CN102212311A - Colorful ultraviolet (UV) light solidifying paint - Google Patents
Colorful ultraviolet (UV) light solidifying paint Download PDFInfo
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Abstract
The invention provides a colorful ultraviolet (UV) light solidifying paint. The paint comprises the following components in parts by weight: 25-55 parts of polyurethane acrylate prepolymer, 10-60 parts of acrylate monomer, 5-50 parts of solvent, 1-10 parts of photoinitiator, 1-15 parts of pigment, 0.5-10 parts of dispersing agent and 0.1-2 parts of auxiliary, wherein the acrylate monomer is a mixture of a single-functionality monomer, a double-functionality monomer and a high-functionality monomer. According to the invention, the paint is used so as to overcome the problems such as large volatility, difficult construction and the like in the existing colorful UV light solidifying paint, has the characteristics of low volatile organic compound (VOC), good decorative effect, rapid curing speed and the like, is easy to construct, is suitable for flow line production, and can be used for decoration of base materials such as plastic, wood, metal and the like.
Description
Technical field
The present invention relates to a kind of coating, particularly a kind of colored UV photo-cured coating.
Background technology
UV-light coating resulted from eighties of last century seventies, had obtained the development of advancing by leaps and bounds at nearly 20 years.It adopts reactive thinner is that viscosity-controlling agent, ultraviolet light irradiation are the curing means, has characteristics such as energy-conserving and environment-protective, production efficiency height.Its Application Areas has been expanded to fields such as makeup, computer, thermal sensing element, decoration panel and medical devices by fields such as initial mobile phone, DVD, walkmans.
Though UV-curing technology production efficiency height, do not contain volatile organic solvent (VOC), because the restriction of UV-curing technology itself, existing ultraviolet-curing paint is also based on transparent varnish, and colored UV photo-cured coating product seldom.
Though there is certain technical bottleneck in colored UV Color paint, people never stopped its research, and existing a large amount of documents and patent occur.The UV curing chromatic coating of researchs such as Zhai Yuanping reports adopts the UV varnish raw material to be equipped with pigment and forms, and the photocuring light pricker colo(u)r coating of reports such as Xiao Kunfu has mainly been investigated the collocation, solvent, light trigger, selection of pigment of resin to the optical fiber coatings Effect on Performance.Patent CN101870846A has reported high-performance ultraviolet cured colored paint and preparation method thereof, has wherein adopted organic solvent for the viscosity that reduces lacquer; A kind of UV curing color decorative coating that CN101407651A invented adopts mixing acrylic resin, solvent, pigment, auxiliary agent etc. to make a kind of not solvent-laden colored UV coating; JP2001-31892 has reported a kind of quick-setting colo(u)r coating; US7553879 has introduced a kind of priming paint of outdoor good stability, in order to improve the photostabilizer that outdoor stability has added picture titanium dioxide and so on, and suitably adopts the organic solvent as solvent.Above patent and document have all carried out research or invention to coloured UV coating, it can roughly be divided into two classes, one class is to add pigment to obtain the colored lacquer of UV on the basis of UV varnish, and another kind of is to add pigment and organic solvent obtains the colored lacquer of the moderate UV of viscosity on the basis of UV varnish.The problem that the former exists is clearly, and the system of regulating viscosity by solvent is not that to have the too high constructional difficulties of viscosity be exactly to add the problem that too much reactive thinner makes coating property decline fully; The problem that the latter exists is the feature of environmental protection that the adding of too much organic solvent has reduced UV coating, is unworthy advocating.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the defective that existing colored UV photo-cured coating exists, the colored UV photo-cured coating of good, the easy construction of the feature of environmental protection, quick solidifying is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is:
A kind of colored UV photo-cured coating, described coating comprises the component of following parts by weight:
Described acrylic ester monomer is the monomeric mixture of single functionality, difunctionality and polyfunctionality.
The polyurethane acrylate prepolymer aggressiveness that the present invention selects for use is selected from a kind of or its mixture of polyfunctionality polyurethane acrylate prepolymer aggressiveness and difunctionality polyurethane acrylate prepolymer aggressiveness, and promptly all and water or organic solvent, reactive thinner all have polyurethane acrylic resin or its water dispersion of excellent compatibility.As aliphatic polyurethane triacrylate UV XP2587, the U100 of Bayer A.G 400, the CN9245/CN132 of Sartomer, the 611B-85/6123 in Changxing; The polyurethane acrylate prepolymer aggressiveness also can adopt the synthetic mode to prepare.
Described polyurethane acrylate prepolymer aggressiveness is selected from bifunctional, trifunctional, many officials and rolls into a ball one or more mixture of urethane acrylate.
