CN1844229A - UV curable aqueous resin composition - Google Patents
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- CN1844229A CN1844229A CN 200610035463 CN200610035463A CN1844229A CN 1844229 A CN1844229 A CN 1844229A CN 200610035463 CN200610035463 CN 200610035463 CN 200610035463 A CN200610035463 A CN 200610035463A CN 1844229 A CN1844229 A CN 1844229A
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Abstract
The invention discloses a composition of vis-UV cured water resin, which consists of (A) 10-70 mass % of water epoxy acrylate solidified and modified by the ray; (B) 0 mass % -10 mass % of water acrylate monomer or water acrylate prepolymer; (C) 1 mass % -5 mass % of photochemical initiator; (D) 0.1 mass % -8 mass % of adjuvant; (E) 10 mass % -60 mass % of deionized water or alcoholic dissolvent; the composition can be used for water UV solidifying paint solidified by vis-UV, water UV solidified finishing and water UV solidified ink binding material; the external appearance of the vis-UV cured water composition is lacte or lacte liquid with blue rays; it can be diluted with water, the viscosity can be adjusted and the inducration speed is fast; it is nontoxic, ordorless, safety and environment-friendly; after the solidification by the ultraviolet, its film is neat and smooth, is of high glossiness, and is of good flexibility, scratch resistance, water resistance and solvent resistance.
Description
Technical field
The invention belongs to the UV curable aqueous finishing agent in the light industry field, be specifically related to a kind of UV curable aqueous resin composition.
Technical background
Base materials such as paper, leatheroid or natural leather, plastics, metal, timber are widely used in the human lives, but raising along with people's living standard, use properties and performance performance to above-mentioned materials are all had higher requirement, and it is exactly a kind of efficient and simple method that glazing is covered with paint, lacquer, colour wash, etc.Above-mentioned materials surface irregularity without glazing is covered with paint, lacquer, colour wash, etc. lacks gloss, and color is not bright-coloured yet, particularly at poor-performings such as water-repellancy, anti-greasy dirt, chemical-resistant, Bearable dry and wet wipe and crash worthinesses.For example, UV-light photocuring gloss oil has become high-grade printed matter at present, and particularly in the first-selected kind of surface-treateds such as front cover such as paper article packaging box, book, magazine, yet UV-light photocuring gloss oil cost is high, and smell is relatively large.Can not be applicable to packing glazing operations such as cigarette, food, medicine, articles for children especially.UV curable aqueous resin composition is a kind of novel finishing agent that has ultraviolet light polymerization oiliness finishing agent and aqueous coating agent advantage concurrently, is a new research direction in current radiation curing field.Water-based UV finishing agent can address this problem well.Since use water as thinner, nontoxic, tasteless, no skin irritation, safer.Water-based UV finishing agent has fast, the rete luminance brightness height of dried coating film, and firm heat-resisting, the surface that can make printing of dry back face is light, level and smooth very, and the refractive power effect makes picture and text produce the sense of intensive main body, and color is more bright-coloured, and printing has high-grade sense.In addition, do not have solvent evaporates behind the UV ink printing, dry back ink film thickness is attenuate seldom, so under same printing condition, the ink film thickness of UV printing ink is thicker than solvent ink, when when printing tertiary color or the 4th look, printing for the site, because after the color stack, China ink layer obvious thickening, cause the stock air spots, under certain scraper pressure, printing ink is wandering to pocket, causes dot gain and the form and aspect distortion that causes.Water-based UV printing ink also can address this problem well.
The environment-friendly advantage of the existing water as solvent of UV curable aqueous resin composition has characteristics such as fast drying, the floor space of being satisfied with the suitability for industrialized production requirement are little, energy-conservation again concurrently, belongs to environmentally friendly machine.
Summary of the invention
The purpose of this invention is to provide a kind of UV curable aqueous resin composition, have good luster for the aqueous coating agent of industry uV curables such as papery product, leatheroid or natural leather, plastics, metal, timber and water-based UV printing ink provide a kind of quick photocuring polyfunctional group water-base resin of excellent property, gained to film with binder, characteristics such as smooth smooth, water-fast, excellent chemical resistance, good hand touch, snappiness are good.
The invention provides a kind of UV curable aqueous resin composition, it comprises:
(A) in the water soluble photo-curable modified epoxy acrylic ester resin of solid part weight 10～70%;
(B) 0%～10% water-and acrylate monomer or water-soluble acrylic ester prepolymer by weight;
(C) 1%～5% light trigger by weight;
(D) 0.1%～8% auxiliary agent by weight;
(E) by weight 20%～80% deionized water or water and alcohol mixed solvent.
