CN100491485C - Photocurable leather coating composition - Google Patents
Photocurable leather coating composition Download PDFInfo
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- CN100491485C CN100491485C CNB011365900A CN01136590A CN100491485C CN 100491485 C CN100491485 C CN 100491485C CN B011365900 A CNB011365900 A CN B011365900A CN 01136590 A CN01136590 A CN 01136590A CN 100491485 C CN100491485 C CN 100491485C
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Abstract
The photocurable leather coating composite includes: (A). 5-60 wt% of mixture formed from at least one kind of polyurethane (methyl) acrylate prepolymer and at least one kind of epoxy (methyl) acrylate prepolymer; (B). 10-30 wt% of the monomer selected from styrenes, (methyl) acrylates and vinyl ethers which can be polymerized with the above-mentioned component A; (C). 1%-15 wt% of photoinitiator or photoinitiator and initiation adjuvant which can be polymerized with free radical and (D) 5-30 wt% of adjuvant.
Description
Invention field
The present invention relates to the composition on the leather substrate, covered with paint, lacquer, colour wash, etc., it can UV-light and radiation of visible light under in-situ solidifying.
Background technology
Without the leather of covering with paint, lacquer, colour wash, etc., grain is coarse, lacks gloss, and color is not bright-coloured yet, poor-performings such as its water-repellancy, anti-greasy dirt, Bearable dry and wet wipe and crash worthiness.And the leather through covering with paint, lacquer, colour wash, etc. because its surface imposes the coatings of one deck excellent property, makes its surface smoothing careful, glossy, bright-colored and uniformity; Simultaneously, make also that leather is heat-resisting, cold-resistant, oil resistant is dirty, be easy to performances such as maintenance and improve greatly, and improved the physical and mechanical properties of leather surface, prolonged the work-ing life of leather.
The dope layer of leather surface generally have the end, in, the top three layers.Bottom generally adopts positively charged ion back cover coating agent back cover, reduces the priming paint agent and too much infiltrates in the leather, and is very little to the feel influence of leather.Undercoat comprises soft resin, pigment paste, auxiliary agent etc., guarantees the good tackiness of coating, winter hardiness, anti-refrangibility etc.Floating coat adopts soft resin and middle hard resin collocation use, and some pigment pastes, auxiliary agent etc., and is generally hard than undercoat, and the color even unanimity is smooth smooth, and anti-flatiron.Top layer is a protective layer, requires Bearable dry and wet wipe, organic solvent-resistant, anti-collision, good hand touch etc., the outward appearance and the feel of its decision finished leather.
The top layer aqueous coating agent of leather can divide two kinds at present, and a kind of is non-cross-linking type, because it contains hydrophilic radical or emulsifying agent, so water-fast solvent resistance is bad; A kind of is cross-linking type.Because leather substance is long time treatment at high temperature, this has just limited the use of high-temperature cross-linking agent.But a few class cold cross-linking agent of having developed at present all exist toxicity big, to water sensitive, use shortcomings such as restricted.
Disclose some in the prior art and can be used for to nonspecific property the coating composition of leather, for example CN1044666A discloses a kind of light solidifying paint composition, and it is formed by release agent such as acrylic acid alkyl esters and Photoepolymerizationinitiater initiater such as benzophenone-trolamine system etc. through Abietyl modified epoxy acrylic ester prepolymer, activity.In addition, CN1099047A discloses a kind of ultraviolet cured paint composition, and it is made up of the polymeric acrylate (as polyester acrylate, polyether acrylate, bisphenol A epoxy acrylate and/or urethane acrylate) of 10-60%, the reactive thinner monomer (as simple function group monomer or polyfunctional monomer) of 20-80%, light trigger (as benzophenone, 907,1173) and other group agent of 0.5-10%.But these coating compositions are as hide finishes the time, still can not satisfy hide finishes in glossiness, anti-flexion, the anti-requirement of doing aspects such as moist, ventilation property, low-temperature performance.
At the deficiencies in the prior art, the present inventor has carried out deep research, and result's invention can overcome the defective of prior art by adopting the hereinafter described photocurable leather coating composition of the present invention, so the present invention who finishes.
