CN104789039A - Endogenous frosting-effect glass ink and method for producing frosting-effect product by utilizing same - Google Patents
Endogenous frosting-effect glass ink and method for producing frosting-effect product by utilizing same Download PDFInfo
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- CN104789039A CN104789039A CN201510206404.0A CN201510206404A CN104789039A CN 104789039 A CN104789039 A CN 104789039A CN 201510206404 A CN201510206404 A CN 201510206404A CN 104789039 A CN104789039 A CN 104789039A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/104—Polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
The invention discloses endogenous frosting-effect ink and a method for producing a frosting-effect product in a two-stage UV curing method. The ink consists of the following components in parts by weight: 40 to 85 parts of photosensitive oligomer, 3 to 30 parts of active monomer, 0 to 10 parts of photosensitive agent, 1 to 20 parts of stuffing, 0 to 3 parts of flatting agent, 0 to 3 parts of defoaming agent, 0 to 3 parts of polymerization inhibitor and 0 to 5 parts of adhesion promoter. The two-stage UV curing process comprises a low-energy UV light curing step and a high-energy UV light curing step. The ink is good in mobility, excellent in printing property, high in production efficiency and true in UV curing layer frosting effect, and no waste water and no waste gas are produced; and the endogenous frosting-effect glass ink has the characteristics of high hardness, scratch resistance, excellent adhesion force, excellent water resistance, excellent acid-alkali resistance and the like.
Description
Technical field
The present invention relates to ink manufacturing technology field, be specifically related to a kind of interior raw type frosting effect glass ink and utilize interior raw type frosting effect glass to be produced the method for frosting effect product by the mode of two sections of ultra-violet curings.
Background technology
Mat glass is conventional ambetti kind, and traditional technology adopts fluoric-containing acid liquid corrosion carved glass, and form frosting effect pattern, this method can produce waste water containing fluorine, not only endangers the healthy of operator, and can polluted underground water source.
Also mat glass can be produced at the ink of glass surface printing or coating frosting effect.At present, market is produced the ink of mat glass by direct print process, divide have two types according to drying mode, one is from dry/heat curing-type, and another kind is that UV solidifies (ultra-violet curing) type.The ink of this two type all belongs to outer addition type, namely relies on the filler adding special shape in ink, as solid particulates such as PP (polypropylene) sand streak wax powder, makes cured layer surface produce rough frosting effect.The frosting effect of coating depends on shape, consumption, the Particle size and distribution of added filler, and the hardness of filler itself, the transparency and physical and chemical index affect wear resistance and other physicochemical property of coating to a great extent.Conventional frosting effects fillers comprises polypropylene or polyethylene sand streak wax, tetrafluoroethylene wax powder, nylon powder, PMMA (polymethylmethacrylate) fine particle etc., the hardness of these polymer packings is not high, when addition is larger, not only can affect printing performance, also can reduce the attachment fastness of coating to ground.
Though have the low feature of cost from dry/thermoset frosting effect ink, a large amount of organic solvents that ink includes in printing and bake process can evaporate in air, contaminate environment, and baking time is longer, and efficiency is low, and energy consumption is high.In addition, the filler particles with frosting effect floats over cured film surface, causes that coatingsurface hardness is low, scratch resistance is poor, and frosting effect is true to nature not.
UV solidification frosting effect glass ink in the market also relies in ink and adds a large amount of solid particulate, to produce frosting effect, as UV-GM-52N curing glass/metal frosting ink that Hangzhou Ke Wang special ink company produces, the UV glass frosting ink for screen printing etc. that Hangzhou permanent base oil ink paint company is produced.After silk screen printing, the solid particulate in ink layer is exposed more or less forms rough frosting effect surface on cured film surface, produces frosting effect glassy product by UV illumination.Though this technique has the advantage such as fast setting, energy-conserving and environment-protective, but surface hardness is not high, water tolerance and wearing no resistance, solvent resistance, acid-and base-resisting are not good yet, in addition, owing to the addition of a large amount of solid packing, the poor fluidity of UV frosting effect ink, thixotropy is strong, printing adaptability is poor, usually because of printing defects, produce substandard products, therefore common UV solidifies frosting ink and never obtains large batch of applying.
