CN102924987A - Thermal-ultraviolet dual-curing water-based colored coating composition - Google Patents

Thermal-ultraviolet dual-curing water-based colored coating composition Download PDF

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Publication number
CN102924987A
CN102924987A CN2012103919589A CN201210391958A CN102924987A CN 102924987 A CN102924987 A CN 102924987A CN 2012103919589 A CN2012103919589 A CN 2012103919589A CN 201210391958 A CN201210391958 A CN 201210391958A CN 102924987 A CN102924987 A CN 102924987A
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China
Prior art keywords
component
water
coating composition
colored coating
acrylate
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CN2012103919589A
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Chinese (zh)
Inventor
梁亮
郭婧
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Guangdong University of Technology
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Guangdong University of Technology
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Priority to CN2012103919589A priority Critical patent/CN102924987A/en
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Abstract

The invention discloses a thermal-ultraviolet dual-curing water-based colored coating composition which comprises the following components: (a) an emulsion polymer containing at least one acetacetate group, wherein the glass transition temperature of the polymer is 0-100 DEG C; (b) a water-soluble polyfunctional-group acrylate monomer or polymer; (c) a photoinitiator; and (d) a water-based color paste. The composition effectively overcomes the restriction of color to ultraviolet curing in conventional ultraviolet curing, and greatly enhances the ultraviolet curing efficiency and film coating property of the water-based colored system.