Summary of the invention
The invention provides a kind of photocurable leather coating composition, it comprises:
(A) mixture formed of at least a urethane (methyl) acrylic ester prepolymer of 5%-60% and at least a epoxy (methyl) acrylic ester prepolymer by weight;
(B) by weight 10%-30% can be selected from styrenic, (methyl) esters of acrylic acid, vinyl ethers monomer with said components A polymeric;
(C) light trigger that is used for radical polymerization of 1%-15% or light trigger and aided initiating by weight;
(D) auxiliary agent of 5%-30% by weight.
In preferred embodiments, component (B) is polyfunctionality (methyl) acrylate monomer.
Detailed Description Of The Invention
Generally speaking, the ultraviolet light polymerization finishing agent is mixed by prepolymer, monomer and light trigger.When the UV-light of suitable wavelength and light intensity was throwed this coating, light trigger wherein just resolved into radical.Polyaddition reaction fast takes place in the unsaturated group that these radicals can then cause on prepolymer and the monomer.Because what adopt is polyfunctional monomer and prepolymer, and the chemical property of this class free radical reaction, so coating can change into the insolubility cross-linked structure rapidly.The advantage of this technology is: save energy, do not have volatile solvent, set time is short, saves the place.
The photocuring that is fit to be coated with decorative composition usually by about 5%-60% (weight percent) but the prepolymer of at least two kinds of illumination curing formed.Be coated with the gross weight of decorative composition in this, the preferred amounts of photo curable prepolymer is about 20%-60% (weight percent).For the balance that obtains various performances can adopt one, two, three and the mixture of higher functionalized oligopolymer, wherein functionality refers to be present in the quantity of the functional group of radiation-hardenable in the prepolymer.
Prepolymer comprises the functional groups carbon containing backbone structure thereon of a radiation-hardenable usually.The example of prepolymer comprises urethane (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate and polyethers (methyl) acrylate.The example of urethane (methyl) acrylate comprises the reaction product that the reaction by (methyl) acrylate of hydroxyl and polyvalent alcohol and organic multiple isocyanate makes.The example of low molecular weight polyols comprises ethylene glycol, propylene glycol, butyleneglycol etc.The example of organic multiple isocyanate comprises tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.The example of (methyl) acrylate of hydroxyl comprises (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester.
Polyester (methyl) acrylic ester prepolymer comprises polyester polyol and (methyl) acrylic acid dehydrating condensation product.The example of polyester polyol comprises the reaction product of low molecular weight polyols and diprotic acid, for example ethylene glycol, polyoxyethylene glycol, hexanaphthene dimethyl alcohol, 3-methyl isophthalic acid of polyvalent alcohol wherein, 5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexylene glycol and TriMethylolPropane(TMP) or its oxyalkylene adduct, diprotic acid is hexanodioic acid, succsinic acid, phthalic acid, hexahydro-phthalic acid and terephthalic acid for example, or its acid anhydrides.
The epoxy acrylate class is for example adduct of (methyl) vinylformic acid reaction of Resins, epoxy and unsaturated carboxylic acid, comprises for example (methyl) acrylate of diglycidyl ether of epoxy (methyl) acrylate of epoxy (methyl) acrylate, phenol or cresol-novolac epoxy resin of bisphenol A type epoxy resin and polyethers.
The example of polyethers (methyl) acrylate comprises polyalkylene glycol two (methyl) acrylate, for example polyoxyethylene glycol two (methyl) acrylate and polypropylene glycol two (methyl) acrylate, and oxyalkylene modified product.
Be preferably the mixture of at least a urethane acrylate and a kind of epoxy acrylate among the component A among the present invention.Because urethane acrylate provides good sticking power to coating, guarantee that coating has excellent resistance to low temperature, but set time is long, the cost height.Epoxy acrylate then has short benefit set time, and cost is low, with the two use that combines, can learn from other's strong points to offset one's weaknesses, and obtains needed optimum performance.The example of preferred prepolymer has Ebecryl 264 (UCB), and its molecular weight is about 2000, solidifies Tg and is about 42 ℃.Another example of preferred oligopolymer is bisphenol A epoxy acrylate (factory orientalizes), its molecular weight about 500.
The number-average molecular weight of component A is generally 400-5000, is preferably 500-3000, most preferably is 500-2000.
