CN103408977B - A kind of clean taste wear-resistant ultraviolet ray solidified paint and preparation method thereof - Google Patents
A kind of clean taste wear-resistant ultraviolet ray solidified paint and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of clean taste wear-resistant ultraviolet ray solidified paint and preparation method thereof, described coating consists of the following composition: UV-cured resin, response type acrylate monomer, light trigger, defoamer, flow agent and wetting dispersing agent.Coating provided by the invention is the wear-resisting UV photo-cured coating of clean taste of the coating process such as spraying, roller coat, showering for suite room furniture, cabinet, door-plate.Also there is superior abrasion resistance and levelling effect simultaneously, plate face is smooth, also GB18582-2009 and GB/T9756-2009 is met except short construction period, not containing hazardous and noxious substances such as benzene, formaldehyde and free TDIs, and heavy metal content is well below European standard, an environmental-protecting performance excellence, and the forward and backward benzene content (mg/M that constructs
2) be not more than the functional product of 0.003 effect, be clean taste wear-resistant ultraviolet ray solidified paint.
Description
Technical field
The present invention relates to paint field, be specifically related to a kind of clean taste wear-resistant ultraviolet ray solidified paint and preparation method thereof.
Background technology
Ultraviolet-curing paint, English name is ultravioletcuringcoating, is called for short UV coating material solidified, and its first part of patent was born in nineteen forty-seven, and the advantages such as repainting hours is short, production efficiency is high because having, environmental protection, develop very rapid.
But nitro paint, unsaturated polyester coating, polyurethane coating are all worse than UV photo-cured coating due to its feature of environmental protection, efficiency, production cost.Particularly in environmental protection, be also worse than UV photo-cured coating.Normally used formula in existing UV photo-cured coating technology is analyzed and tested detection, in conjunction with the experimental data in market, regular understanding can be summed up, namely the mechanism of benzene is produced in formula be made up of multiple acrylic compound, Light Curing, some compounds, just containing benzene by before illumination, do not increase after illumination; Illustrate that benzene is residual or pollution in the fabrication process, if be raw material with benzene compound, be finally all difficult to thoroughly remove totally.Not containing benzene before some compound illumination, but after illumination, benzene content increases, and illustrates that this compound is by photo-labile, can decomposite free benzene molecular.One or two monosubstituted phenyl ring is all contained in the structure of most UV photo-cured coating; and be all connected with carbonyl (or phosphoryl), there is larger cleavable, thus discharge free benzene molecular; create irritating smell, very large impact is caused on environment, life health.Domestic " clean taste " coating concept has the multiple approximate concept obscured at present, and such as a lot of coating producer all releases low taste coating (ultraviolet-curing paint), but has a small amount of irritating smell to produce in preparation or use procedure.
CN201210452274.5 discloses a kind of waterborne glass coatings containing modification infusorial earth and preparation method thereof, it is made up of the raw material of following weight parts: acrylic ester emulsion 55-65, water-compatible amino resin 8-10, dipropylene 1-3, pure water 10-15, fatty acid polyglycol ester 0.4-0.6, defoamer polypropylene glycerol aether 0.2-0.4, Aerosol OT 0.2-0.6, zinc oxide 0.3-0.5, adhesion promoter BOK-M-2080.2-0.4, flow agent L-3500.3-0.5, modification infusorial earth 0.3-0.5, aerosil 0.1-0.3, aqueous silane coupling agent A8000.8-1.2.
CN01128598.2 discloses a kind of environment-friendly ink.It solve the problem that traditional ink environmental pollution is more serious, drip irrigation device of the present invention is: it is by adopting water-soluble acrylic ester 10-30 part, water soluble amino resin 1-30 part, or water-soluble amino-acid ester 0-30 part, or water-soluble epoxy ester 0-30 part, solubility promoter 1-50 part, or colorant 0-20 part, water 30-80 part.
Domestic also have some to report in clean taste coating, as Chinese patent application CN200910197319.7(publication number CN102040907A) a kind of solidify after without the UV-light carpentry matt varnish of remaining irritating smell, be made up of the component of following weight percent: modification acrylate 35-50%, functional monomer 35-45%, defoamer 0.1-0.3%, flow agent 0.3-1%, matting agent 0-11%, light trigger 5-7%, dispersion agent 0-1.0%.Without remaining irritating smell after the paint solidification that this patent proposes, but hardness of film after coated solidified, all poor ultraviolet-curing paint of film scrape resistant and wear resisting property aspect.