Description

A kind of heat-UV-light dual cure water-based colored coating composition
Technical field
The present invention relates to a kind of aqueous pigmented coating composition, particularly a kind of heat-UV-light dual cure water-based colored paint composition.
Background technology
Ultraviolet solidified aqueous coating not only has the characteristics than other water-borne coatings quick solidifyings, and the performance of its film forming matter coating is more outstanding, is environmental friendliness coating.Yet the research of relevant UV-curable waterborne colored coating rarely has report.When in the ultraviolet curable coating system, pigmented system being cured, because pigment to Optical Absorption, shielding and reflex action, has affected light trigger to the ultraviolet Optical Absorption, reduce the efficiency of initiation of light trigger, cause the colored coating system to be difficult to completion of cure, its performance is reduced greatly.The main method that present people address this problem is from selecting the light trigger aspects of different photodestruciton wavelength, utilize the window effect of light to improve the not good problem of colored coating solidification effect, the document of having reported mostly is as research object take solvent system.And for the coloured aqueous coating system of ultraviolet light polymerization, because light trigger rarely has report in the immiscible property of water-based system.The research of the Color paint photocuring being carried out with the selection of initiator such as " research of New Photoinitiator System for Pigmented UV Curing Coatings " of the reports such as Wang Ying; Chinese patent CN101407651 has reported " a kind of UV curing color decorative coating "; CN101870846 has reported " a kind of high performance ultraviolet cured colored paint and preparation method thereof " etc.
Summary of the invention
Main purpose of the present invention is for providing a kind of heat-UV-light dual cure water-based colored coating composition, and it comprises following component:
(a) contain the emulsion polymer of at least one acetoacetic acid group, the second-order transition temperature of described polymkeric substance is between 0 ~ 100 ℃;
(b) water-soluble multi-functional acrylate's monomer or contain in multi-functional acrylate's the water-based UV cured resin one or both;
(c) light trigger; And
(d) aqueous color paste;
Wherein component (a) is that (a)/(b) is 15:1 to 1:1 with the weight ratio of component (b); Component (c) adds up to 100 weight parts in component (a) and component (b), and its content is 0.6 ~ 0.9 weight part; Component (d) adds up to 100 weight parts in component (a) and component (b), and its content is 20 ~ 60 weight parts; The volatilizable alkali that also contains capacity in the said composition, so that the acetoacetic acid group (a) is converted into enamine, under the condition of heating, enamine is converted into acetoacetic acid group again, with the two key generation Michael reactions of the C=C among the water-soluble multi-functional acrylate, realize ultraviolet light polymerization.
Wherein component (a) is 10:1 to 2:1 with the further preferred weight ratio (a)/(b) of component (b).
The acrylic ester emulsion polymkeric substance that wherein contains at least one acetoacetic acid group in the component (a); The acrylate of acetoacetic acid group is the acetoacetyl propyl methacrylate, AAEM, acetoacetyl allyl ester, acetoacetyl butyl methacrylate, 2,3-diacetyl acetic acid ylmethyl propyl acrylate and analogue thereof.
Wherein the alkali of volatile must be capacity, the carboxyl that contains in the polymkeric substance (a) can be neutralized, and makes acetoacetic acid group be converted into enamine, and employed alkali is the analogue of ammoniacal liquor, triethylamine or other amine.
Further elaboration of the present invention:
Described component (a) can be to be polymerized by the function monomer that contains acetoacetic acid group and other acrylic ester monomers.
The function monomer that contains acetoacetic acid group that the present invention is included can be selected the acrylate that contains acetoacetyl; such as the acetoacetyl propyl methacrylate; the acetoacetyl allyl ester; the acetoacetyl butyl methacrylate; 2; 3-diacetyl acetic acid ylmethyl propyl acrylate and analogue thereof, all things considered is so long as the monomer that can make hydroxyl and diketene or the reaction of other acetylation reagents generate acetoacetyl all can.
Other acrylic ester monomers of the included component of the present invention (a) can be selected C 1~ C 20(methyl) alkyl acrylate, C 2~ C 20Vinyl esters of carboxylic acids, C 3~ C 6The unsaturated nitrite that contains vinyl, greater than C 20The aromatic ethylene monomer, vinyl halide, C 2~ C 5And with the aliphatic hydrocarbon of two keys.Preferred acrylic ester monomer can be C 1~ C 8Alkyl (methyl) acrylate, such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl or (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, 2-ethyl (methyl) Ethyl acrylate, vinyl acetate such as vinyl acetate, propionate, aromatic ethylene monomer such as vinylbenzene, alpha-methyl styrene, ethene halogenide such as vinylchlorid, vinylidene chloride, dienes monomer such as divinyl, isoprene.Further preferred acrylic ester monomer can be C 1~ C 8Alkyl (methyl) acrylate and vinylbenzene.
Also can comprise a certain amount of unsaturated carboxylic acid or acid anhydrides that contains the alpha-beta vinyl in the described component (a), can select (methyl) vinylformic acid, toxilic acid or maleic anhydride, methylene-succinic acid.Be preferably vinylformic acid, methacrylic acid.
The second-order transition temperature of described component (a) is preferably 5 ~ 90 ℃ between 0 ~ 100 ℃, more preferably 20 ~ 90 ℃.