The photo curable decorative composition that is coated with that is fit to can be selected from styrenic, (methyl) esters of acrylic acid, vinyl ethers monomer (B) with said components A polymeric by about 10%-30% (weight percent) at least a usually and formed.Be coated with the gross weight of decorative composition in this, the preferred amounts of the monomer of radiation-hardenable (B) is about 20%-30%.This monomer contains at least one can carry out illumination curing polymeric functional group.But the monomer that preferred functional group wherein can carry out copolymerization with the functional group of illumination curing in the prepolymer.Wherein, component (A) is 1:1 to 5:1 with the weight ratio of monomer (B).
Monomer (B) comprises styrenic, (methyl) acrylate, vinyl ether and composition thereof.The example of styrenic and derivative thereof comprises vinylbenzene, alpha-methyl styrene etc.(methyl) acrylate comprises (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester; (methyl) alkyl acrylate, for example (methyl) butyl acrylate, (methyl) isobutyl acrylate and (methyl) acrylic acid-2-ethyl polyhexamethylene; Alicyclic alkyl (methyl) acrylate, for example (methyl) cyclohexyl acrylate; Aryl (methyl) acrylate that replaces, for example (methyl) vinylformic acid benzyl ester; (methyl) vinylformic acid alcoxyl base ester, for example (methyl) vinylformic acid-2-methoxy ethyl ester and (methyl) vinylformic acid-2-ethoxyethyl group ester; (methyl) vinylformic acid iso-borneol thiazolinyl ester; With (methyl) acrylate that contains alkoxysilyl.Oxyalkylene adds the acrylate of phenol, for example (methyl) vinylformic acid phenoxy group ethyl ester, and the product of halogen nucleophilic substitution; The list of glycol (methyl) acrylate, for example list (methyl) acrylate of list (methyl) acrylate of list (methyl) acrylate of the list of ethylene glycol (methyl) acrylate, methoxyl group ethylene glycol, Tetraglycol 99 and triglycol; The example that contains the useful monomers of two or more ethylenic unsaturated groups comprises alkylene glycol two (methyl) acrylate, for example ethylene glycol bisthioglycolate (methyl) acrylate and propylene glycol two (methyl) acrylate; Low-molecular-weight polyalkylene glycol two (methyl) acrylate, for example glycol ether two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, dipropylene glycol two (methyl) acrylate and tripropylene glycol two (methyl) acrylate, with and the product of oxyalkylene modification; Polyvalent alcohol many (methyl) acrylate, for example trimethylolpropane tris (methyl) acrylate, tetramethylolmethane two or three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, two TriMethylolPropane(TMP) four (methyl) acrylate, Dipentaerythritol five or six (methyl) acrylate, with and the product of oxyalkylene modification; With two or three (methyl) acrylate with the modification of isocyanuric acid oxyalkylene.
The example of vinyl ether comprises hexanaphthene dimethyl alcohol divinyl ether, hydroxyethyl vinyl ether and triethylene glycol divinyl ether.
The example of other component (B) comprises N-vinyl pyrrolidone, N-caprolactam, acryloyl morpholine, N-vinyl formamide and N-vinyl acetamide.
The preferred aliphatic poly acrylate that uses is as two functionality component (B) 1,6 hexanediol diacrylates and three-functionality-degree thinner Viscoat 295.1,6 hexanediol diacrylate is a kind of linear chain structure, gives the good snappiness of filming.Contain 3 two keys in the Viscoat 295, can improve the curing speed of filming.
But the decorative composition that is coated with of suitable illumination curing is made up of at least a light trigger (C) of about 1%-15% (weight percent) usually, and it is undertaken by the intramolecularly cracking.Be coated with the gross weight of decorative composition in this, but the preferred amounts of the component of illumination curing (B) is about 3%-10%.In general, along with the increase of light trigger consumption, curing speed is accelerated.We test discovery and are increased to after the certain numerical value when the light trigger consumption, and the light trigger consumption increases, and curing speed is not accelerated.