Said components (A) adopts isocyanic ester, 2, and 2-dimethylol propionic acid (DMPA), hydroxyl acrylate monomer and polyvalent alcohol carry out graft modification to Epocryl, preferred amount of solid content 30～60%.
Above-mentioned isocyanic ester is hexa-methylene diisocyanate resin (HDl), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI); Preferred employing isocyanic ester is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI).
Above-mentioned hydroxyl acrylate monomer is Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA).
Above-mentioned Epocryl is bisphenol A epoxy acrylate, phenolic aldehyde epoxy acrylate, epoxidized oil acrylate.
Above-mentioned polyvalent alcohol is polyester polyol or polyether glycol, and its molecular weight can be selected 500～3000 scopes.
The described water-and acrylate monomer of said components (B) comprises the single functionality or the polyfunctional acrylic ester of alkoxide.
Said components (C) is water-soluble or water-insoluble light trigger, and described light trigger is 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, 1-hydroxyl-1-phenylcyclohexane ketone or any mixture between them, preferable amount 1～4%.
The auxiliary agent that said components (D) is selected for use has wetting agent, flow agent, defoamer, mould inhibitor, anti-pinhole agent, matting agent, and wherein wetting agent is selected polyxyethylated (benzene) phenolic ether class wetting agent for use; Anti-pinhole agent is selected silicone oil for use; Matting agent is selected aerosil for use; Defoamer is selected modified polyorganosiloxane for use; Mould inhibitor is selected benzoglyoxaline Urethylane (derosal) for use; Flow agent is selected water-soluble silicon oil for use.
The deionized water or the alcoholic solvent of said components (E), water be soft water mainly as solvent, alcoholic solvent is with ethanol or water and 1: 1 mixture of alcoholic acid.
Thing UV curable aqueous resin composition of the present invention, component A adopts isocyanic ester, 2, and 2-dimethylol propionic acid (DMPA), hydroxyl acrylate monomer and polyvalent alcohol carry out graft modification to Epocryl and prepare UV curable aqueous resin.An amount of water-and acrylate monomer or water-soluble acrylic ester prepolymer can be adjusted curing speed, and gloss, water tolerance and the hardness of water-base resin film forming matter of UV curable aqueous resin, but the salient features of film forming matter is determined by UV curable aqueous resin (A).Described UV curable aqueous resin can be with aliphatics or aromatic polyisocyanate, 2, and 2-dimethylol propionic acid, polyvalent alcohol, hydroxyl acrylate monomer, Epocryl and deionized water are that raw material is synthetic.The polyisocyanates that uses has hexa-methylene diisocyanate resin (HDl), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), wherein uses HDI, the UV curable aqueous resin of IPDI synthetic to have good weathering resistance and yellowing resistance.Can use the compound of introducing the band carboxyl is 2, the 2-dimethylol propionic acid; Can use the compound of hydroxyl acrylate monomer that Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA) are arranged; Spendable Epocryl has bisphenol A epoxy acrylate and epoxidized oil acrylate; Spendable polyvalent alcohol comprises polyester polyol or polyether glycol.UV curable aqueous resin can be prepared into the stable emulsion that the solids content scope is 10-80wt%.Under the room temperature lucifuge, the stability of this emulsion was greater than 10 months.
Thing UV curable aqueous resin composition B component of the present invention is water-and acrylate monomer or water-soluble acrylic ester prepolymer.Described water-and acrylate monomer comprises the single functionality or the polyfunctional acrylic ester of alkoxide, comprising: (methyl) acrylic acid hydroxy alkyl ester, for example (methyl) 2-hydroxyethyl acrylate and (methyl) vinylformic acid-2-hydroxypropyl ester; The list of glycol (methyl) acrylate, for example list (methyl) acrylate of list (methyl) acrylate of the list of ethylene glycol (methyl) acrylate, methoxyl group ethylene glycol, 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; Described water-soluble acrylic ester prepolymer comprises 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 or above-mentioned monomeric any mixture.
Thing UV curable aqueous resin composition component C of the present invention is a light trigger.Described light trigger comprises 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, 1-hydroxyl-1-phenylcyclohexane ketone or any mixture between them.