CN200480029306.4 relates to a kind of coating agent of radiation-hardenable, it comprises at least one per molecule and has two ethylenical unsaturated double bonds and containing aliphatic urethane (methyl) acrylate of the Embedded polytetrahydrofuran diol of at least one, and at least one monomer belongs to unsaturated reactive thinner.
Preparing varnish for woodwork manufacturing enterprise, all having no irritating odor before using the construction of varnish and after construction and can purify air, and the wear-resistant ultraviolet ray solidified special effective function coating of taste is then that art technology is blank only always.
Summary of the invention
The object of this invention is to provide one and be to provide a kind of clean taste wear-resistant ultraviolet ray solidified paint.
Another object of the present invention is the preparation method proposing above-mentioned coating.
The present invention is the 3rd object is the application proposing above-mentioned coating.
The clean taste wear-resistant ultraviolet ray solidified paint of one provided by the invention, consists of the following composition: ultraviolet light polymerization aminoresin, response type acrylate monomer, light trigger, defoamer, flow agent and wetting dispersing agent.
Concrete, described coating is grouped into by the one-tenth of following weight part: ultraviolet light polymerization aminoresin 40-60 part, response type acrylate monomer 30-55 part, light trigger 3.0-10 part, defoamer 0.2-0.5 part, flow agent 0.2-1.0 part and wetting dispersing agent 0.5-2.0 part.
Preferably, described coating is grouped into by the one-tenth of following weight part: ultraviolet light polymerization aminoresin 50-60 part, response type acrylate monomer 34-44 part, light trigger 3.0-5.0 part, defoamer 0.4-0.5 part, flow agent 0.2-0.5 part and wetting dispersing agent 0.8-1.5 part.
Further preferably, described coating is grouped into by the one-tenth of following weight part: 60 parts, ultraviolet light polymerization aminoresin, response type acrylate monomer 34.2 parts, light trigger 4.0 parts, defoamer 0.5 part, flow agent 0.3 part and wetting dispersing agent 1.0 parts.
In above-mentioned coating:
Described weight part can be the known weight unit of field of medicaments such as μ g, mg, g, kg, also can be its multiple, as 1/10,1/100,10 times, 100 times etc.
Described ultraviolet light polymerization aminoresin is solid content 95-98% ultraviolet curable amino acrylate.
Described response type acrylate monomer is tetrahydrofuran (THF) acrylate monomer (THFA).
Described light trigger is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone or 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, is preferably 1-hydroxycyclohexyl phenyl ketone.
Described defoamer is acrylate solvent solution;
Described flow agent is fluorine-carbon modified polyacrylic ester or polyether siloxane copolymer, is preferably polyether siloxane copolymer;
Described wetting dispersing agent is polyether-modified polydimethylsiloxanecopolymer copolymer or amber ester block copolymer, is preferably polyether-modified polydimethylsiloxanecopolymer copolymer.
Present invention also offers a kind of method preparing coating, it comprises the following steps:
1) ultraviolet light polymerization aminoresin and response type acrylate monomer are mixed in proportion, dispersed with stirring 20-25 minute;
2) under dispersed with stirring, wetting dispersing agent, flow agent is added, dispersed with stirring 10 minutes;
3) in step 3) gained mixture, defoamer dispersed with stirring 5-10 minute is added.
And adding of light trigger, adding wetting dispersing agent, flow agent, adding after dispersed with stirring, also can add dispersed with stirring together with defoamer, adding separately fashionable, dispersed with stirring 10-20 minute, mixing with defoamer and add, dispersed with stirring 10-15 minute.
Present invention also offers the application of above-mentioned coating in surface-coated.The method of surface-coated is spraying, roller coat or showering.Glue spread is respectively: spraying 80 ~ 120g/m
2; Roller coat 10 ~ 15g/m
2; Showering 120 ~ 140g/m
2.
When using coating surface of the present invention to apply, should be noted following item:
1, sand paper must be used before construction to surperficial sanded to be coated, fine and smooth surface after coating, can be obtained.
2, coating of the present invention is after coating construction, also need (flow time >=2 minute allow after the levelling of coated article own, then use ultraviolet light polymerization process at 30-40 DEG C of temperature baking levelling.
Clean taste wear-resistant ultraviolet ray solidified paint provided by the invention has the following advantages:
1, in coating provided by the invention,
Solid content in coating is on the low side, and the wear resistance of overall coating does not just reach requirement, can make the paint film deliquescing after application, after corrosive chemical substance contacts with paint film, coating can be made to produce irritating smell, affect the quality of paint film; When its solid content height, the hardness of paint film increases, will be corrosion-resistant.