The suitable example of the light trigger of free radical type comprises bitter almond oil camphor and alkyl oxide thereof, for example bitter almond oil camphor, benzoin methyl ether, bitter almond oil camphor ethyl ether and bitter almond oil camphor isopropyl ether; Acetophenones, methyl phenyl ketone, 2 for example, 2-dimethoxy-2-phenyl methyl phenyl ketone (BDK), 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 1-hydroxy acetophenone, 2,2-dimethyl-2-hydroxy acetophenone (1173), 1-hydroxycyclohexylphenylketone (184) and 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinyl-propane-1-ketone (907); Anthraquinone, for example 2-tertiary butyl anthraquinone, 1-chloroanthraquinone and 2-amyl anthraquinone; Thioxanthone, for example 2,4-dimethyl thioxanthone (DMTX), 2,4-diethyl thioxanthone (DETX), 2 (or 4)-isopropyl thioxanthones (1TX), 2-clopenthixal ketone (CTX) and 2,4-di-isopropyl thioxanthone; Ketal, for example methyl phenyl ketone dimethyl ketal and benzil dimethyl ketal; Benzophenone, for example benzophenone; And xanthone; Acyl group is seen oxygen compound as 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide (TPO), two (2; 4, the 6-trimethylbenzoyl)-phenyl phosphine oxide (819), two (2, the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide (BAPO), 2,4,6-trimethylbenzoyl phenyl ethoxy phosphine oxide (TPO-L).
These light triggers can use separately, or are used in combination with the aided initiating of amine, dimethylaminobenzoic acid ester class etc.Dimethylaminobenzoic acid ester class, for example ethyl-right-(dimethylamino) benzoic ether (EDAB), octyl group-right-(dimethylamino) benzoic ether (ODAB); Alkyl alcohol radical amine is thanomin, Yi Bingchunan, diethanolamine, diisopropanolamine (DIPA), trolamine, tri-isopropanolamine, methyldiethanolamine etc. for example; The esters of acrylic acid reactive thinner or the prepolymer of amine modification.Good promoter action is arranged is well-known to aided initiating to carrying the Hydrogen initiator, and it has the oxygen inhibition of overcoming effect to radical polymerization simultaneously.Good promoter action is arranged is well-known to aided initiating to carrying the Hydrogen initiator, and it has the oxygen inhibition of overcoming effect to radical polymerization simultaneously.
The addition of aided initiating is preferably based on 0.1-10 part of 100 parts of leather finish compositions or littler, more preferably 0.5-5 part.
The photo curable decorative composition that is coated with that is fit to is made up of at least a auxiliary agent (D) of about 5%-30% (weight percent) usually.Be coated with the gross weight of decorative composition in this, the preferred amounts of auxiliary agent is about 5%-30% (weight percent).Because the special extensibility requirement of hide finishes, use softening agent as auxiliary agent this moment.
Softening agent divides two classes: internal plasticization and physical plasticizing.Plastifying the time, be distributed in the intermolecular lower-molecular substance of membrane-forming agent and play similar lubricant outside, weakened relevant power, under the effect of additional stress, macromole can relatively move to each other.The example of physical plasticizing such as tritolyl phosphate, dibutyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP).Internal plasticization is to introduce softening agent in building-up process.Internally plasticized effect is to shield the active group that causes molecular interaction, or in polymer chain, insert motion, resilient, do not have the segment of molecular interaction.The structure and the building-up process that are decided by them for the necessary elasticity of synthetic membrane-forming agent (polyacrylic ester and carbamate).Preferred example is a dimixo-octyl phthalate.Auxiliary agent D) also comprises auxiliarys such as defoamer, flow agent.
Characteristics of the present invention are UV-curing technology is applied to leather finish, its coating is a cross-linked structure, operating process has no irritating odor, and provides that a kind of curing speed is fast, glossiness is high, anti-flexion, Bearable dry and wet wipe, low wet performance be good, the good advantage of anti-water good solubility-resistence.
Embodiment
The present invention will further explain by following each embodiment, but not be subject to these embodiment.
