CN102585157A - Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin - Google Patents
Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin Download PDFInfo
- Publication number
- CN102585157A CN102585157A CN201210064714XA CN201210064714A CN102585157A CN 102585157 A CN102585157 A CN 102585157A CN 201210064714X A CN201210064714X A CN 201210064714XA CN 201210064714 A CN201210064714 A CN 201210064714A CN 102585157 A CN102585157 A CN 102585157A
- Authority
- CN
- China
- Prior art keywords
- ultraviolet light
- light polymerization
- coating
- vacuum plating
- urethane acrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating primer coating resin and a preparation method thereof. The prescription comprises the following raw materials by weight: 10 to 30 parts of aliphatic series diisocyanate, 5 to 25 parts of (methyl) crylic acid hydroxyl ester, 40 to 100 parts of polyester (ether) dihydric alcohol, 3 to 8 parts of absolute ethyl alcohol, polymerization inhibitor and initiator. The polymerization inhibitor and the initiator occupy 0.01% to 0.05% of the total raw materials. The ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating primer coating resin is formed by reactions like ammonia esterification and is suitable for vacuum coating in the fields of automobiles, household appliances, daily packaging, process decoration and the like.
Description
Technical field
The present invention relates to a kind of ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face and resinize, can be widely used in the finish paint coating of numerous areas vacuum platings such as light fixture part, automobile decoration part, minaudiere, toy and the small articles of daily use.
Background technology
Vacuum coating technology was begun to show in nineteen thirties, and nineteen seventies just obtains large development.Along with the development of decorative plastic plated film and continually developing of plastics substituting metal goods, what vacuum coating technology was more is applied in the plastic-metal goods.On plastics, carry out vacuum plating, can give plastics metal appearance, high added value, improve over-all propertieies such as wear resistance, be widely used in the light fixture part, automobile decoration part, minaudiere, many civil areas such as the toy and the small articles of daily use.Vacuum-coating generally approaches (being no more than 0.2 μ m), and some mechanical properties such as wear resistance are relatively poor.Finish paint not only plays the effect of protective coating, also can give mechanical properties such as the good hardness of vacuum plating goods, wear resistance.Vacuum metallizing coating plays crucial effects in vacuum coating technology, its performance quality will directly influence the performance of goods, therefore, develops high performance vacuum metallizing coating the vacuum plating industrial expansion is had great importance.
Ultraviolet-curing paint is new in recent years one type of coating new variety of rising, this coating have the solid content height, dry rapidly, save advantage such as the energy, be widely used in the processing and other fields of bamboo and wood products, printed matter and plastics.We are to the special technical requirement of plastic vacuum coating coating; New ultra-violet line curing vacuum coating finish paint coating (R&D) in research and development; Make it have good glossiness, fullness ratio and fast drying, to the plastics firm binding force, and coating hardness is high; Advantages such as wear resistance is strong are applicable to plastic vacuum coating decorative paint ideal coating variety.
The ultraviolet-curing paint reactive behavior is high, wide in variety; Commonly used have polyester acrylate, polyether acrylate, epoxy acrylate, urethane acrylate, a trimeric cyanamide propenoate etc., mainly contains urethane acrylate and epoxy acrylate coating at present and be used for vacuum coating technology [referring to document 1].In invention disclosed patent and correlation technique, how with the characteristics that are modulated to of formulation for coating material, synthetic and the technology of preparing of matrix resin still is in [referring to document 2] among the control of external each famous brand company (BAYER, SATORMER and UCB etc.).
Vacuum-coating approaches (being no more than 0.2 mm) usually, and mechanical properties such as wear resistance are relatively poor.Finish paint not only plays the effect of protective coating, also can give mechanical properties such as the good hardness of vacuum plating goods, wear resistance.The salient features of finish paint requires to comprise: coating is had higher sticking power, and this is the basis that coating shields; Should have enough wear resistancies, avoid the machinery scratch with protection vacuum-coating as thin as a wafer; Have higher barrier, promptly itself will have water-fast preferably, erosion resistance and weathering resistance, stop oxygen etc. the mordant material of plated film directly to be contacted vacuum-coating, the protective coating protect it from corrosion; Finish paint composition itself can not contain the component or the impurity that might corrode coating; For the vacuum plating occasion of the outstanding luminance brightness of needs, finish paint also should guarantee the higher transparency and surface luster.Some technique for vacuum coating need not finish paint, and when being chromium, stainless steel like Coating Materials, its coating good corrosion resistance, hardness height and scratch resistance are strong, therefore to product properties when less demanding, and can coating finish.
At present, the ultraviolet-curing vacuum coating coating technology has versatility with the polyfunctionality urethane acrylate as the matrix resin of finish paint prescription, and its effect mainly is to give the good kindliness of cured film and certain sticking power; Usually also add epoxy acrylate with raising hardness, fast setting performance and good adhesion property, but its too high fragility has limited its consumption in prescription again, so its consumption can not be too high; Because the monomeric vacuum volatilization character of single functionality can not transform again in system fully in addition, therefore the consumption of single functionality reactive thinner can not be too high in the prescription, and this causes dope viscosity excessive, uses inconvenient.