The present invention selects ultraviolet light polymerization aminoresin to be the ultraviolet curable amino acrylate of color inhibition.In coating, 95-98% is required to the solid content of UV-cured resin, solid content is on the low side, hardness, the wear resistance of overall coating just do not reach requirement, the paint film deliquescing after application can be made, after corrosive chemical substance contacts with paint film, coating can be made to produce irritating smell, affect the quality of paint film; When its solid content height, the hardness of paint film increases, will be wear-resisting.Therefore, contriver selects the ultraviolet curable amino acrylate resin of solid content 95-98%;
Response type acrylate monomer, film scraping and wiping resistance performance is improved, curing speed is slack-off, surface hardness increases, this is because monomer ratio increase means the increase of system double bond density, just need the time more grown that all double bonds are reacted completely, cross-linking density increases simultaneously, hardness of paint film raises, and wear resistance is strengthened.
2, the selecting of response type monomer: response type monomer is also called bridging agent, because response type monomer can make the pungent odour in the some of film and air and toxicity participate in reacting, irritating smell is reduced, therefore, the selection of monomer just to be seemed particularly important on the impact of film performance.What the present invention selected is tetrahydrofuran (THF) acrylate monomer, the percentage composition reduction that the monomer in coating is total, adds the wear resistance of film, hardness fullness ratio, solves each side problems such as the forward and backward smell of coating application, wear resistance.
3, now a lot of formulas in order to reduce coating manufacturing cost, the raw material used and reactive thinner quality aspect all poor.Solvent-based system also containing part inside UV-light resin component.As the solvent-based system of routine, the irritating smell of the ultraviolet-curing paint that the existing market of workmen's reflection when constructing is applied itself is larger, simultaneously because selecting monomer system to be contain solvent-based system partly, in the process of construction, not only irritating smell is larger, and be all be difficult to carry out in stability of gloss, make workmen cannot accept these series product.
In the clean taste abrasion-resistant coating systems of UV-light that the present invention proposes, the resin selected is curable amino acrylate resin, it itself is also a clean taste wear resistant resin, response type monomer aspect is also wear-resisting clean taste monomer, to multiple base material have good sticking power, ultra-low-smell and wear-resisting, anti-yellowing property aspect all very well, shrinking percentage is low, solidification rate is fast, solvent resistant, acid-basicity are all fine.
4, coating of the present invention is mainly the wear-resisting UV photo-cured coating of clean taste of the coating process such as spraying, roller coat, showering for suite room furniture, cabinet, door-plate.Also there is superior abrasion resistance and levelling effect simultaneously, plate face is smooth, also GB18582-2009 and GB/T9756-2009 is met except short construction period, not containing benzene, formaldehyde and free TDI (Toluene-2,4-diisocyanate, 4-vulcabond) etc. hazardous and noxious substances, and heavy metal content is well below European standard, an environmental-protecting performance excellence, and the forward and backward benzene content (mg/M that constructs
2) be not more than the functional product of 0.003 effect, be clean taste wear-resistant ultraviolet ray solidified paint.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Described ultraviolet light polymerization aminoresin is solid content 95-98% ultraviolet curable amino acrylate, and ultraviolet curable amino acrylate resin ZC-5601 is purchased from Guangzhou Zuan Shuo Chemical Industry Science Co., Ltd;
Described response type acrylate monomer is tetrahydrofuran (THF) acrylate monomer (THFA), purchased from Tianjin proud son of heaven Chemical Co., Ltd.;
Described light trigger is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone or 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, and wherein 1-hydroxycyclohexyl phenyl ketone is purchased from Beijing Yingli Technology Development Co., Ltd;
Described defoamer is acrylate solvent solution, and acrylate solvent solution BYK-055 is purchased from BYK company;
Described flow agent is fluorine-carbon modified polyacrylic ester or polyether siloxane copolymer, and wherein polyether siloxane copolymer TEGO-410 is purchased from Di Gao company;
Described wetting dispersing agent is polyether-modified polydimethylsiloxanecopolymer copolymer or amber ester block copolymer, and wherein polyether-modified polydimethylsiloxanecopolymer copolymer BYK-P-104 is purchased from BYK company.