Be mixed with present composition embodiment by above description and according to the method for routine, wherein the composition weight umber among each embodiment is listed in the table below respectively in 1:
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Polyurethane acroleic acid | 30 | 30 | 47 | 47 | 40 | 40 | 35 | 35 | 50 | |
| Epoxy acrylate | 25 | 25 | 5 | 5 | 20 | 20 | 20 | 20 | 50 | |
| HDDA | 10 | 10 | 30 | 30 | 15 | 15 | 30 | 30 | 19 | 17 |
| TMPTA | 15 | 15 | 5 | 5 | 15 | 15 | 5 | 5 | 10 | 10 |
| 1173 | 2 | 2 | ||||||||
| 184 | 8 | 5 | 3 | 3 | ||||||
| 907 | 5 | 3 | 3 | 5 | ||||||
| TPO | 3 | |||||||||
| Benzophenone | 3 | |||||||||
| Trolamine | 3 | 3 | ||||||||
| Softening agent | 10 | 10 | 5 | 5 | 5 | 5 | 5 | 5 | 10 | 15 |
| Defoamer | 2 | 2 | 3 | 3 | 2 | 2 | 2 | 2 | 2 | 2 |
| Flow agent | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
Abbreviation in the table 1 has following connotation:
HDDA:1,6-hexylene glycol two propernoic acid esters
TMPTA: Viscoat 295
Softening agent: dimixo-octyl phthalate
Defoamer: the product B YK-067 of Bi Ke company
Flow agent: the product B YK-355 of Bi Ke company
In order to test the above-listed decorative composition that is coated with, it is applied on the cattle hide, adopt 500 watts of high voltage mercury lamp radiations, solidify back test and the following performance index:
The tensile strength of leather, the elongation at break of leather, xerotripsis performance, wet rubbing performance, anti-refrangibility, ventilation property, glossiness, hardness.
Measure the purpose of tensile strength, be to understand sample distortion situation under external force and reactive force that they can bear, this is one of important indicator of identifying the leather mechanical property.According to measurement result, can judge the quality and the durable situation of finished leather to a great extent.Tensile strength is meant sample being subjected to that axial force stretches during fracture, suffered power on the unit cross-sectional area.
Leather belongs to elastic-plastic material, under external force, deform.The distortion of leather is divided into recoverable deformation and tension set, when making leather goods and use, necessarily requires it that to a certain degree tension set is arranged, otherwise just none fixed shape of leather goods.Yet, also there is not good method accurately to characterize the plastoelastic deformation of leather at present, can only understand related properties with the experiment of the elongation of measuring the leather sample.Elongation at break is the sample length that begins to be subjected to being stretched to when breaking and extended and the length ratio of former part of the force, represents with percentage.
Leather goods in use can be needed wiping by pickup unavoidably, and this just requires to remove from office certain Bearable dry and wet wipe.With pulvinus coloured light leather sample that rubs of rotation, the revolution of pulvinus is weighed to the degree on the friction materials with staining when writing down sample again and making any difference, and measures the ability of the Bearable dry and wet wipe of light leather.
Leather goods in use can constantly be subjected to flecition.Because the fibrous bundle of grain layer is than the more very thin fragility of reticular layer, therefore under repeated flex, slight crack often appears earlier in grain layer.In addition, covering with paint, lacquer, colour wash, etc. film also can be under flecition repeatedly and weaken with the fastness that combines of removing from office body, flakes, falls phenomenons such as slurry.In order to check the anti-crooked fastness of leather, national Specification carries out folding endurance test with the light leather instrument.This experiment is sample method for folding in accordance with regulations to be placed in the folder up and down of instrument carry out reciprocal flexion.Measure that leather body and surface thereof produce variable color, fluffing, crackle, flake, fall slurry, broken flexion number of times when phenomenon such as wearing.
Ventilation property is one of good character of leather, is meant in certain pressure and certain hour the volume of the air that the sample unit surface is seen through.
Glossiness is measured with the glossiness tester according to GB.
Hardness is measured with the pendulum-type sclerometer according to GB.
Every The performance test results can see the following form 2:
Table 2
Annotate: the GB requirement of every index is
The tensile strength of leather〉15Mpa
The elongation at break of leather＜55% (upper leather)
The xerotripsis performance〉4.0
The wet rubbing performance〉3.0
Anti-refrangibility〉20,000 times
Claims (7)
1. photocurable leather coating composition, it comprises:
(A) mixture formed of a kind of urethane (methyl) acrylic ester prepolymer of 5%-60% and a kind of epoxy (methyl) acrylic ester prepolymer by weight, wherein, the weight ratio of urethane (methyl) acrylic ester prepolymer and epoxy (methyl) acrylic ester prepolymer is 1:1 to 5:1;
(B) by weight 10%-30% can with the polyfunctionality of component polymeric described in (A) (methyl) acrylate monomer;
(C) light trigger that is used for radical polymerization of 1%-15% or light trigger and aided initiating by weight;
(D) auxiliary agent that is selected from softening agent, defoamer, flow agent and composition thereof of 5%-30% by weight.