Early stage patented technology has the patent of invention of [referring to documents 3] such as Hu Hui: " vacuum plating ultraviolet curing coating " (number of patent application: 99115485.1; 2001); At the bottom of having described a kind of ultraviolet-curing vacuum coating, finish paint; Priming paint is made up of acrylic acid modified bisphenol A epoxide resin, polyvalent alcohol and Hydroxyethyl acrylate and toluene two different hydrogen acid ether affixtures, reactive diluent, light trigger, auxiliary agent; Finish paint is made up of polyester acrylate, phenolic aldehyde epoxy acrylate, reactive thinner, light trigger, adhesion promoter, auxiliary agent, and all by after certain weight percent proportioning, mixing and stirring makes above-mentioned composition.Shortcomings such as but the vacuum plating ultraviolet curing coating that obtains generally speaking, and thermotolerance is not high, and sticking power is bad, and weathering resistance is bad.
And the invention disclosed patent has in the recent period:
He Jigang [referring to document 4]: " a kind of primer of ultraviolet-curing vacuum coating, finish paint " (patent publication No.: CN101250339A, 2008).Utilize multifunctional aliphatic urethane acrylate, epoxy acrylate, multifunctional reactive monomers, at the bottom of light trigger etc. have prepared ultraviolet light polymerization, finish paint.Finish paint promotes resin, light trigger, thinner, any proportioning of auxiliary agent to form by high official's ability aliphatic urethane acrylate, macromolecular resin, two sense aliphatic urethane acrylates, trifunctional aliphatic urethane acrylate, sticking power.After vacuum plating, vacuum coating is done the external coating of UV vacuum plating finish paint and handled, prevent the metallic diaphragm oxidation, finish paint is given its excellent surface abrasion resistance property and splendid feel.
Li Min etc. [referring to document 5]: " ultraviolet curing vacuum metallizing coating " (patent publication No.: CN101280154A; 2008) UV cured polyurethane acrylate vacuum plating priming paint and finish paint have been prepared; In base paint formulation, being matrix resin with phenol aldehyde modified propenoate wherein, is solvent with the N-BUTYL ACETATE.A kind of ultraviolet curing vacuum metallizing coating is provided, has comprised ultraviolet curing vacuum metallizing base paint and ultraviolet curing vacuum metallizing coating materials, in finish paint, added Epocryl as composite resin.It is high that this coating has higher thermotolerance, good sticking power and weathering resistance.Said ultraviolet curing vacuum metallizing coating materials comprises the polyurethane acrylate resin of 0.5 ~ 50 weight part; The epoxy acrylic resin of 5 ~ 40 weight parts; The N-BUTYL ACETATE of 20 ~ 40 weight parts, the pimelinketone of 10 ~ 30 weight parts, the ethanol of 5 ~ 20 weight parts; 0.3 the adhesion promoter of ~ 6 weight parts, the light trigger of 0.5 ~ 15 weight part.Ultraviolet curing vacuum metallizing coating of the present invention, the hot height of this resistant, sticking power is good, good weatherability.
Zhu Hengguo etc. [referring to document 6]: " but recoat vacuum plating single-component photocureable coating, ME and application of directly spraying as vacuum plating " (patent publication No.: CN101280154A, 2009) but to the present invention relates to recoat vacuum plating single-component photocureable coating, ME and as the directly application of spraying of vacuum plating.Raw material: pure acrylic acid ester resin 20 ~ 80%; Vinyl chloride-vinyl acetate resin 1 ~ 20%; Six functionality propenoate 1 ~ 20%; Cellulose acetate butyrate 1 ~ 20%; Three-functionality-degree monomer 1 ~ 15%; Single functionality monomer 1 ~ 25%; Light trigger 1 ~ 15%; Flow agent 0.2 ~ 2%; Skimmer 0.05 ~ 0.5%; Adhesion promoter 0.05 ~ 0.5%; Solvent 1 ~ 30%.Technology: get the raw materials ready, respectively light trigger and cellulose acetate butyrate are dissolved into liquid with the single functionality monomer; Pure acrylic acid ester resin, vinyl chloride-vinyl acetate resin and six functionality propenoate, three-functionality-degree monomer and light trigger liquid, cellulose acetate butyrate liquid, flow agent, skimmer, adhesion promoter, solvent are successively dropped in the container successively, with dispersion machine stirred for several minute; Promptly get with strainer filtering.
Wu Yumin etc. [referring to document 7]: " the special-purpose primer of ultraviolet-curing vacuum coating of a kind of high-performing car lamp reflector " (patent publication No.: CN 101864204 A; 2010) disclose the special-purpose primer of ultraviolet-curing vacuum coating of a kind of high-performing car lamp reflector, the composition of this priming paint and proportioning are: matrix resin 40 ~ 80%, assisted resin 8 ~ 50%; Reactive thinner 10 ~ 40%; Light trigger 0.5 ~ 10%, auxiliary agent 0.05 ~ 8%, solvent 0 ~ 50%.The invention also discloses a kind of novel photocuring multipolymer, as before the vehicle lamp coating with the matrix resin of UV priming paint.Do not need the BMC base material is carried out pre-treatment, directly sprays posterior photocuring with this resin UV coating prepared; The gained film adhesive is excellent; Resistance to elevated temperatures is good, toasts phenomenons such as can not occurring sending out color foaming in 2 hours down in 240 ℃ behind the vacuum aluminum-coated formation mirror surface.