Embodiment 1: the clean wear-resisting UV photo-cured coating of taste
1, raw-material weight per-cent is as table 1:
| Composition | Weight (kg) | Weight percentage (%) |
| ZC-5601 UV-cured resin | 50.2 | 50.2 |
| Response type acrylate monomer THFA | 44 | 44 |
| Light trigger 1-hydroxycyclohexyl phenyl ketone | 4.0 | 4.0 |
| Defoamer BYK-055 | 0.5 | 0.5 |
| Flow agent TEGO-410 | 0.3 | 0.3 |
| Wetting dispersing agent BYK-P-104 | 1.0 | 1.0 |
| Add up to | 100 | 100 |
2, preparation method:
1), after first ZC-5601, THFA being stirred, 22 minutes are disperseed with dispersion machine (Yixing City lean machinery GFJ-B-75Kw);
2) then under agitation add BYK-P-104, TEGO-410 middling speed and disperse 10 minutes, disperse 20 minutes after stirring.
3) add defoamer again, light trigger disperses 10 minutes, to obtain final product.
Embodiment 2: the clean wear-resisting UV photo-cured coating of taste
1, raw material weight per-cent is as table 2:
Table 2: embodiment 2 proportioning raw materials
| Composition | Weight (kg) | Weight percentage (%) |
| ZC-5601 UV-cured resin | 42 | 42 |
| Response type acrylate monomer THFA | 52.2 | 52.2 |
| Light trigger 1-hydroxycyclohexyl phenyl ketone | 4.0 | 4.0 |
| Defoamer BYK-055 | 0.5 | 0.5 |
| Flow agent TEGO-410 | 0.3 | 0.3 |
| Wetting dispersing agent BYK-P-104 | 1.0 | 1.0 |
| Add up to | 100 | 100 |
2, preparation method:
1) high speed dispersion 25 minutes after first ZC-5601, THFA being stirred;
2) then under agitation add BYK-P-104, TEGO-410 middling speed and disperse 10 minutes, then light trigger is added in stirring dispersion machine, disperse 10 minutes after stirring;
3) add defoamer again and disperse 5 minutes, to obtain final product.
Embodiment 3: the clean wear-resisting UV photo-cured coating of taste
1, raw-material weight per-cent is as table 3:
Table 3: embodiment 3 proportioning raw materials
| Composition | Weight (kg) | Weight percentage (%) |
| ZC-5601 UV-cured resin | 60 | 60 |
| Response type acrylate monomer THFA | 34.2 | 34.2 |
| Light trigger 1-hydroxycyclohexyl phenyl ketone | 4.0 | 4.0 |
| Defoamer BYK-055 | 0.5 | 0.5 |
| Flow agent TEGO-410 | 0.3 | 0.3 |
| Wetting dispersing agent BYK-P-104 | 1.0 | 1.0 |
| Add up to | 100 | 100 |
2, preparation method:
1) disperse 20 minutes after first ZC-5601, THFA being stirred;
2) then under agitation add BYK-P-104, TEGO-410 middling speed and disperse 10 minutes, then light trigger is added in stirring dispersion machine, high speed dispersion 10 minutes after stirring;
3) add BYK-055 middling speed again and disperse 10 minutes, to obtain final product.
Experimental example: Product checking
1, detection method: the embodiment 5 to embodiment 1-3 and CN200910197319.7(CN102040907A) coating that provides detects, and concrete detection method is as follows:
Solid content: GB/T1725-79(second method);
Outward appearance: GB1727-79;
Fineness: GB/T1724-1979;
Sticking power: GB/T9286-1979;
Wear resistance: GB T1768-1979 (1989)=(750 500r) 0.03g;
Smell is tested: 60 DEG C of constant temperature 30min, evaluates its smell.
2, detected result: see 4.
The Product checking result of table 4: embodiment 1-3 and comparative example
Table 4 result shows:
The coating that the embodiment of the present invention 1 provides, 60 DEG C of laggard promoting the circulation of qi taste tests of constant temperature 30min, evaluate its smell size, evaluation of estimate scope is 0-5, and numerical value less expression smell is lower.Smell test (evaluating during 60 DEG C of constant temperature 30min), its oder levels is 1 grade.Wear resistance GB T1768-1979 (1989)=0.05, similar with ideal effect.Respectively by the method for spraying, roller coat, showering, front sand paper of constructing, to surperficial sanded to be coated, 40 DEG C of temperature bakings after coating, then uses treatment with ultraviolet light.Then test, coming to the same thing of test.This product before use, use after not only without benzene volatilization, and use on the same day of can accomplishing to construct the same day.
Embodiment 2 carries out smell test at 60 DEG C of constant temperature 30min, evaluates its smell size, and evaluation of estimate scope is 0-5, and numerical value less expression smell is lower.Smell test (evaluating during 60 DEG C of constant temperature 30min), its oder levels is 2 grades, wear resistance GB T1768-1979 (1989)=0.04, close with ideal effect.Coating prepared by the present embodiment is tested with spraying, roller coat, showering respectively, coming to the same thing of test.
