparation method thereof, and automobile window film |
| CN104559698B (en) * | 2014-12-11 | 2017-06-06 | 惠州市长润发涂料有限公司 | A kind of color inhibition UV transparent primings for electrostatic spraying |
| CN105086808A (en) * | 2015-07-30 | 2015-11-25 | 东莞英铭化工有限公司 | Anti-falling photocureable coating |
| KR102107736B1 (en) | 2015-08-03 | 2020-05-07 | 주식회사 엘지화학 | Coating composition for flexible plastic film |
| KR101862252B1 (en) | 2015-08-03 | 2018-05-29 | 주식회사 엘지화학 | Flexible plastic film |
| KR101862251B1 (en) * | 2015-08-03 | 2018-05-29 | 주식회사 엘지화학 | Flexible plastic film |
| CN105348474B (en) * | 2015-12-07 | 2018-02-16 | 南昌航空大学 | A kind of preparation method of the ultraviolet light solidification selfreparing polyurethane based on furans maleimide structure |
| CN107083090B (en) * | 2017-06-02 | 2019-07-09 | 京钻（厦门）科技有限公司 | A kind of preparation method and applications of self-regeneration film forced fluid |
| CN109722073A (en) * | 2017-10-27 | 2019-05-07 | 南昌欧菲光科技有限公司 | Self-repair type coating, self-repair type flexible cover plate and preparation method thereof and touch screen |
| CN110628318A (en) * | 2019-10-14 | 2019-12-31 | 广东昊辉新材料有限公司 | UV spraying bright white paint and preparation method thereof |
| CN111073498B (en) * | 2020-01-02 | 2021-07-23 | 湖南宏泰新材料有限公司 | UV (ultraviolet) curing self-repairing antistatic coating |
| CN112574605B (en) * | 2020-11-30 | 2022-05-06 | 上海甘田光学材料有限公司 | Photochromic film and preparation method thereof |
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