Wang Jian etc. [referring to document 8] have studied on the PC substrate, and living oligomer, reactive thinner and light trigger etc. have been inquired into some fundamental principles of design priming paint timing to the influence of vacuum plating UV primer performance.With the aliphatic urethane acrylate resin is matrix resin; Composite with epoxy acrylate and amino acrylates; Selectivity adds Viscoat 295, Bing Xisuandingzhi, hexanediyl, tri (propylene glycol) diacrylate isoreactivity thinner, has made the vacuum plating UV priming paint of excellent performance.
Above-mentioned cited patent of invention and correlation technique are characteristics with the ratio and the debugging of composition of raw materials all, and its matrix resin is main with outsourcing all, lack the gordian technique of the synthetic and preparation of matrix resin.
The vacuum metallizing coating that with the urethane acrylate is the matrix resin preparation is except that most plastic basis materials are had the good adhesion; Also have outstanding comprehensive mechanical properties such as chemical resistance, wear resistance and elasticity; Therefore be widely used in the photocuring vacuum metallizing coating; But have viscosity higher because of hydrogen bond action makes it, need to add a large amount of reactive thinners in the preparation coating.Reactive thinner is simple function or polyfunctional acrylic ester mostly, the adding of reactive thinner, and the viscosity that reduces coating on the one hand is beneficial to application; On the other hand, can improve the curing speed of system, increase cross-linking density, the flexibility of control coating strengthens sticking power, gives the coating excellent mechanical property.But should note the add-on of reactive thinner, suitable add-on just can get a desired effect.At present, the research and development of vacuum plating top-coat resin are main with urethane acrylate and epoxy acrylate, and its representational research and development system is mainly:
1, urethane acrylate (PUA) coating mainly discloses in document 9～15;
2, epoxy acrylate coating mainly discloses in document 16～22;
3, other system; The end capped three arm star polyisobutene of acryloxy or methacryloxy in document 23, have been synthesized; Add polyfunctional acrylic ester, light trigger; The UV that has prepared excellent performance solidifies flexible paint, and paint film is to base materials such as plastics, and especially aluminium base has extraordinary sticking power.Sepeur etc. [referring to document 24] have prepared plastics with high abrasion UV coating with inorganic softening aluminium stone, methacryloxy silane, propenoate quasi-oligomer, solidify inorganic-organic network structure that the back forms, and make paint film have wear resistance preferably.
At present, these coating all exist time of drying long, hardness is low, the shortcoming that wears no resistance, causes existing in actual use a lot of problems, can't satisfy the demand of plated film bound pair high-performance vacuum metallizing coating.
Reference
1 pair of iron of fine quality, Zhou Jiyi. the UV-cured polyurethane acrylate progress. chemical propellant and macromolecular material, 2009,7 (2): 6-14
2 great waves forever, Liu Xiaoxuan. vacuum metallizing coating progress, coatings industry, 2011,41 (5): 64-68
3 Hu Hui etc. are at the bottom of the ultraviolet-curing vacuum coating, finish paint. Chinese patent CN 1281011 A, 2001
4 what is lucky just, at the bottom of a kind of ultraviolet-curing vacuum coating, finish paint. Chinese patent CN 200810027249,2008.
5 Li Min etc., ultraviolet curing vacuum metallizing coating. Chinese patent, CN200710039179.1,2008
6 Zhu Heng states etc., but recoat vacuum plating single-component photocureable coating, ME and the application that directly sprays as vacuum plating. Chinese patent, publication number: CN 10,128 0154 A, 2009
The 7 Wu Yu people etc., the special-purpose primer of ultraviolet-curing vacuum coating of a kind of high-performing car lamp reflector, Chinese patent, publication number: CN 101864204 A, 2010
8 Wang Jian, Gu Bin, Shen Xuefeng. the development of vacuum plating UV priming paint. Shanghai coating, 2007,46 (9): 1-4.
9 Xu?Jianwen，Pang?Wenmin，Shi?Wenfang．Synthesis?of?UV-curable?organic-inorganic?hybrid?urethane?acrylates?and?properties?of?cured?films,?Thin?Solid?Films,?2006(5l4):?69-75．
10 Gianni?A?D，Bongiovanni?R，Priola?A，
et?a1.,?UV-cured?fluorinated?comings?for?plastics：Effect?of?the?photoinitiator?and?of?the?substrate?filler?on?adhesion,?International?Journal?of?Adhesion?&?Adhesive,?2004(24):?513-518．
11 Srba?Tasic，Branislav?Bozic，Branko?Dunjic．Synthesis?of?new?hyperbranched?urethane?acrylates?and?their?evaluation?in?UV-curable?coatings,?Progress?in?Organic?Coatings,?2004(51):?321-328．
12 Moon,?Jeong?Ho?
et?a1.,?A?study?on?UV-curable?coatings?for?HD-DVD:?Primer?and?top?coats,?Progress?in?Organic?Coatings,?2007,?59(2):?106-114
13 Jan?Welkard，Wolfgang?Fischer，Claus?Kobusch，Wolfram?Kuttner．Elastic?coating?system?comprising?UV-curable?urethane?(meth)?acrylates?containing?isocyanate?groups?and?its?use,?United?States?Patent?US6,465,539?B1,?2002.