Thing UV curable aqueous resin composition component D of the present invention is an auxiliary agent.Auxiliary agent can improve the film forming quality of UV curable aqueous resin composition.Available auxiliary agent comprises: wetting agent, anti-pinhole agent, sanitas, matting agent, frostproofer etc.The adding of moistening flatting agent and defoamer can guarantee that film coated surface sprawls smooth smooth.Wetting agent can be selected polyxyethylated (benzene) phenolic ether class wetting agent, flow agent, the optional water-soluble silicon oil of using of anti-pinhole agent for use; Matting agent can be selected aerosil for use; Defoamer can be selected modified polyorganosiloxane for use.The zero pour of water needs to add frostproofer than common organic solvents height in transportation and storage.In addition, be easy to generate mould in the water-based system, need to add mould inhibitor, mould inhibitor can be selected benzoglyoxaline Urethylane (derosal) for use.
Thing UV curable aqueous resin composition component E of the present invention is the mixed solvent of deionized water or alcohol and water.Water is soft water, and alcoholic solvent can be with the mixture of ethanol or water and ethanol (1: 1), and they are mainly used in the viscosity of regulating UV curable aqueous resin composition as solvent.
That the application of the UV curable aqueous resin composition of proposition of the present invention not only has is energy-efficient, product is nontoxic, pollution-free, has the water easy cleaning, the coating scumbling, and the formed film glossiness of coating height, good hand touch, have very good water tolerance, anti-, can significantly improve the apparent mass of institute's coated object around bent fatigability.Reaching the effect that solvent borne is covered with paint, lacquer, colour wash, etc. aspect the decoration as the top layer brightening agent.
The preparation method of UV curable aqueous resin composition of the present invention is after above-mentioned each component is mixed in proportion, at 40 ℃ of-45 ℃ of following stir abouts about 1 hour, filter the back with 200 order filter clothes and pack, both obtained UV curable aqueous resin composition of the present invention.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described, but is not subject to these embodiment.
Synthetic example 1
Agitator is being housed, in the four-hole boiling flask of thermometer and prolong, drop into 2 of 34g respectively, the 2-dimethylol propionic acid, the 120g epoxy acrylic resin, after 500g gathers tetramethylene glycol (Mn=2000) dissolving, add appropriate amount of catalysts dibutyl tin laurate and stopper MEHQ, drip the 205g tolylene diisocyanate with 60 droplets/minute speed then, after waiting to dropwise temperature-stable, be warming up to 60 ℃-70 ℃ reactions 1.5 hours, add 60g Hydroxyethyl acrylate insulation 30min again, be warming up to 85 ℃ then and react 2h again, isocyano in reaction system disappears substantially, be cooled at last below 50 ℃, slowly add the 25g triethylamine, about 1 hour, slowly add a certain amount of deionized water at 40～50 ℃ of following stir abouts, stir fast, both can obtain water-based emulsion, and filter the back with 200 order filter clothes and pack, promptly get water-soluble uV curable modified epoxy acrylate resin A-1 of the present invention.
Synthetic example 2
Agitator is being housed, in the four-hole boiling flask of thermometer and prolong, drop into 2 of 34g respectively, the 2-dimethylol propionic acid, the 120g epoxy acrylic resin, after the 500g polyester polyol JW-2503 dissolving, add appropriate amount of catalysts dibutyl tin laurate and stopper MEHQ, drip the 225g isophorone diisocyanate with 60 droplets/minute speed then, after waiting to dropwise temperature-stable, be warming up to 60 ℃-70 ℃ reactions 1.5 hours, add 60g Hydroxyethyl acrylate insulation 30min again, be warming up to 85 ℃ then and react 2h again, isocyano in reaction system disappears substantially, be cooled at last below 50 ℃, slowly add the 25g triethylamine, about 1 hour, slowly add a certain amount of deionized water at 40～50 ℃ of following stir abouts, stir fast, both can obtain water-based emulsion, and filter the back with 200 order filter clothes and pack, promptly get water-soluble uV curable modified epoxy acrylate resin A-2 of the present invention.
Embodiment 1
Aqueous aromatic photocuring modified epoxy acrylate resin (A-1) 45%
4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone 4%
Water-based flow agent 1%
Deionized water 50%
If after above-mentioned each component is mixed in proportion, stir down about 1 hour at 40 ℃-45 ℃, after the filtration of 200 order filter clothes, promptly get uV curable papery product aqueous coating agent of the present invention, outward appearance is the liquid of milky white colour band blue light.This finishing agent is applied to art paper, artificial PU leather, aluminium sheet (material), and 50 ℃ of following levellings 5 minutes through 1000W high voltage mercury lamp (lamp is apart from 25cm) irradiation, solidify the back and survey its film forming matter performance, and gained the results are shown in Table 1.