2. according to the composition of claim 1, it comprises
(A) mixture formed of a kind of urethane (methyl) acrylic ester prepolymer of 20%-60% and a kind of epoxy (methyl) acrylic ester prepolymer by weight, wherein, the weight ratio of urethane (methyl) acrylic ester prepolymer and epoxy (methyl) acrylic ester prepolymer is 1:1 to 5:1;
(B) by weight 20%-30% can with the polyfunctionality of component polymeric described in (A) (methyl) acrylate;
(C) light trigger that is used for radical polymerization of 1%-15% or light trigger and aided initiating by weight;
(D) by weight the mixture of the softening agent of 5%-30%, defoamer and flow agent as auxiliary agent.
3. according to the composition of claim 1 or 2, wherein
(B) polyfunctionality described in (methyl) acrylate is the mixture that 1,6 hexanediol diacrylate and Viscoat 295 are formed.
4. according to the composition of claim 1, wherein
(C) light trigger described in is selected from 2,2-dimethyl-2-hydroxy acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto)-phenyl]-2-morpholinyl-propane-1-ketone and benzophenone at least a.
5. according to the composition of claim 1, wherein
(C) comprise the aided initiating of 0.1%-10% by weight in.
6. according to the composition of claim 5, wherein
(C) light trigger described in is a trolamine.
7. according to the composition of claim 1, wherein
(D) softening agent described in is a dimixo-octyl phthalate.
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| CNB011365900A CN100491485C (en) | 2001-10-19 | 2001-10-19 | Photocurable leather coating composition |
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| CNB011365900A CN100491485C (en) | 2001-10-19 | 2001-10-19 | Photocurable leather coating composition |
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| CN100491485C true CN100491485C (en) | 2009-05-27 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329466C (en) * | 2005-03-01 | 2007-08-01 | 浙江大学 | Method for preparing solvent-free low-viscosity UV-cured polyurethane acrylate leather coating agent |
| CN101177553B (en) * | 2007-11-30 | 2010-05-19 | 华南理工大学 | Composite ultraviolet solidified aqueous coating and preparation method thereof |
| CN102031696B (en) * | 2009-09-24 | 2012-05-23 | 湖州凯恩涂层有限公司 | Ultraviolet curing coating for label fabrics |
| CN103540246A (en) * | 2013-10-16 | 2014-01-29 | 烟台德邦科技有限公司 | No-clean ultraviolet (UV) curable conformal coating |
| CN106752880A (en) * | 2017-03-15 | 2017-05-31 | 建德市顺发化工助剂有限公司 | A kind of glossy leather finishing agent of ultraviolet light solidfication water polyurethane acrylate |
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| CN1196370A (en) * | 1997-04-02 | 1998-10-21 | 三星电管株式会社 | Coating composition for cathode ray tube and method of coating same |
| CN1258701A (en) * | 1998-12-31 | 2000-07-05 | 中国科学院近代物理研究所 | Electron beam radiation cured paint for wooden material and its application |
| CN1297972A (en) * | 2000-06-07 | 2001-06-06 | 湖南亚大化工建材有限公司 | Ultravoilet cured paint without irritation |
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|---|---|---|---|---|
| US5418016A (en) * | 1991-03-03 | 1995-05-23 | Air Products And Chemicals, Inc. | Coating process using radiation curable compositions |
| CN1196370A (en) * | 1997-04-02 | 1998-10-21 | 三星电管株式会社 | Coating composition for cathode ray tube and method of coating same |
| CN1258701A (en) * | 1998-12-31 | 2000-07-05 | 中国科学院近代物理研究所 | Electron beam radiation cured paint for wooden material and its application |
| CN1297972A (en) * | 2000-06-07 | 2001-06-06 | 湖南亚大化工建材有限公司 | Ultravoilet cured paint without irritation |
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