Described component (b) must be can be good with component (a) consistency water-based multi-functional acrylate.Water-based multi-functional acrylate's monomer can be selected from contain two hydroxyls, trihydroxy-or more polyhydric vinylformic acid alcohol ester.Be preferably oxyethyl group diacrylate, oxyethyl group Viscoat 295, oxyethyl group neopentylglycol diacrylate or propoxy-neopentylglycol diacrylate, oxyethyl group Viscoat 295 (EOTMPTA, Sartomer more preferably 454).The water-based UV resin that contains the multi-functional acrylate can be from epoxy acrylate, urethane acrylate, polyester acrylate is selected in ammonia-acrylate, as long as can select with the water-based UV resin that Michael reaction occurs under heating condition (a) component.
Described component (c) can be can be dissolved in the light trigger of water-based system or be slightly soluble in the water light trigger, can select 2-hydroxyl-2,2-dimethyl acetophenone (Darocur 1173), 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone (Irgacure 2959), two (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure of phenyl 819DW), 2,4,6-trimethylbenzene formyl radical diphenyl phosphine oxide and analogue thereof.Because different light trigger has in various degree absorption to the light of different-waveband, two or more light trigger has been used in conjunction with obvious synergy, improves light-initiated efficient.
Described component (d) has good dispersion in water, they can be the mill bases of organic or inorganic, gorgeous beauty and gorgeous good bright serial pigment such as the vapour bar, the instant pigment of X Fast of river, sea chemical industry, the U/S series of section's enlightening, the super disperse aqueous mill base of the water-based of fine landscape, but be not limited to this, all and water-based system have the pigment of good consistency all can be in selection range.
Beneficial effect of the present invention:
The present invention applies to the dual cure means in the aqueous pigmented coating system, attempts to reach the purpose of improving ultraviolet aqueous colored coating curing performance by the mode that changes the single curing of UV-light.Heat-UV-light dual cure includes heat and two solidification processs of UV-light, and curing process is not subjected to the impact of pigments system, can remedy the deficiency of ultraviolet light polymerization in pigmented system; The ultraviolet light polymerization process makes the complete crosslinking curing of coating on the basis of thermofixation, finally obtain high performance aqueous pigmented coating.
Color had improved the efficient of aqueous pigmented system ultraviolet light polymerization and the performance of filming greatly to the restriction of ultraviolet light polymerization when said composition had effectively overcome conventional ultraviolet light polymerization.
Following embodiment is used for that the present invention will be further described, in no case with since limit the scope of the invention.It should be appreciated by those skilled in the art, in the situation that do not depart from technical conceive of the present invention and scope that claims are put down in writing, can carry out various modifications or change to the present invention.
Embodiment
Embodiment one
Composition Massfraction
Acrylic ester emulsion (Tg=35 ℃) 60
EOTMPTA 11.5
Light trigger (2959:819DW=1:1) 0.5
Aqueous color paste (section's enlightening, bright red 4032-S) 28
The implementation step is as follows:
(1) adopt emulsion polymerization to make the acrylic ester emulsion with nucleocapsid structure, the emulsion of the milky white colour band blue light that finally obtains, pH value are 8, and solid content is 47 ± 2%.
(2) take by weighing acrylic ester emulsion, water-based multi-functional acrylate, light trigger, pigment according to prescription, fully stir, film after mixing, then put into electric heating constant-temperature blowing drying box in 60 ℃ of lower dry 10 min, be placed on again under the uv cure machine of 2 * 5.6 kw irradiation 10 seconds.
(3) coating hardness is measured by GB GB/T6739-1996 " hardness of film pencil assay method ".
(4) coating adhesion is pressed GB/T9286-98, adopts cross-hatching to measure.
(5) coating is soaked in 25 ℃ the water, the time of record the coating whiting, bubbling or coming off is to measure the water resistance of coating.
The cotton balls that (6) will soak into ethanol is in back and forth wiping of coatingsurface, and one is designated as once back and forth, and the number of times of wiping during the record coating damage is to measure the anti-ethanol performance of coating.
The coating performance test result is as follows:
Hardness: 4H
Sticking power: 0 grade
Water tolerance:〉48h without the whiting wrinkling
Anti-ethanol: 93 times
Outward appearance: smooth smooth.
Embodiment two
Composition Massfraction
Acrylic ester emulsion (Tg=45 ℃) 40
Water-based UV cured resin 19.5
Light trigger (1173:819DW=1:1) 0.5
Aqueous color paste (section's enlightening, yellow 2014-S) 40
Specific implementation method is with embodiment one.
The coating performance test result is as follows:
Hardness: 3H
Sticking power: 1 grade
Water tolerance:〉48h without the whiting wrinkling
Anti-ethanol: 72 times
Outward appearance: smooth smooth.
Embodiment three
Composition Massfraction
Acrylic ester emulsion (Tg=35 ℃) 50
EOTMPTA 14.5
Light trigger (819DW) 0.5
Aqueous color paste (section's enlightening, ultramarine 6153-SA) 35
Specific implementation method is with embodiment one.
The coating performance test result is as follows:
Hardness: 2H
Sticking power: 1 grade
Water tolerance:〉48h without the whiting wrinkling
Anti-ethanol: 50 times
Outward appearance: smooth smooth.
Embodiment four
Composition Massfraction
Acrylic ester emulsion (Tg=35 ℃) 45
Water-based UV cured resin 23
EOTMPTA 8.5
Light trigger (2959:819DW=1:1) 0.5
Aqueous color paste (section's enlightening, carbon black 9007-SB) 23
Specific implementation method is with embodiment one.
The coating performance test result is as follows:
Hardness: 4H
Sticking power: 0 grade
Water tolerance:〉48h without the whiting wrinkling
Anti-ethanol: 80 times
Outward appearance: smooth smooth.