The basic material that the synthesis of polyurethane acrylate is adopted is IPDI, TDI, HDI, HMDI, MDI, the pure and mild polyether Glycols of polyester binary, single functionality, difunctionality, polyfunctional acrylic ester class monomer.
The synthetic urethane acrylate both can be made by isocyanic ester, dibasic alcohol, alkene class end-capping reagent, and that can introduce on this three's basis also that hydrophilic radical makes all has the polyurethane acrylate prepolymer aggressiveness or the urethane acrylate water dispersion of excellent compatibility with water and oil.
Described isocyanic ester is one or several the mixture among IPDI, TDI, HDI, HMDI, the MDI; Described dibasic alcohol is one or several the mixture in polyoxyethylene glycol, polypropylene glycol, PEP-101, polytetrahydrofuran diol or the polyester diol that made by binary acid and the polycondensation of di-alcohols material; Described water-based group is mainly introduced by the dibasic alcohol or the diamine material that contain ehter bond, carboxyl, sulfonate, tertiary amine.Be lower than 800 PPG/PEG, DMPA, DMBA, N methyldiethanol amine, sulfonate polyether Glycols etc. as lower molecular weight.
Described alkene class end-capping reagent is meant the compound that has a hydroxyl and at least one two key simultaneously.One or more of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, pentaerythritol triacrylate, TriMethylolPropane(TMP) dual-allyl ether for example, but be not limited to above-mentioned listed.
Described solvent is one or several the mixture in No. 200 solvent oils, normal hexane, hexanaphthene, benzene, toluene, chloroform, methyl alcohol, Virahol, propyl carbinol, ethanol, ethyl acetate, acetone, butanone, methylethylketone, ethylene glycol fourth diether, a condensed ethandiol ether, tetrahydrofuran (THF), the water, but is not limited to above-mentioned listed.
Described polyfunctional acrylic ester class monomer is one or more the mixture in three-functionality-degree, four functionality, five functionality or the six functionality acrylic ester monomers.
Described polyfunctionality monomer be selected from Viscoat 295 (TMPTA), pentaerythritol triacrylate (PETA), tetramethylol methane tetraacrylate (PETTA), Dipentaerythritol five acrylate (DPPA), double pentaerythritol methacrylate (DPHA), third oxidation, three light methylpropane triacrylates (PO-TMPTA), three contract trimethylolpropane tetra-acrylate (DTMPTTA) one in or several mixtures.
Described UV curing color decorative coating, it is characterized in that, described difunctionality acrylic ester monomer is selected from propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), 1, the mixture of one or more of 4-butylene glycol diacrylate (BDDA), 1,6 hexanediol diacrylate (HDDA), neopentylglycol diacrylate (NPGDA).
Described single functionality acrylic ester monomer is selected from one or more mixture of isodecyl acrylate (IDA), Isooctyl acrylate monomer (EHA), Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (MICA), isobornyl acrylate (IBOA), lauryl acrylate (LA), methacrylic acid tetrahydrofuran (THF) methyl esters (THFFA), methacrylic acid iso-borneol vinegar (IBOA).
Described initiator is selected from 1-hydroxy-cyclohexyl phenyl ketone (184); 2-hydroxyl-aminomethyl phenyl propane-1-ketone (1173); 4; 6 (trimethylbenzoyl) diphenyl phosphine oxide (TPO); phenyl two (2; 4; the 6-trimethylbenzoyl) phosphine oxide (819); 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone (907); 2-sec.-propyl thia is feared ketone (ITX); benzoin dimethylether (BDK); 4-(N; the N-dimethylamino) ethyl benzoate (EPD); benzophenone (BP); N; the different monooctyl ester of N-dimethylaminobenzoic acid (EHA); 4-methyldiphenyl ketone (MBZ); the combination of one or several of 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone (369), but be not limited to above listed.
Described pigment characteristics are with water, oil body system organic and inorganic toner or the mill base with good consistency to be arranged all, as the instant pigment of Xfast of extra large river chemical industry, the gorgeous beauty of vapour crust and COLORMAX series, the U/S series of section's enlightening, the vapour crust of gorgeous good bright serial pigment and extra large river chemical industry
Excellent wall look
-S, Clariant Hostatint water and oil applicable series but be not limited thereto, all and system have the pigment of excellent compatibility all can be in choosing scope.
In order to allow mill base disperse better, reduce phenomenons such as loose colour grows dim, having selected the solution of wax class, aliphatic amide type, acid polyester, lower molecular weight unsaturated polycarboxylic acid polymkeric substance or itself and polysiloxane interpolymer is wetting dispersing auxiliary, as BYK-P104S/104/110, EFKA6225, TEGO Dispers652/651, sea this FX 365 of name etc.