Embodiment 2
Aqueous aromatic photocuring modified epoxy acrylate resin (A-1) 45%
4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone 4%
Polyethylene glycol acrylate 5%
Deionized water 46%
The sample making method is with embodiment 1, and the gained film performance the results are shown in Table 1.
Embodiment 3
Water-based aliphatics photocuring modified epoxy acrylate resin (A-2) 70%
4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone 4%
Deionized water 26%
The sample making method is with embodiment 1, and the gained film performance the results are shown in Table 1.
Embodiment 4
Water-based aliphatics photocuring modified epoxy acrylate resin (A-2) 60%
4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone 4%
Water-based flow agent 1%
Deionized water 35%
The sample making method is with embodiment 1, and the gained film performance the results are shown in Table 1.
2. anti-ethanol dips in ethanol with certain load Wiping film surface with cotton, observes the wiping number of times of film rupture; 3. anti-xanthochromia, paint film shone (1000W high voltage mercury lamp, lamp is apart from 25cm) 10min under ultraviolet lamp after, with the more xanthochromic degree of former film.</entry></row></tbody></tgroup></table></tables>
Claims (10)
1. UV curable aqueous resin composition is characterized in that it comprises:
(A) in the water soluble photo-curable modified epoxy acrylic ester resin of solid part weight 10～70%;
(B) 0%～10% water-and acrylate monomer or water-soluble acrylic ester prepolymer by weight;
(C) 1%～5% light trigger by weight;
(D) 0.1%～8% auxiliary agent by weight;
(E) by weight 20%～80% deionized water or water and alcohol mixed solvent.
2. according to the UV curable aqueous resin composition of claim 1, it is characterized in that: said components (A) adopts isocyanic ester, 2,2-dimethylol propionic acid (DMPA), hydroxyl acrylate monomer and polyvalent alcohol carry out graft modification to Epocryl, preferred amount of solid content 30～60%.
3. according to the UV curable aqueous resin composition of claim 2, it is characterized in that: above-mentioned isocyanic ester is hexa-methylene diisocyanate resin (HD1), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI); Preferred employing isocyanic ester is toluene diisocyanate (TDI), isophorone diisocyanate (IPDI).
4. according to the UV curable aqueous resin composition of claim 2, it is characterized in that: above-mentioned hydroxyl acrylate monomer is Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA).
5. according to the UV curable aqueous resin composition of claim 2, it is characterized in that: above-mentioned Epocryl is bisphenol A epoxy acrylate, phenolic aldehyde epoxy acrylate, epoxidized oil acrylate.
6. according to the UV curable aqueous resin composition of claim 2, it is characterized in that: above-mentioned polyvalent alcohol is polyester polyol or polyether glycol, and its molecular weight can be selected 500～3000 scopes.
7. according to the UV curable aqueous resin composition of claim 1, it is characterized in that: the described water-and acrylate monomer of said components (B) comprises the single functionality or the polyfunctional acrylic ester of alkoxide.
8. according to the UV curable aqueous resin composition of claim 1, it is characterized in that: said components (C) is water-soluble or water-insoluble light trigger, described light trigger is 4 '-(2-hydroxy ethoxy)-2-hydroxyl-2 methyl phenyl ketone, 1-hydroxyl-1-phenylcyclohexane ketone or any mixture between them, preferable amount 1～4%.
9. according to the UV curable aqueous resin composition of claim 1, it is characterized in that: the auxiliary agent that said components (D) is selected for use has wetting agent, flow agent, defoamer, mould inhibitor, anti-pinhole agent, matting agent, and wherein wetting agent is selected polyxyethylated (benzene) phenolic ether class wetting agent for use; Anti-pinhole agent is selected silicone oil for use; Matting agent is selected aerosil for use; Defoamer is selected modified polyorganosiloxane for use; Mould inhibitor is selected the benzoglyoxaline Urethylane for use; Flow agent is selected water-soluble silicon oil for use.
10. according to the UV curable aqueous resin composition of claim 1, it is characterized in that: the deionized water or the alcoholic solvent of said components (E), water be soft water mainly as solvent, alcoholic solvent is with ethanol or water and 1: 1 mixture of alcoholic acid.
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