Application publication number is that the Chinese invention patent application of CN 104387838A (application number is 201410739835.9) discloses a kind of silk-screen protection ink composite and screen printing method; acid-proof ink and ultra-fine rubber powder is comprised in described ink composite; median size≤the 0.04mm of described ultra-fine rubber powder, and the quality of described rubber powder accounts for 5 ~ 20% of described acid-proof ink quality.This screen printing method comprises: steps A, mixed with solidifying agent by acid-proof ink, toward wherein adding thinner and ultra-fine rubber powder obtains a kind of silk-screen protection ink composite; Step B, use silk-screen protection ink composite and silk-screen half tone carry out silk screen printing to glass.Although this technical side can produce the product of glass surface privileged site containing frosting effect, acid-proof ink is improving, and there is certain deficiency.
Summary of the invention
For the technological deficiency that outer addition type frosting effect ink exists, the invention provides a kind of interior raw type frosting effect glass ink, good fluidity, printing is good, do not produce waste water, waste gas, obtain frosting effect by UV solidification, frosting effect is true to nature, and it is high to have hardness, the excellent feature of damage resistant, sticking power, water tolerance, resistance to acids and bases.
An ink for interior raw type frosting effect, total mass part, by 100 parts, is made up of the component of following mass parts:
As preferably, the ink of described interior raw type frosting effect, total mass part, by 100 parts, is made up of the component of following mass parts:
Further preferably, the ink of described interior raw type frosting effect, total mass part, by 100 parts, is made up of the component of following mass parts:
In the present invention, ink belongs to the ink that interior raw type UV solidifies frosting effect.The ink printing rear surface of interior raw type frosting effect does not directly form frosting effect, because there is chemical reaction in UV-irradiation process, generates microgel, thus forms frosting effect surface.
Described photosensitive oligomer is one in urethane acrylate, polyester acrylate, epoxy acrylate, amino acrylates, aromatic acid acrylate half ester, organosilicon (phosphorus) modification acrylate or its mixture.Photosensitive oligomer should control within the scope of 30-85 part, preferred 40-80 part.The functionality of photosensitive oligomer is higher, and coating curing film hardness is higher, and in formula, the content of high functionality oligopolymer increases, and cured film hardness increases, but shrinking percentage also can increase, and sticking power reduces.The number-average molecular weight of described photosensitive oligomer is 500 ~ 15000.
When adopting aromatic acid acrylate half ester, performance is relatively undesirable, as further preferably, described photosensitive oligomer is one in urethane acrylate, polyester acrylate, epoxy acrylate, amino acrylates, organosilicon (phosphorus) modification acrylate or its mixture.
Described urethane acrylate, as Changxing, Taiwan chemistry 6148J-75,6170,6196,6195-100, Sartomer of the U.S. CN984, CN968, CN977, CN968, CN9006, Bayer Bitterfeld GmbH chemistry U400, U200, U100,5290 of Taiwan double bond chemistry, 5812, Qing Te company of the U.S. EB270, EB8254, EB1290, two to ten functional group's aliphatics or the aromatic urethane acrylate such as Zhong Shan section field 3620,3910.
Described polyester acrylate, as Qing Te company of the U.S. EB741, EB450, EB811, EB870, Changxing, Taiwan chemistry 6312-100,6311-100,6336-100, DR-E509, two to ten eight functional group's polyester acrylates such as Taiwan double bond chemical industry 220,2288,245,2015.
Described epoxy acrylate, as Changxing, Taiwan chemistry DR-G908,625C-45, the CN2202 of Sartomer of the U.S., Jiangsu three wooden company 6104-80,6105-80 etc.