14 Wang Dong, Tang Hao, Tang Jie, Shen Shengjun, Liu Jinjun. ultra wear-resisting vacuum plating UV coating. the national science and technology achievement.
15 Srivastava?A,?Agarwal?D,?Mistry?S,?Singh?J．UV?curable?polyurethane?acrylate?coatings?for?metal?surfaces,?Pigment?and?Resin?Technology,?2008,?37(4):?217-223.
16 are beautiful, Liu Fangfang, Cao Yaqiong, Wang Chao. the study on the synthesis progress of epoxy acrylic ester prepolymer. and bonding, 2009,5:57-60.
17 Wang Feng, Hu Jianqing is coated with big duckweed .UV and solidifies oligopolymer and coating progress thereof, thermosetting resin, 2007,22 (3): 41-45.
18 Wang Feng are coated with big duckweed .UV cured epoxy acrylic coating progress, thermosetting resin, 2007,22 (4): 36-40.
19 Stefan?O,?Stelian?V,?
et?a1.,?Epoxy?urethane?acrylate．Euro.?Polym.?J.,?2000(36):?373-378.
20 Lee are according to building Gao Yanmin, Zhang Lihua. the research of the organic-silicon-modified propylene oxide acid esters of hybrid polymer, electroplate and application 2009,28 (2): 50-52.
21 Wang Xiao are beautiful, Liu Junlong, Sun Xiangshan, Wang Wei, the research of organic dibasic acid modified epoxy acrylic ester and photocuring film properties thereof, Dalian Polytechnic College journal, 2007,26 (3): 237-240.
22 Gong build clock. ultraviolet curing vacuum metallizing coating, Shanghai coating, 2000,1:3-5.
23 Puskas，Judit?E，Kaszas?Gabor?
et?a1.,?New?polyisobutylene-based?UV-curable?flexible?coatings,?Polymer?Bulletin,?1988,?20(3):?253-260.
24 Sepeur?S，Kunze?N，Werner?B，Schmidt?H.?UV?curable?hard?coatings?on?plastics,?Thin?Solid?Films,?1999,?351(1):?216-219。
Summary of the invention
The present invention is directed to long, weak point such as hardness is low, wear no resistance existing solvent type vacuum plated film coating time of drying; The ultraviolet light polymerization coating materials resin that has prepared a kind of excellent combination property; Have the solid content height, dry rapidly, save advantages such as the energy, hardness is high, wear resistance is good, can satisfy the demand of plated film bound pair high-performance vacuum metallizing coating.
The invention provides a kind of ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face and resinize, it is mainly processed by aliphatic diisocyanate, polyvalent alcohol triacrylate, trivalent alcohol, initiator, stopper etc., and the raw material weight proportioning is following:
Aliphatic diisocyanate 20 ~ 45;
Polyvalent alcohol triacrylate 40 ~ 75;
Trivalent alcohol 3 ~ 8;
Absolute ethyl alcohol 3 ~ 8;
Initiator, stopper account for 0.01 ~ 0.05% of above-mentioned raw materials total amount.
The preferred feedstock proportioning is following:
Aliphatic diisocyanate 20 ~ 45;
Polyvalent alcohol triacrylate 40 ~ 75;
Trivalent alcohol 10 ~ 25;
Absolute ethyl alcohol 3 ~ 8;
Initiator, stopper are 0.01 ~ 0.05% of raw material total amount.
Described ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized; It is characterized in that, described aliphatic diisocyanate adopt following one or more: hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI).
Described ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized, and it is characterized in that, described polyvalent alcohol triacrylate adopts following a kind of or two kinds: pentaerythritol triacrylate, Dipentaerythritol five propenoate.
Described ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized; It is characterized in that, described trivalent alcohol adopt following one or more: glycerine (molecular weight 92), polyether-tribasic alcohol (molecular weight 150), polyether-tribasic alcohol (molecular weight 200).
Described ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized, and it is characterized in that, described initiator adopt following one or more: dibutyl tin laurate, stannous octoate, zinc naphthenate.
Described ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized; It is characterized in that, described stopper adopt following one or more: phenol, p methoxy phenol, to anisole diphenol, 2,2; 6,6-tetramethyl--piperidine NO free radical (TEMPO).
The present invention also provides a kind of vacuum plating finish paint coating, and it comprises like above-mentioned arbitrary ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face resinizes, and proper amount of diluting.