Embodiment 3 carries out smell test at 60 DEG C of constant temperature 30min, evaluates its smell size, and evaluation of estimate scope is 0-5, and numerical value less expression smell is lower.Smell test (evaluating during 60 DEG C of constant temperature 30min), its oder levels is 1 grade, wear resistance GB T1768-1979 (1989)=0.024, excellent with ideal effect.Coating prepared by the present embodiment, respectively with the method coating of spraying, roller coat, showering, is then tested, coming to the same thing of test.
From embodiment 1,2,3 and CN200910197319.7(CN102040907A) compare in the carrying out of coating and find out: the present invention uses resin and response type monomer and other composition proportion, all can obtain wear resisting property to fill a prescription preferably, ultraviolet curable amino acrylate resin, plentiful type aminoresin, low smell, fast setting, high crosslink density, have splendid surface hardness after film forming, scraping and wiping resistance performance is given prominence to, and crosses machine xanthochromia low.Add in system, promote film forming rate of drying, promote hardness of film, improve film scrape resistant and wear resisting property.The present invention selects response type monomer to be tetrahydrofuran (THF) acrylate monomer, the sticking power aspect of multiple base material is improved, low-shrinkage, ultra-low-smell and this product wear-resisting before use, use after not only without benzene volatilization, and use on the same day of constructing the same day can be accomplished.
Although above with general explanation, embodiment and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (5)
1. a clean taste wear-resistant ultraviolet ray solidified paint, it is characterized in that, described coating is grouped into by the one-tenth of following weight part: ultraviolet light polymerization aminoresin 50-60 part, response type acrylate monomer 34-44 part, light trigger 3.0-5.0 part, defoamer 0.4-0.5 part, flow agent 0.2-0.5 part and wetting dispersing agent 0.8-1.5 part, described ultraviolet light polymerization aminoresin is the ultraviolet curable amino acrylate of solid content 95-98%, described response type acrylate monomer is tetrahydrofuran (THF) acrylate monomer, described light trigger is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-acetone or 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl) phenyl]-1-butanone, described defoamer is acrylate solvent solution, described flow agent is fluorine-carbon modified polyacrylic ester or polyether siloxane copolymer, described wetting dispersing agent is polyether-modified polydimethylsiloxanecopolymer copolymer or amber ester block copolymer.
2. coating according to claim 1, it is characterized in that, described coating is grouped into by the one-tenth of following weight part: 60 parts, ultraviolet light polymerization aminoresin, response type acrylate monomer 34.2 parts, light trigger 4.0 parts, defoamer 0.5 part, flow agent 0.3 part and wetting dispersing agent 1.0 parts.
3. prepare a method for the coating described in claim 1 or 2, it is characterized in that, comprise the following steps:
1) ultraviolet light polymerization aminoresin and response type acrylate monomer are mixed in proportion, dispersed with stirring 20-25 minute;
2) under dispersed with stirring, add wetting dispersing agent, flow agent, dispersed with stirring 10 minutes, obtains mixture;
3) light trigger is added step 2) described in mixture in, dispersed with stirring 20-25 minute, then adds defoamer dispersed with stirring 5-10 minute;
Or add light trigger and defoamer, dispersed with stirring 10-15 minute.
4. method according to claim 3, is characterized in that, described step 3) mixture fineness≤30 μm after dispersed with stirring.
5. the application of the coating described in claim 1 or 2 in surface-coated.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487033A (en) * | 2002-08-07 | 2004-04-07 | 珠海东诚化工有限公司 | Ultraviolet ray cured paint for surface treatment or alumium ou aluminium sections |
| CN1486960A (en) * | 2002-08-07 | 2004-04-07 | 珠海东诚化工有限公司 | Ultraviolet light cured ceramic paint |
| CN102807805A (en) * | 2011-05-31 | 2012-12-05 | 比亚迪股份有限公司 | Ultraviolet curing coating composition and preparation method thereof |
-
2013
- 2013-08-27 CN CN201310379612.1A patent/CN103408977B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1487033A (en) * | 2002-08-07 | 2004-04-07 | 珠海东诚化工有限公司 | Ultraviolet ray cured paint for surface treatment or alumium ou aluminium sections |
| CN1486960A (en) * | 2002-08-07 | 2004-04-07 | 珠海东诚化工有限公司 | Ultraviolet light cured ceramic paint |
| CN102807805A (en) * | 2011-05-31 | 2012-12-05 | 比亚迪股份有限公司 | Ultraviolet curing coating composition and preparation method thereof |
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