Described amino acrylates, as Jiangsu three wood public 6117,6115,6113, etc.
Described aromatic acid acrylate half ester, as Sartomer of the U.S. SB400, SB401, SB500E50 etc.
Described organosilicon (phosphorus) modification acrylate, as double bond chemical industry 347-1, upper Hypon profit chemical industry PAC7210, PAC7389 etc.
Described reactive monomer is one in many (more than three) functional monomer, difunctional monomer, monofunctional monomer or its mixture.Reactive monomer is mainly used in regulating ink viscosity and cross-linking density, and its consumption should control within the scope of 3-30 part, preferred 5-18 part.
Described polyfunctional monomer is dipentaerythritol acrylate (DPHA), tetramethylol methane tetraacrylate (PETA), two-trimethylolpropane tetra-acrylate (DiTMP4A), pentaerythritol triacrylate (PET3A), Viscoat 295 (TMPTA), three (2-hydroxyethyl) isocyanurate triacrylate (THEICTA), one or more in tripropoxy Viscoat 295 (TMP3POTA).
Described difunctional monomer is tripropylene glycol diacrylate (TPGDA), 1,6 hexanediyl esters (HDDA), neopentylglycol diacrylate (NPGDA), Ethoxylated bisphenol A acrylate (BPA4EODA), ethoxylated neopentylglycol diacrylate (NPG2PODA), one or more in methacrylate hydroxyl acetophos acid esters (PM-2).
Described monofunctional monomer is as hydroxyethyl methylacrylate (HEMA), Rocryl 410 (HPMA), isobornyl acrylate (IBOA), iso-borneol methacrylic ester (IBOMA), HEMA phosphoric acid ester (HEMAP), one or more in ethoxylation phenoxy group acrylate (PH3EOA).
Described photosensitizers is 1-hydroxy cyclohexyl phenylketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), benzoin dimethylether (651), 2.4.6-trimethyl benzoyl diphenyl base phosphine oxide (TPO), isopropyl thioxanthone (ITX), 2; one in 4-diethyl thioxanthone (DETX), benzophenone (BP), 4-phenyl benzophenone (PBZ), 4-(N, N-dimethylamino) ethyl benzoate (EDAB), 4-benzoyl-4 '-methyl-diphenyl sulfide (BMS) or its mixture.In ink during photosensitizers large usage quantity, curing speed is fast, but the shelf lives shortens, and when photosensitizers consumption is less, curing speed is slow.UV glass frosting total ink is in 100 parts, and photosensitizers content should control within the scope of 0-10 part, preferred 0-5 part, more preferably 0-3 part.
Described filler is one in talcum powder, calcium carbonate, silicon-dioxide, silicon powder, white carbon black, organobentonite, aluminium sesquioxide or its mixture.Change the filler content in ink, adjustable ink viscosity, rheological and the cured film transparency, UV glass frosting total ink is in 100 parts, and filler content should control within the scope of 1-20 part, preferred 1-10 part.
In the present invention, flow agent and defoamer can adopt prior art, can adopt commercially available prod.
Described stopper is one or more (comprising two kinds) in Resorcinol, MEHQ, three (N-nitroso-N-phenylhydroxylamine azanol) aluminium salt etc.
Described adhesion promoter is sour modification acrylate or coupling agent, and it can improve UV coating to the attachment fastness of glass substrate and water tolerance.Acid modification acrylate as Zhan Xin chemical company of U.S. EB168, Guangzhou Boxing science and technology B-55, Changxing, Taiwan chemistry 3500A, 648-1, the special chemical industry SC1400 in U.S. of Korea S source, Japanese chemical drug chemical industry PM-2, Hangzhou Jesse's card chemical industry JSC-7300 modified phosphate etc.Coupling agent is as aluminate coupling agent, titanium aluminate coupling agent, silane coupling agent etc.In above-mentioned coupling agent, two (methyl aceto acetate) aluminic acid diisopropyl ester (HY-1804), sec.-propyl three oleic acid acyl-oxygen titanic acid ester (HY-105), sec.-propyl three (Witco 1298 Soft Acid) titanic acid ester (HY-109), gamma-amino triethyl TMOS (KH-550), Ν-β (aminoethyl)-γ-aminopropyl dimethoxy silane (KH-602), γ-methacryloxypropyl trimethoxy silane (KH-570) etc. are ideal, only need add a small amount of coupling agent, better effect can be obtained.