With above-mentioned ultraviolet-curing vacuum coating face resinize or vacuum plating finish paint application of paints in the vacuum plating application techniques of plastic basis material (like PP, PC, ABS etc.); Promptly with before the button of digital electronic goods such as vacuum plating PVD technology plating mobile phone, MP3, digital camera, form, the shell; Substrate surface is done the application of above-mentioned priming paint and handled, increased the planeness and the attachment fastness of vacuum coating; After vacuum plating, vacuum coating is done the external coating of vacuum plating UV finish paint and handled, prevent the metallic diaphragm oxidation, have the distinctive texture of metal, gloss, and improved surface abrasion resistance property and feel largely.
Use above-mentioned ultraviolet-curing vacuum coating face to resinize and the application product has the following advantages:
1. the face outward appearance of resinizing is colourless (or being faint yellow) transparent liquid, is convenient to color matching and preparation gloss oil;
2. the face solid content height of resinizing, solid content is more than 90%;
3. the strong adhesion between finishing coat and the metallic diaphragm, 0 grade of sticking power (cross-hatching);
4. about 50 m/min of laser curing velocity (1 kW, light source and coating distance 10 cm);
5. the finishing coat surface strength is high,>2H (pencil hardness meter method);
6. the face good stability of resinizing, the storage time is more than six months.
Embodiment
Following examples medium ultraviolet photocuring vacuum plating face is resinized and the screening formulation discussed is at random; These prescriptions are the indefiniteness embodiment; It just is used to specify the present invention, and those skilled in the art can be protection scope of the present invention according to thinking of the present invention and the prescription that the proportioning of selecting materials filters out fully.
The present invention is through the kind of strict control reaction monomers; The selection in the proportioning of reaction mass, order of addition(of ingredients), temperature of reaction and reaction times makes the UV-cured polyurethane acrylate coating resin that makes have high firmness, high abrasion and laser curing velocity faster.Embodiment is:
(1) order of addition(of ingredients) and the charging process (structure of the first step control molecule through controlling raw material; Second step was introduced the photosensitive group unsaturated double-bond), obtain molecular structure control better, the product of excellent combination property, and synthesis technique is mature and stable.
(2) through selecting suitable trivalent alcohol molecular weight (92,150,200) to come adjusting range resinize intensity and wear resistance behind the photocuring; The face two kinds of performances of resinizing behind the photocuring are all better.
(3) through the content and the two distributions of key on main chain of the two keys of control photosensitive group, the laser curing velocity that the face that makes is resinized is preferable.
(4) through the proportioning of control trivalent alcohol and aliphatic diisocyanate, the ratio of regulating hard and soft chain segment in the molecular backbone chain is resinized the synthetic face and is had higher hardness, avoids coating more crisp simultaneously.
(5) through the temperature of reaction and the reaction times in each stage of control, synthesis technique is stable, synthetic face resinize hardness and wear resisting property excellence, and laser curing velocity is very fast.
Embodiment 1:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Isophorone diisocyanate 31.40;
Pentaerythritol triacrylate 55.90;
Polyether-tribasic alcohol (150) 7.70;
Absolute ethyl alcohol 5.00;
Stannous octoate (initiator) 0.02;
P methoxy phenol (stopper) 0.01.
1, base polyurethane prepolymer for use as is synthetic: polyether-tribasic alcohol (150) slowly is added drop-wise in the reaction vessel that isophorone diisocyanate is housed, and reinforced finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%;
Embodiment 2:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Isophorone diisocyanate 33.40;
Pentaerythritol triacrylate 51.70;
Polyether-tribasic alcohol (200) 9.90;
Absolute ethyl alcohol 5.00
Zinc naphthenate (initiator) 0.02
To anisole diphenol (stopper) 0.01
1, base polyurethane prepolymer for use as is synthetic: polyether-tribasic alcohol (200) slowly is added drop-wise in the reaction vessel that isophorone diisocyanate is housed, and behind reinforced the finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%.
Embodiment 3:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Hexamethylene diisocyanate 40.40;
Pentaerythritol triacrylate 56.00;
Glycerine (92) 8.70;
Absolute ethyl alcohol 5.00;
Stannous octoate (initiator) 0.02;
P methoxy phenol (stopper) 0.01.
1, base polyurethane prepolymer for use as is synthetic: glycerine (92) slowly is added drop-wise in the reaction vessel that hexamethylene diisocyanate is housed, and behind reinforced the finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%;
Embodiment 4:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Hexamethylene diisocyanate 33.40;
Pentaerythritol triacrylate 51.70;
Polyether-tribasic alcohol (200) 9.90;
Absolute ethyl alcohol 7.00
Zinc naphthenate 0.02
TEMPO (stopper) 0.02% (double bond content)
1, base polyurethane prepolymer for use as is synthetic: polyether-tribasic alcohol (200) slowly is added drop-wise in the reaction vessel that hexamethylene diisocyanate is housed, and reinforced finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%.
Embodiment 5:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Isophorone diisocyanate 31.40;
Pentaerythritol triacrylate 55.90;
Polyether-tribasic alcohol (150) 7.70;
Absolute ethyl alcohol 5.00;
Stannous octoate (initiator) 0.02;
TEMPO (stopper) 0.02% (double bond content).