In order to prevent the sedimentation of mill base, we have improved the thixotropy of coating, add silicon-dioxide toward the system the inside, organobentonite, and hydrogenated castor wet goods thixotropic agent is as DegussaA300 and A200, sea this BENTONE 27 of name etc.
In order to increase the surperficial smooth property of coating, improve the planeness of film, obtain better decorative effect we to have selected polyacrylic, cellaburate polydimethylsiloxane, PSI, organic radical modified polyorganosiloxane, fluorine be the flow agent of tensio-active agent as system, as BYK333/346, EFKA3600, BNK-222, TEGO Wet/Wet KL 245 etc.
Described defoamer is selected from polyethers, polyether-modified silicon, fluorine modified organic silicon class, polysiloxane-based, adopts to press down to steep, break bubble or press down bubble and break the collocation of steeping to reach best defoaming effect.As BYK1770/1730, EFKA-2580, sea this defoamer of name DF7005/DF 7010, TEGO FOAMEX825/AIAEX901W etc.
The colorama of the present invention's preparation is coating material solidified, all adopts low poison solvent, and the prescription that has can also water or part water to replace organic solvent, good environmental protection.In addition, select the good resin of photosensitive property a certain amount of strong solvent of reasonably arranging in pairs or groups, therefore the coating material solidified characteristics with easy construction, quick solidifying of colorama that make have very big promotion and application to be worth.
Embodiment
Embodiment one
| Composition | Weight fraction |
| UV?XP2587 | 45 |
| TPGDA | 10 |
| 4,4 ', 4 "-the trimethylammonium triphenylamine | 5 |
| ?LA | 5 |
| Solvent | 20 |
| Light trigger (weight ratio 907: ITX: 1173=1: 0.3: 5) | 6 |
| ?COLORMAX?RED | 7 |
| ?BYK-P104S | 0.7 |
| ?DegussaA300 | 0.5 |
| Flow agent (mixture of weight ratio BYK333 and BNK222) | 0.5 |
| ?BYK1770 | 0.3 |
Concrete implementation step is as follows:
(1) with resin, monomer, part defoamer (account for total amount 20%～80%), thixotropic agent rotating speed are that 1200 rev/mins high speed dispersor disperses 15min;
(2) toner or mill base and wetting dispersing agent, part defoamer (account for total amount 20%～40%), partial solvent (account for solvent total amount 5%～50%) loose till the system uniform and smooth being ground on the three-roller, cross 300 order nets then;
(3) solid photoinitiator is mixed in proportion the back dissolving by the mixed solvent the inside of proportioning;
(4) product that step 1, step 2 and step 3 are obtained and solvent, usefulness rotating speeds such as flow agent, remaining defoamer, solvent are that 600 rev/mins dispersion machine stirs 5min;
(5) cross 300 mesh filter screens, obtain the UV colored paint.
Embodiment two
| Composition | Weight fraction |
| Polyurethane acrylate resin | 46 |
| ?HDDA | 10 |
| ?IDA | 10 |
| Solvent | 18 |
| Light trigger (weight ratio 184: 1173=2: 3) | 6 |
| ?X-fast?yellow | 8 |
| ?BYK110 | 0.9 |
| Thixotropic agent (weight ratio DegussaA300: A200=2: 1) | 0.5 |
| ?BYK346 | 0.4 |
| ?Byk1170 | 0.2 |
Specific implementation method is with embodiment one.
Embodiment three
| Composition | Weight fraction |
| Urethane acrylate (synthesizing) | 50 |
| Solvent (weight ratio TMPTA: HDDA: LA=0.5: 1.5: 3) | 10 |
| Solvent | 20 |
| Light trigger (weight ratio TPO: 819: 184=1: 0.5: 3) | 7 |
| Clariant Hostatint orchid | 5 |
| Dispersion agent (weight ratio BYK-P104S: BYK-104=2: 1) | 0.8 |
| Hai Mingsi BENTONE 27 | 0.5 |
| BYK346 | 0.8 |
| Defoamer (FOAMEX825, AIAEX901W mixture) | 0.2 |
Specific implementation method is with embodiment one.
Embodiment four
With IPDI, PPG400, DMPA, 0.1% catalyzer reacted 2.5 hours under 70 degree, added HEMA and an amount of stopper end capping then 2 hours, added ammoniacal liquor, promptly obtain 002 urethane acrylate after 20% the emulsifying water, ensuing implementation method is with embodiment one.
Embodiment five
Specific implementation method is with reference to embodiment four and embodiment one.