In in the present invention, the preparation of the ink of raw type frosting effect, can be obtained by the mixing of each component.
Present invention also offers a kind of method utilizing the Printing ink producing frosting effect product of interior raw type frosting effect, adopt two sections of UV curings, namely the certain thickness ink coating of silk screen printing is used, first issue biochemical reaction in low strength UV rayed, generate microgel, thus form rough frosting effect surface.Now the surface of ink is not solidified completely, and Procuring coating is solidified completely under higher-strength UV rayed again, the final high rigidity UV cured film forming glass frosting effect.
Interior raw type frosting effect ink of the present invention generates microgel because there is chemical reaction in UV-irradiation process, thus forms frosting effect.The present invention disobeys outer interpolation solid packing and forms frosting surface.
Coatingsurface smooth after interior raw type frosting effect ink of the present invention printing, directly do not form frosting effect, only have after the UV-irradiation of some strength, coating could form rough frosting effect glass surface.
Utilize a method for the Printing ink producing frosting effect product of interior raw type frosting effect, comprise the following steps:
The ink of raw type frosting effect in base material is coated with, adopt two sections of ultraviolet (UV) curing process, comprise low-yield ultraviolet (UV) rayed and high energy UV (UV) rayed two procedures, obtain frosting effect product.
The intensity of described low-yield ultraviolet light irradiation is 3-200mw/cm
2;
The light-struck intensity of described high energy UV is 201-350mw/cm
2.
Described base material is one or more (comprising two kinds) in glass, metal base, plastic basis material etc., and in the present invention, the ink of raw type frosting effect had both been applicable to printed glass, also can print various metal and plastic basis material.
UV frosting effect glass of the present invention adopts two sections of UV curing process, comprise low-yield UV rayed and high-energy UV rayed two procedures, the i.e. ink (UV ink) of the certain thickness interior raw type frosting effect of silk screen printing on the base materials such as glass, first with low-yield UV-irradiation coatingsurface, form frosting effect, after coating is solidified completely by stronger UV-irradiation again, so both taken into account surperficial frosting effect, can enhance productivity again.On base material, in coating, the thickness of the ink of raw type frosting effect is 10 ~ 50 microns, and thickness general control is more suitable at 10-50 micron, and be greater than 50 microns of solidifications comparatively slow, waste ink, too thin lower than 10 microns of layer of ink, frosting effect is poor simultaneously.
Regulate lamp distance, UV light intensity can be changed; Before and after changing, UV lamp spacing, can regulate the distribution of UV light intensity.
The UV-lamp that generation ultraviolet uses is high voltage mercury lamp, medium pressure mercury lamp, metal halid lamp, Non-polarized lamp etc., and high voltage mercury lamp is because of cheap, and UV energy is even, uses ideal.
When ultraviolet ray intensity is less than 3mw/cm
2time, even if illumination is for a long time, ink coating is also difficult to form frosting effect.When light intensity is greater than 230mw/cm
2time, coating fast setting, surface is solidification thoroughly, frosting effect cannot be formed, and produce local dead skin (local frosting, local are commonly called as without the one of frosting phenomenon), cause the frosting surface of formation uneven, cured film compared with crisp, shrinking percentage is large, poor to substrate adhesion, even there is no sticking power.
Low-yield UV-irradiation intensity control is at 3-200mw/cm
2suitable in scope, preferred 30-200mw/cm
2.