1, base polyurethane prepolymer for use as is synthetic: polyether-tribasic alcohol (150) slowly is added drop-wise in the reaction vessel that isophorone diisocyanate is housed, and reinforced finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%;
Embodiment 6:Ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of the present invention is resinized, and is processed than raw material by following weight
:
Hexamethylene diisocyanate 33.40;
Pentaerythritol triacrylate 51.70;
Polyether-tribasic alcohol (200) 9.90;
Absolute ethyl alcohol 5.00
Zinc naphthenate 0.02
TEMPO (stopper) 0.01
1, base polyurethane prepolymer for use as is synthetic: polyether-tribasic alcohol (200) slowly is added drop-wise in the reaction vessel that hexamethylene diisocyanate is housed, and reinforced finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
2, polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the pentaerythritol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
3, the absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system, the reaction times is 0.5 ~ 1 hour, and reaction finishes; Obtain the UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%.
Embodiment 7: spraying vacuum plating finish paint formulation for coating material and technology (recommendation)
Resinize and composite thinner is re-dubbed coating materials with the face of the method for embodiment 1 preparation, carry out photocuring according to following proportioning and processing condition.
Proportioning: face is resinized 100 parts
100 parts of composite thinners
Working viscosity: (25 ° of C are coated with 4#) 13 ~ 14 s
Construction temperature, humidity: 10 ~ 30 ° of C, 60 ~ 80%
UV predominant wavelength: 365 nm
Photocuring power: 80 W/cm
Light application time: 30 s
Luminous range: 15 cm
Implementing process:The finish paint paint spay-coating on Plastic Resin sheet material (cleaning in advance), in 40 ± 5 oC levellings, 2 ~ 5 min, is solidified final vacuum and aluminizes under 1000 W mercury lamp irradiation.
The preparation method of used composite thinner: select a kind of reactive thinner (like among TPGDA, TMPTA or the HDDA any); Being equipped with 2-3 kind (like propyl carbinol and Virahol, butanone and pimelinketone, vinyl acetic monomer and N-BUTYL ACETATE, benzene and toluene) organic reagent again is mixed with composite thinner (example of filling a prescription: vinyl acetic monomer/Virahol/propyl carbinol=2:1:1), viscosity to the working viscosity of regulating the base paint system also can.
Coating (finish paint) Performance Detection:
Viscosity (25oC, is coated with 4
#Cup): 13 ~ 16 s
Pencil hardness: 2H
The 60o glossiness:>90
Snappiness (mm): < 3 mm
Sticking power (hundred lattice methods): < 1 grade
Ethanol-tolerant test: qualified
Claims (10)
1. a ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face is resinized, and it is characterized in that: processed by following weight proportioning raw material:
Aliphatic diisocyanate 20 ~ 45;
Polyvalent alcohol triacrylate 40 ~ 75;
Trivalent alcohol 5 ~ 15;
Absolute ethyl alcohol 3 ~ 8;
Initiator, stopper are 0.01 ~ 0.05% of above-mentioned raw materials total amount.
2. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized; It is characterized in that, described aliphatic diisocyanate adopt following one or more: hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI).
3. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum metallizing coating resin according to claim 1; It is characterized in that described polyvalent alcohol triacrylate adopts following a kind of or two kinds: pentaerythritol triacrylate, Dipentaerythritol five propenoate.
4. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized; It is characterized in that, described trivalent alcohol adopt following one or more: glycerine (molecular weight 92), polyether-tribasic alcohol (molecular weight 150), polyether-tribasic alcohol (molecular weight 200).
5. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized; It is characterized in that, described initiator adopt following one or more: dibutyl tin laurate, triethylene diamine, stannous octoate and zinc naphthenate.
6. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized; It is characterized in that; Described stopper adopt following one or more: phenol, p methoxy phenol, to anisole diphenol, 2; 2,6,6-tetramethyl--piperidine NO free radical (TEMPO).
7. ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized, and it is characterized in that by weight, proportioning raw materials is following:
Aliphatic diisocyanate 20 ~ 45;
Polyvalent alcohol triacrylate 40 ~ 75;
Trivalent alcohol 10 ~ 25;
Absolute ethyl alcohol 3 ~ 8;
Initiator, stopper are 0.01 ~ 0.05% of above-mentioned raw materials total amount.
8. the preparation method that ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 1 is resinized is characterized in that:
(1) base polyurethane prepolymer for use as is synthetic: trivalent alcohol slowly is added drop-wise in the reaction vessel that aliphatic diisocyanate is housed, and behind reinforced the finishing, insulation reaction obtains base polyurethane prepolymer for use as;
(2) polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the polyvalent alcohol triacrylate mixture that contains initiator, stopper then; After dropwising, react, reaction obtains polyurethane acrylic ester oligomer after finishing;
(3) absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer, with unreacted isocyano in the termination system, reaction finishes to obtain UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%.