All similar in the more embodiment operation, only need to get final product according to different base materials and application demand transposing matrix resin, solvent, light trigger, auxiliary agent etc.This colour UV photo-cured coating can adopt the form of construction work of roller coating, showering, spraying to construct.Make colored paint sticking power on PVC/PC/ABS/ vacuum plating/Cortex Fraxini mandshuricae plank by above scheme and all be better than secondary, anti-75% ethanol is more than 24 hours, alkaline-resisting more than 24 hours, acidproof more than 48 hours, the cold cycling of tolerance 40 degrees below zero and 40 degree does not ftracture for 10 times, anti-15% salt solution is more than 60 hours, hardness can be regulated between 3H at HB, abrasion resistance index 3000 change more than, and can regulate by filler.
Claims (10)
1. colored UV photo-cured coating is characterized in that described coating comprises the component of following parts by weight:
2. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described polyurethane acrylate prepolymer aggressiveness is selected from one or both in polyfunctionality polyurethane acrylate prepolymer aggressiveness and the difunctionality polyurethane acrylate prepolymer aggressiveness.
3. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described polyurethane acrylate prepolymer aggressiveness comprises following two big classes: a class is to be prepared from by isocyanic ester, dibasic alcohol, alkene class end-capping reagent; One class is to be prepared from by isocyanic ester, dibasic alcohol, alkene class end-capping reagent and the material that contains hydrophilic radical.
4. according to the described colored UV photo-cured coating of claim 3, it is characterized in that:
Described isocyanic ester is one or several the mixture among IPDI, TDI, HDI, HMDI, the MDI;
Described dibasic alcohol is one or several the mixture in the polyester diol that gets of polyoxyethylene glycol, polypropylene glycol, PEP-101, polytetrahydrofuran diol, binary acids and di-alcohols polycondensation;
Described alkene class end-capping reagent is meant compound or the multiple mixture that has a hydroxyl and have the compound of two keys at least that has a hydroxyl and have two keys at least;
The described material that contains hydrophilic radical is to contain the dibasic alcohol of ehter bond, carboxyl, sulfonic group, tertiary amine group or the compound of diamine.
5. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described solvent is one or several the mixture in alkane, halohydrocarbon, aromatic hydrocarbons, ketone, alcohols, ester class, ethers, the water.
6. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described pigment is and water, organic solvent, reactive thinner, all compatible organic and inorganic toner or the mill base of polyurethane acrylate prepolymer aggressiveness.
7. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described acrylic ester monomer is to contain two keys, two two keys or the acrylic ester monomer of a plurality of pairs of keys or the derivative of acrylic ester monomer.
8. according to the described colored UV photo-cured coating of claim 1; it is characterized in that described light trigger is selected from 1-hydroxy-cyclohexyl phenyl ketone; 2-hydroxyl-aminomethyl phenyl propane-1-ketone; 2; 4; 6 (trimethylbenzoyl) diphenyl phosphine oxide; phenyl two (2; 4; the 6-trimethylbenzoyl) phosphine oxide; 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone; 2-sec.-propyl thia is feared ketone; benzoin dimethylether; 4-(N; the N-dimethylamino) ethyl benzoate; benzophenone; N, the different monooctyl ester of N-dimethylaminobenzoic acid; 4-methyldiphenyl ketone; the mixture of one or more of 2-phenyl benzyl-2-dimethyl amine-1-(4-morpholine benzyl phenyl) butanone.
9. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described dispersion agent is one or more in the solution of wax class, aliphatic amide type, acid polyester, the unsaturated polycarboxylic acid polymkeric substance of lower molecular weight, the unsaturated polycarboxylic acid polymkeric substance of lower molecular weight and polysiloxane interpolymer.
10. according to the described colored UV photo-cured coating of claim 1, it is characterized in that described auxiliary agent is one or more in thixotropic agent, defoamer and the flow agent; Described thixotropic agent is selected from one or more in aerosil, organobentonite, hydrogenated castor oil, the polyamide wax; It is in the tensio-active agent one or more that flow agent is selected from polyacrylic, cellaburate polydimethylsiloxane, PSI, organic radical modified polyorganosiloxane, fluorine; Defoamer is selected from polyethers, polyether-modified silicon, fluorine modified organic silicon class, in polysiloxane-based one or more.
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| CN 201110117999 CN102212311A (en) | 2011-05-09 | 2011-05-09 | Colorful ultraviolet (UV) light solidifying paint |
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| CN 201110117999 CN102212311A (en) | 2011-05-09 | 2011-05-09 | Colorful ultraviolet (UV) light solidifying paint |
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