UV-irradiation intensity can be regulated by the spacing (lamp distance) changing ultraviolet lamp and ground.Lamp is apart from larger, and light intensity is more weak, and lamp is apart from less, and light is stronger.
The quality of frosting effect, both relevant with ultraviolet lighting intensity, relevant with the rayed time again.
High-energy UV rayed refers to that employing is not less than 200mw/cm
2the UV rayed ink coating of intensity, makes coating solidify completely as early as possible, enhances productivity.When ultraviolet ray intensity is less than 200mw/cm
2time, the coating curing time is longer, and even cannot solidify, production efficiency is low; When ultraviolet ray intensity is greater than 350mw/cm
2time, coating curing is very fast, but shrinking percentage is comparatively large, poor adhesive force.
The light intensity of high-energy UV-light controls at 201-350mw/cm
2suitable in scope, preferred 210-300mw/cm
2.
Only use described low-yield UV rayed frosting ink coating, can make ink solidification equally, just set time is very long, and efficiency is lower.
Compared with prior art, tool of the present invention has the following advantages:
Interior raw type frosting effect ink of the present invention has good mobility and printing, has environmental protection, the advantage such as energy-conservation and efficient.Through the coating that two sections of UV curing process are produced, frosting uniform in effect, fine and closely woven, hardness is high, and sticking power, water tolerance, resistance to acids and bases, solvent resistance are all better than addition type frosting ink, cut at glass, there will not be in edging procedure come off, the bad phenomenon such as embrittlement.Obtain frosting effect product by UV solidification, as mat glass, the advantages such as frosting effect is true to nature, and it is high to have hardness, and damage resistant, sticking power, water tolerance, resistance to acids and bases are excellent, are conducive to market-oriented utilization and extention, have broad application prospects.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that existing outer addition type UV solidifies mat glass, and wherein a is before UV solidification, and b is after UV solidification;
Fig. 2 is the schematic diagram that UV solidifies raw type frosting effect ink generation frosting effect in the present invention on glass, and wherein c is before UV solidification, and d is after UV solidification.
Embodiment
Embodiment 1
Urethane acrylate (Sartomer of U.S. CN9006) 57 parts, epoxy acrylate (Changxing, Taiwan chemistry DR-G908) 17 parts, Viscoat 295 (TMPTA) 8 parts, tripropylene glycol diacrylate (TPGDA) 5 parts, Rocryl 410 (HPMA) 3 parts, 1-hydroxycyclohexyl phenyl ketone (UV-184) 1 part, 4-phenyl benzophenone (PBZ) 1 part, talcum powder 5 parts, defoamer (German Bi Ke chemistry BYK-1790) 0.5 part, stopper (MEHQ) 0.5 part, adhesion promoter (sour modification acrylate, Zhan Xin chemical company of U.S. EB168) 2 parts, flow agent (German Bi Ke chemistry BYK-354) 1 part, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 50mw/cm by intensity
2uV rayed coating 50 seconds, then use 280mw/cm
2high-energy UV rayed 3 seconds.
Embodiment 2
Aromatic acid acrylate half ester SB40015 part, polyester acrylate 6336-10035 part, amino acrylates 611715 parts, dipentaerythritol acrylate (DPHA) 8 parts, neopentylglycol diacrylate (NPGDA) 7 parts, Rocryl 410 (HPMA) 6 parts, 1-hydroxy cyclohexyl phenylketone (184) 0.5 parts, isopropyl thioxanthone (ITX) 0.5 part, white carbon black 9 parts, defoamer (German Bi Ke chemistry BYK-1790) 0.5 part, stopper (MEHQ) 0.5 part, adhesion promoter (gamma-amino triethyl TMOS KH-550) 2 parts, flow agent (German Bi Ke chemistry BYK-354) 1 part, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 70mw/cm by intensity
2uV rayed coating 45 seconds, then use 250mw/cm
2high-energy UV rayed 5 seconds.