9. the preparation method that ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face according to claim 8 is resinized is characterized in that:
(1) base polyurethane prepolymer for use as is synthetic: trivalent alcohol slowly is added drop-wise in the reaction vessel that aliphatic diisocyanate is housed, and behind reinforced the finishing, insulation reaction 2 ~ 3 hours obtains base polyurethane prepolymer for use as;
(2) polyurethane acrylic ester oligomer is synthetic: base polyurethane prepolymer for use as is cooled to 50 ° below the C; Drip the polyvalent alcohol triacrylate mixture that contains initiator, stopper then; After dropwising, reacted 2 ~ 3 hours, reaction obtains polyurethane acrylic ester oligomer after finishing;
(3) absolute ethyl alcohol that takes by weighing is joined in the polyurethane acrylic ester oligomer; With unreacted isocyano in the termination system; Reaction times is 0.5 ~ 1 hour, and reaction finishes to obtain UV-cured polyurethane acrylate coating resin, its solid content (weight %) >=90%.
10. vacuum plating finish paint coating, it comprises like each ultraviolet light polymerization polyfunctionality urethane acrylate vacuum plating face of claim 1-7 resinizes, and proper amount of diluting.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210064714.XA CN102585157B (en) | 2012-03-13 | 2012-03-13 | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210064714.XA CN102585157B (en) | 2012-03-13 | 2012-03-13 | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102585157A true CN102585157A (en) | 2012-07-18 |
| CN102585157B CN102585157B (en) | 2014-04-09 |
Family
ID=46474453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210064714.XA Active CN102585157B (en) | 2012-03-13 | 2012-03-13 | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585157B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214653A (en) * | 2013-04-25 | 2013-07-24 | 广东工业大学 | Ultraviolet cured waterborne polyurethane surface-coating resin and preparation method and application thereof |
| CN103289558A (en) * | 2013-05-29 | 2013-09-11 | 江苏兰陵高分子材料有限公司 | Ultraviolet curing coating for steel surface and preparation method thereof |
| CN104086742A (en) * | 2014-06-27 | 2014-10-08 | 广东工业大学 | Preparation method of acid and alkali resistant ultraviolet-curing adhesive film resin for glass base material |
| CN104830222A (en) * | 2015-04-28 | 2015-08-12 | 中科院广州化学有限公司南雄材料生产基地 | Dual-curable polyurethane paint with low surface energy and preparation method thereof |
| CN105463940A (en) * | 2014-09-03 | 2016-04-06 | 昆山市生力包装材料有限公司 | Production method for environment-friendly vacuum aluminized laser paper |
| CN110408315A (en) * | 2019-08-23 | 2019-11-05 | 东莞泰合复合材料有限公司 | A kind of water-based gloss oil and its preparation method and application |
| CN110616411A (en) * | 2019-09-23 | 2019-12-27 | 海盐鑫中岳电子科技有限公司 | PVD vacuum coating process and coated workpiece |
| CN111533879A (en) * | 2020-05-25 | 2020-08-14 | 江苏开磷瑞阳化工股份有限公司 | Oligomer for polyurethane acrylate vacuum plating primer, preparation method of oligomer and vacuum plating primer containing oligomer |
| CN111675793A (en) * | 2020-05-13 | 2020-09-18 | 广东深展实业有限公司 | Waterborne polyurethane modified acrylic resin and preparation method and application thereof |
| CN111732888A (en) * | 2020-07-07 | 2020-10-02 | 嘉善三思光电技术有限公司 | Photocuring vacuum coating paint, preparation method and application thereof, and LED display screen formed by photocuring vacuum coating paint and used for subtropical island basements |
| CN112029067A (en) * | 2020-09-08 | 2020-12-04 | 珠海市金团化学品有限公司 | Photo-curing water-based acrylic acid dispersion and preparation method and application thereof |
| CN112225868A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Two-three functionality mixed polyurethane acrylate resin and preparation method thereof |
| WO2023284618A1 (en) * | 2021-07-15 | 2023-01-19 | 道生天合材料科技(上海)股份有限公司 | Resin composition, polyurethane material, polyurethane composite material, and preparation methods |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760061A (en) * | 2008-11-26 | 2010-06-30 | 李岳 | Light-cured polyurethane coating and preparation method thereof |
-
2012
- 2012-03-13 CN CN201210064714.XA patent/CN102585157B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760061A (en) * | 2008-11-26 | 2010-06-30 | 李岳 | Light-cured polyurethane coating and preparation method thereof |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214653A (en) * | 2013-04-25 | 2013-07-24 | 广东工业大学 | Ultraviolet cured waterborne polyurethane surface-coating resin and preparation method and application thereof |
| CN103214653B (en) * | 2013-04-25 | 2016-04-20 | 广东工业大学 | Resinize and its preparation method and application in a kind of ultraviolet light solidfication water polyurethane face |
| CN103289558A (en) * | 2013-05-29 | 2013-09-11 | 江苏兰陵高分子材料有限公司 | Ultraviolet curing coating for steel surface and preparation method thereof |