Claims (10)

1. heat-UV-light dual cure water-based colored coating composition is characterized in that it comprises:
The emulsion polymer that contains at least one acetoacetic acid group, the second-order transition temperature of described polymkeric substance is between 0 ~ 100 ℃;
Water-soluble multi-functional acrylate's monomer or contain in multi-functional acrylate's the water-based UV cured resin one or both;
Light trigger; And
Aqueous color paste;
Wherein component (a) is 15~1:1 with the weight ratio of component (b) for (a)/(b); Component (c) adds up to 100 weight parts in component (a) and component (b), and its content is 0.6 ~ 0.9 weight part; Component (d) adds up to 100 weight parts in component (a) and component (b), and its content is 20 ~ 60 weight parts; The volatilizable alkali that also contains capacity in the said composition, so that the acetoacetic acid group (a) is converted into enamine, under the condition of heating, enamine is converted into acetoacetic acid group again, with the two key generation Michael reactions of the C=C among the water-soluble multi-functional acrylate, realize ultraviolet light polymerization.
2. described heat-UV-light dual cure water-based colored coating composition according to claim 1, it is characterized in that: described component (a) is 10~2:1 with the weight ratio (a)/(b) of component (b).
3. described heat-UV-light dual cure water-based colored coating composition according to claim 1 is characterized in that: the acrylic ester emulsion polymkeric substance that contains at least one acetoacetic acid group in the described component (a); The acrylate of acetoacetic acid group is acetoacetyl propyl methacrylate, AAEM, acetoacetyl allyl ester, acetoacetyl butyl methacrylate, 2,3-diacetyl acetic acid ylmethyl propyl acrylate and analogue thereof.
4. described heat-UV-light dual cure water-based colored coating composition according to claim 1, it is characterized in that: the alkali of described volatile must be capacity, the carboxyl that contains in the polymkeric substance (a) can be neutralized, and make acetoacetic acid group be converted into enamine; Employed alkali is the analogue of ammoniacal liquor, triethylamine or other amine.
5. described heat-UV-light dual cure water-based colored coating composition according to claim 1 is characterized in that: described component (b) is water-soluble multi-functional acrylate's monomer that can mix with component (a) or the water-based UV cured resin that contains the multi-functional acrylate.
6. described heat-UV-light dual cure water-based colored coating composition according to claim 5, it is characterized in that: above-mentioned water-soluble multi-functional acrylate's monomer is oxyethyl group diacrylate, oxyethyl group Viscoat 295, oxyethyl group neopentylglycol diacrylate, propoxy-neopentylglycol diacrylate and analogue thereof.
7. described heat-UV-light dual cure water-based colored coating composition according to claim 5, it is characterized in that: the above-mentioned multi-functional acrylate's of containing water-based UV cured resin is epoxy acrylate, urethane acrylate, polyester acrylate, ammonia-acrylate and analogue thereof.
8. described heat-UV-light dual cure water-based colored coating composition according to claim 1 is characterized in that: described light trigger is the light trigger that can mix with component (a) and component (b); The light trigger of above-mentioned use is 2-hydroxyl-2; 2-dimethyl acetophenone, 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 '; 2 '-dimethyl ethyl ketone, phenyl two (2; 4; the 6-trimethylbenzoyl) phosphine oxide, 2; 4,6-trimethylbenzene formyl radical diphenyl phosphine oxide and analogue thereof.
9. described heat-UV-light dual cure water-based colored coating composition according to claim 1, it is characterized in that: described aqueous color paste can mix with component (a) and component (b).
10. described heat-UV-light dual cure water-based colored coating composition according to claim 1, it is characterized in that: not containing any organic solvent in the described composition, is 100% solventless coatings.
CN2012103919589A 2012-10-16 2012-10-16 Thermal-ultraviolet dual-curing water-based colored coating composition Pending CN102924987A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061667A (en) * 2015-08-11 2015-11-18 合肥乐凯科技产业有限公司 Acrylate emulsion and application thereof
CN105602430A (en) * 2016-02-29 2016-05-25 张家港康得新光电材料有限公司 Pre-coated composition, UV cured product and preparation method of UV solidified product
CN114096622A (en) * 2019-07-11 2022-02-25 共荣社化学株式会社 Curable resin composition, cured film, coated resin molded article, and multilayer film
CN115819735A (en) * 2022-12-07 2023-03-21 江西科技师范大学 Liquid crystal elastomer and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0705855A2 (en) * 1994-10-06 1996-04-10 Air Products And Chemicals, Inc. Water borne crosslinkable compositions
US5712339A (en) * 1995-04-05 1998-01-27 Sartomer Company Aqueous polymer dispersions
WO2004003074A1 (en) * 2002-05-31 2004-01-08 Cray Valley Iberica Dual cure emulsions
CN1844229A (en) * 2006-05-16 2006-10-11 广东工业大学 UV curable aqueous resin composition
CN101374918A (en) * 2006-01-30 2009-02-25 瓦尔斯帕供应公司 Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods
US20120157610A1 (en) * 2010-12-15 2012-06-21 Eastman Chemical Company Acetoacetate-functional monomers and their uses in coating compositions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0705855A2 (en) * 1994-10-06 1996-04-10 Air Products And Chemicals, Inc. Water borne crosslinkable compositions
US5712339A (en) * 1995-04-05 1998-01-27 Sartomer Company Aqueous polymer dispersions
WO2004003074A1 (en) * 2002-05-31 2004-01-08 Cray Valley Iberica Dual cure emulsions
CN101374918A (en) * 2006-01-30 2009-02-25 瓦尔斯帕供应公司 Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods
CN1844229A (en) * 2006-05-16 2006-10-11 广东工业大学 UV curable aqueous resin composition
US20120157610A1 (en) * 2010-12-15 2012-06-21 Eastman Chemical Company Acetoacetate-functional monomers and their uses in coating compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061667A (en) * 2015-08-11 2015-11-18 合肥乐凯科技产业有限公司 Acrylate emulsion and application thereof
CN105602430A (en) * 2016-02-29 2016-05-25 张家港康得新光电材料有限公司 Pre-coated composition, UV cured product and preparation method of UV solidified product
CN114096622A (en) * 2019-07-11 2022-02-25 共荣社化学株式会社 Curable resin composition, cured film, coated resin molded article, and multilayer film
CN115819735A (en) * 2022-12-07 2023-03-21 江西科技师范大学 Liquid crystal elastomer and preparation method thereof

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Application publication date: 20130213