Embodiment 3
Urethane acrylate (Sartomer of U.S. CN968) 59 parts, polyester acrylate (Changxing, Taiwan chemistry 6196) 9 parts, epoxy acrylate DR-G9085 part, dipentaerythritol acrylate (DPHA) 7 parts, tripropylene glycol diacrylate (TPGDA) 5 parts, Rocryl 410 (HPMA) 2 parts, benzophenone (BP) 2 parts, benzoin dimethylether (651) 1 parts, organobentonite 6 parts, defoamer (German Bi Ke chemistry BYK-1790) 0.5 part, stopper (MEHQ) 0.5 part, adhesion promoter (sour modification acrylate, Zhan Xin chemical company of U.S. EB168) 2 parts, flow agent (German Bi Ke chemistry BYK-354) 1 part, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 80mw/cm by intensity
2uV rayed coating 40 seconds, then use 250mw/cm
2high-energy UV rayed 4 seconds.
Embodiment 4
Urethane acrylate 362045 parts, urethane acrylate CN900621 part, organosilicon-modified acrylate 347-15 part, three (2-hydroxyethyl) isocyanurate triacrylate (THEICTA) 5 parts, neopentylglycol diacrylate NPGDA 5 parts, hydroxyethyl methylacrylate (HEMA) 6 parts, 1-hydroxy cyclohexyl phenylketone (184) 1 parts, 4-phenyl benzophenone (PBZ) 2 parts, silicon-dioxide 5.5 parts, defoamer (German Bi Ke chemistry BYK-1790) 0.2 part, stopper (MEHQ) 0.5 part, adhesion promoter (sour modification acrylate, Zhan Xin chemical company of U.S. EB168) 2 parts, flow agent (German Bi Ke chemistry BYK-354) 1.8 parts, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 100mw/cm by intensity
2uV rayed coating 25 seconds, then use 230mw/cm
2high-energy UV rayed 5 seconds.
Embodiment 5
Amino acrylates 611727 parts, urethane acrylate 529035 parts, two-trimethylolpropane tetra-acrylate (DiTMP4A) 13 parts, three (2-hydroxyethyl) isocyanurate triacrylate 7 parts, tripropylene glycol diacrylate (TPGDA) 5 parts, Rocryl 410 (HPMA) 5 parts, 0.5 part, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzophenone 0.5 part, talcum powder 4 parts, defoamer (German Bi Ke chemistry BYK-1790) 0.5 part, stopper 0.5 part, adhesion promoter (sour modification acrylate, Zhan Xin chemical company of U.S. EB168) 1 part, flow agent (German Bi Ke chemistry BYK-354) 1 part, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 140mw/cm by intensity
2uV rayed coating 20 seconds, then use 230mw/cm high-energy UV rayed 5 seconds.
Embodiment 6
Urethane acrylate 529045 parts, urethane acrylate 6115J-8010 part, aromatic acid acrylate half ester SB40122 part, tripropoxy Viscoat 295 (TMP3POTA) 7 parts, Rocryl 410 (HPMA) 5 parts, 1-hydroxy cyclohexyl phenylketone (184) 1 parts, 4-phenyl benzophenone (PBZ) 1 part, 6 parts, calcium carbonate, defoamer (German Bi Ke chemistry BYK-1790) 0.5 part, stopper (Resorcinol) 0.5 part, adhesion promoter (sour modification acrylate, Zhan Xin chemical company of U.S. EB168) 1 part, flow agent (German Bi Ke chemistry BYK-354) 1 part, the mixing of above-mentioned each component can be obtained interior raw type frosting effect ink.
Condition of cure: be first 150mw/cm by intensity
2time UV rayed coating 18 seconds, then use 210mw/cm
2high-energy UV rayed 10 seconds.
Comparative example 1
Fill a prescription identical with example 4, condition of cure: be first 10mw/cm by intensity
2uV rayed coating 20 minutes, then use 270mw/cm
2high-energy UV rayed 10 seconds.
Comparative example 2
Fill a prescription identical with example 5, condition of cure: be first 250mw/cm by intensity
2time UV rayed coating 16 seconds, then use 270mw/cm
2high-energy UV rayed 4 seconds.
Comparative example 3
Outer addition type UV glass frosting ink formulations: epoxy acrylate 20 parts, urethane acrylate 14 parts, tripropylene glycol diacrylate (TPGDA) 15 parts, Rocryl 410 (HPMA) 15 parts, 1-hydroxy cyclohexyl phenylketone (184) 4 parts, (1173) 5 parts, 2-hydroxy-2-methyl-1-phenyl-1-acetone, organobentonite 2 parts, 13 parts, wax powder, 10 parts, sub-light powder, phosphoric acid ester (PM-2) 1.5 parts, 201 methyl-silicone oil 0.5 part.
Condition of cure: be 250mw/cm by light intensity
2uV rayed coating one time 15 seconds, make it to solidify completely.
Glass frosting curing membrane performance is evaluated
One, ocular estimate
With visual method, cured film frosting outward appearance is evaluated.
Excellent: translucent, frosting uniform particles, fine and closely woven, surface slip, bubble-free, shrinkage cavity, dead skin and printing reticulate pattern.
Good: translucent, frosting particle is uneven, not fine and closely woven, surface irregularity, has a small amount of shrinkage cavity, dead skin, booty or reticulate pattern.
Difference: opaque, frosting particle is uneven, it is uneven to solidify, and has dead skin, has a large amount of shrinkage cavity, booty or reticulate pattern.
Two, evaluate set time
Can reflect the height of production efficiency the set time required for cured film, set time is shorter, and production efficiency is higher, otherwise production efficiency is lower.
Three, sticking power evaluation
Measure by GB4677.7-84 adhesion test method, tape stripping method.100% is best, and 0% is the poorest.
Four, surface hardness evaluation
Measure by GB6739-1996 hardness of film pencil assay method, numerical value is larger, and hardness is higher.
Five, water tolerance evaluation
Tested glass sample to be immersed in the tap water of 25-30 DEG C 24 hours, to take out and dry up rear test.
Excellent: sticking power 100%, surface hardness and surface luster are all unchanged.
Good: sticking power reduces within 5%, and surface hardness reduces 1H.
Difference: sticking power reduces by more than 5%, matt, surface hardness reduces more than 1H.
Acid resistance is evaluated
By tested glass sample 25-30 DEG C, soak 2 hours in 10% aqueous sulfuric acid, take out and dry up rear test.
Six, alkali resistance evaluation
By tested glass sample 25-30 DEG C, soak 2 hours in 5% (wt) aqueous sodium hydroxide solution, take out and dry up rear test.
Excellent: sticking power 100%, surface hardness and surface luster are all unchanged.
Good: sticking power reduces within 10%, and surface hardness reduces 1H.
Difference: sticking power reduces by more than 10%, matt, surface hardness reduces more than 1H.
Seven, solvent resistance evaluation
Tested glass sample to be immersed in corresponding organic solvent (dehydrated alcohol, dimethylbenzene, pimelinketone) 2 hours, to take out and dry up rear test.
Excellent: sticking power 100%, surface hardness and surface luster are all unchanged.
Good: sticking power reduces within 10%, and surface hardness reduces 1H.
Difference: sticking power reduces by more than 10%, matt, surface hardness reduces more than 1H.
As shown in table 1, embodiment 1-6 is the formula of dissimilar UV resin composition, and the performance of gained frosting cured film is different; Fill a prescription identical, illumination program is different, and the performance difference of cured film is also very large, and comparative example 1 is filled a prescription identical with embodiment 4, and comparative example 2 is filled a prescription identical with embodiment 5, but intensity of illumination difference during its solidification.Comparative example 3 is addition type UV glass frosting ink formulations.
Table 1
Fill a prescription identical, UV rayed program is different, and gained frosting coating performance difference is very large, and UV frosting coating performance test result is in table 2.
Table 2
Fig. 1 is the schematic diagram that existing outer addition type UV solidifies mat glass, Fig. 2 is the schematic diagram that UV solidifies raw type frosting effect ink generation frosting effect in the present invention on glass, visible, coatingsurface smooth after interior raw type frosting effect ink of the present invention printing, directly do not form frosting effect, only have after the UV-irradiation of some strength, coating could form rough frosting effect glass surface.
Claims (10)
1. an ink for raw type frosting effect in, it is characterized in that, total mass part, by 100 parts, is made up of the component of following mass parts:
2. require the ink of raw type frosting effect in described in 1 according to claim, it is characterized in that, described photosensitive oligomer is one in polyester acrylate, epoxy acrylate, amino acrylates, organosilicon-modified acrylate or its mixture.
3. require the ink of raw type frosting effect in described in 1 according to claim, it is characterized in that, described reactive monomer is one in polyfunctional monomer, difunctional monomer, monofunctional monomer or its mixture.
4. the ink of raw type frosting effect in described in 3 is required according to claim, it is characterized in that, described polyfunctional monomer is dipentaerythritol acrylate, tetramethylol methane tetraacrylate, two-trimethylolpropane tetra-acrylate, pentaerythritol triacrylate, Viscoat 295, three (2-hydroxyethyl) isocyanurate triacrylate, one or more in tripropoxy Viscoat 295;
Described difunctional monomer is tripropylene glycol diacrylate, 1,6 hexanediyl esters, neopentylglycol diacrylate, Ethoxylated bisphenol A acrylate, ethoxylated neopentylglycol diacrylate, one or more in methacrylate hydroxyl acetophos acid esters;
Described monofunctional monomer is hydroxyethyl methylacrylate, Rocryl 410, isobornyl acrylate, iso-borneol methacrylic ester, HEMA phosphoric acid ester, one or more in ethoxylation phenoxy group acrylate.
5. the ink of raw type frosting effect in described in 1 is required according to claim; it is characterized in that; described photosensitizers is 1-hydroxy cyclohexyl phenylketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethylether, 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, isopropyl thioxanthone, 2; one in 4-diethyl thioxanthone, benzophenone, 4-phenyl benzophenone, 4-(N, N-dimethylamino) ethyl benzoate, 4-benzoyl-4 '-methyl-diphenyl sulfide or its mixture.
6. require the ink of raw type frosting effect in described in 1 according to claim, it is characterized in that, described filler is one in talcum powder, calcium carbonate, silicon-dioxide, silicon powder, white carbon black, organobentonite, aluminium sesquioxide or its mixture.
7. require the ink of raw type frosting effect in described in 1 according to claim, it is characterized in that, described stopper is one or more in Resorcinol, MEHQ, three (N-nitroso-N-phenylhydroxylamine azanol) aluminium salt.
8. require the ink of raw type frosting effect in described in 1 according to claim, it is characterized in that, described adhesion promoter is sour modification acrylate or coupling agent.
9. utilize a method for the Printing ink producing frosting effect product of the interior raw type frosting effect described in any one of claim 1 ~ 8, it is characterized in that, comprise the following steps:
In base material is coated with, the ink of raw type frosting effect, adopts two sections of ultraviolet curing process, comprises low-yield ultraviolet light irradiation and high energy UV rayed two procedures, obtain frosting effect product;
The intensity of described low-yield ultraviolet light irradiation is 3-200mw/cm
2;
The light-struck intensity of described high energy UV is 201-350mw/cm
2.
10. the method for the Printing ink producing frosting effect product of interior raw type frosting effect according to claim 9, is characterized in that, on base material, in coating, the thickness of the ink of raw type frosting effect is 10 ~ 50 microns.
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