| CN103289558B (en) * | 2013-05-29 | 2015-08-26 | 江苏兰陵高分子材料有限公司 | A kind of ultraviolet-curing paint for steel surface and preparation method |
| CN104086742B (en) * | 2014-06-27 | 2016-08-17 | 广东工业大学 | A kind of preparation method of glass baseplate acid and alkali-resistance ultraviolet light solidified glue film resin |
| CN104086742A (en) * | 2014-06-27 | 2014-10-08 | 广东工业大学 | Preparation method of acid and alkali resistant ultraviolet-curing adhesive film resin for glass base material |
| CN105463940A (en) * | 2014-09-03 | 2016-04-06 | 昆山市生力包装材料有限公司 | Production method for environment-friendly vacuum aluminized laser paper |
| CN104830222B (en) * | 2015-04-28 | 2017-04-12 | 中科院广州化学有限公司南雄材料生产基地 | Dual-curable polyurethane paint with low surface energy and preparation method thereof |
| CN104830222A (en) * | 2015-04-28 | 2015-08-12 | 中科院广州化学有限公司南雄材料生产基地 | Dual-curable polyurethane paint with low surface energy and preparation method thereof |
| CN110408315A (en) * | 2019-08-23 | 2019-11-05 | 东莞泰合复合材料有限公司 | A kind of water-based gloss oil and its preparation method and application |
| CN110616411A (en) * | 2019-09-23 | 2019-12-27 | 海盐鑫中岳电子科技有限公司 | PVD vacuum coating process and coated workpiece |
| CN110616411B (en) * | 2019-09-23 | 2021-09-07 | 海盐鑫中岳电子科技有限公司 | PVD vacuum coating process and coated workpiece |
| CN111675793A (en) * | 2020-05-13 | 2020-09-18 | 广东深展实业有限公司 | Waterborne polyurethane modified acrylic resin and preparation method and application thereof |
| CN111533879A (en) * | 2020-05-25 | 2020-08-14 | 江苏开磷瑞阳化工股份有限公司 | Oligomer for polyurethane acrylate vacuum plating primer, preparation method of oligomer and vacuum plating primer containing oligomer |
| CN111732888A (en) * | 2020-07-07 | 2020-10-02 | 嘉善三思光电技术有限公司 | Photocuring vacuum coating paint, preparation method and application thereof, and LED display screen formed by photocuring vacuum coating paint and used for subtropical island basements |
| CN112029067A (en) * | 2020-09-08 | 2020-12-04 | 珠海市金团化学品有限公司 | Photo-curing water-based acrylic acid dispersion and preparation method and application thereof |
| CN112225868A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Two-three functionality mixed polyurethane acrylate resin and preparation method thereof |
| WO2023284618A1 (en) * | 2021-07-15 | 2023-01-19 | 道生天合材料科技(上海)股份有限公司 | Resin composition, polyurethane material, polyurethane composite material, and preparation methods |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102585157B (en) | 2014-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585157B (en) | Ultraviolet light polymerization polyfunctionality polyurethane acrylate vacuum coating surface coating resin | |
| CN102604035B (en) | Ultraviolet cured two-degree-of-functionality polyurethane acrylic ester base coating resin for vacuum coating | |
| CN103013324B (en) | Self-repair type ultraviolet-cured paint | |
| CN102791484B (en) | Vehicle member and manufacturing method therefor | |
| TWI686314B (en) | Laminated film for decoration of three-dimensional molded products for vacuum forming, manufacturing method thereof, and three-dimensional molded product decoration method | |
| CN101735379B (en) | Preparation method of self-drying low aliphatic chain oxosilane modified water-borne acrylic resin | |
| KR101158462B1 (en) | UV curable resin composition of organic-inorganic hybride type | |
| CN102391699B (en) | Ultraviolet light curing paint | |
| CN102161862A (en) | Ultraviolet (UV) light-curable polyurethane acrylic resin composite | |
| CN102762657A (en) | Radiation curable resin composition, and fingerprint-resistant resin composition containing same | |
| CN102863893A (en) | Ultraviolet curing paint | |
| CN102146254A (en) | UV (ultraviolet) roller-coating metal high-adhesion yellowing-resistant primer | |
| CN102770496A (en) | Radiation curable liquid composition for low gloss coatings | |
| CN102295881A (en) | Preparation method for high-hardness organic-inorganic hybrid ultraviolet light curing coating, and application thereof | |
| CN102329557A (en) | Ultraviolet curing paint | |
| CN101280154B (en) | Ultraviolet curing vacuum metallizing coating | |
| CN102947395A (en) | Curing-type coating-agent composition | |
| CN100471670C (en) | Laminate film | |
| TWI224616B (en) | Coating materials | |
| CN102782065A (en) | Coating agent composition | |
| CN104726014A (en) | Ultraviolet curing coating raw material and coating prepared from same | |
| CN100372899C (en) | Mirror back paint resin and spraying paint | |
| AU2022201104B2 (en) | Amino resin alkyd matting paint | |
| CN102791756A (en) | Actinic-light-curable composition, molded polycarbonate resin object with a cured film, and manufacturing method therefor | |
| CN102585579B (en) | metal powder oriented resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |