CN104789039B - A kind of interior raw type frosting effect glass ink and the method that frosting effect product is produced using it - Google Patents
A kind of interior raw type frosting effect glass ink and the method that frosting effect product is produced using it Download PDFInfo
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- CN104789039B CN104789039B CN201510206404.0A CN201510206404A CN104789039B CN 104789039 B CN104789039 B CN 104789039B CN 201510206404 A CN201510206404 A CN 201510206404A CN 104789039 B CN104789039 B CN 104789039B
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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
Abstract
The invention discloses the method for a kind of ink of interior raw type frosting effect and two sections of UV solidification production frosting effect products.The ink, gross mass part is made up of based on 100 parts the component of following mass parts：40~85 parts of photosensitive oligomer；3~30 parts of activated monomer；0~10 part of sensitising agent；1~20 part of filler；0~3 part of levelling agent；0~3 part of defoamer；0~3 part of polymerization inhibitor；0~5 part of adhesion promoter.Two sections of UV curing process include low energy UV photocurings and high-energy UV photocuring two procedures.The ink mobility of the interior raw type ultraviolet curing frosting effect of the present invention is good, and printing performance is good, and no waste water, waste gas are produced, and production efficiency is high, and UV cured layer frosting effects are true to nature, with hardness height and the excellent feature of damage resistant, adhesive force, water resistance, resistance to acids and bases.
Description
Technical field
The present invention relates to ink manufacturing technology field, and in particular to raw type frosting effect glass ink and using interior in a kind of
The method that raw type frosting effect glass produces frosting effect product by way of two sections of ultra-violet curings.
Background technology
Mat glass is conventional ambetti kind, and traditional handicraft uses fluoric-containing acid liquid corrosion carved glass, forms frosting effect
Fruit pattern, this method can produce waste water containing fluorine, not only endanger the healthy of operating personnel, and can polluted underground water
Source.
The ink for printing or being coated with frosting effect in glass surface can also produce mat glass.At present, in the market passes through straight
The ink that print process produces mat glass is connect, there are two types according to drying mode point, one kind is to do/heat curing-type certainly, another
It is UV solidification (ultra-violet curing) types.The ink of both types belongs to outer addition type, that is, relies on addition special form in ink
The filler of shape, such as PP (polypropylene) sand streak wax powder solid particle, makes solidification layer surface produce rough frosting effect.Apply
The frosting effect of layer depends on adding shape, consumption, granularity and the distribution of filler, and hardness, the transparency of filler in itself
And physical and chemical index largely affects the wearability and other physicochemical properties of coating.Conventional frosting effects fillers include poly-
Propylene or polyethylene sand streak wax, polytetrafluoroethylene (PTFE) wax powder, nylon powder, PMMA (polymethyl methacrylate) fine grained etc., these
The hardness of polymer filler is not high, when addition is larger, can not only influence printing performance, can also reduce coating to the attached of ground
Fastness.
Though there is the characteristics of cost is low from dry/thermosetting frosting effect ink, in printing and baking process in ink
The a large amount of organic solvents contained can be evaporate into air, pollute environment, and baking time is longer, and efficiency is low, high energy consumption.In addition, tool
The filler particles for having frosting effect float over cured film surface, cause that coating surface hardness is low, scratch resistance is poor, and frosting effect is inadequate
It is true to nature.
UV solidification frosting effect glass inks in the market, which are also rested upon, adds a large amount of solid particles in ink, to produce
Raw frosting effect, such as the UV-GM-52N curing glass of Hangzhou Ke Wang special inks company production/metal frosting ink, Hangzhou
UV glass frosting ink for screen printing of the black paint company production of permanent base oil etc..After silk-screen printing, the solid particle or many in ink layer
Or it is exposed on cured film surface less, rough frosting effect surface is formed, frosting effect glass is produced by UV illumination
Product.Though this technique has the advantages that rapid curing, energy-conserving and environment-protective, case hardness is not high, water resistance and wears no resistance, resistance to
Solvent borne, acid and alkali resistance be not also good, further, since a large amount of solid packings are with the addition of, the poor fluidity of UV frosting effect inks,
Thixotropy is strong, and printing adaptability is poor, usually because of printing defects, produces substandard products, therefore common UV solidifies frosting ink always
Large batch of popularization and application are not obtained.
Application publication number is public for CN 104387838A (Application No. 201410739835.9) Chinese invention patent application
Open in a kind of silk-screen protection ink composite and screen printing method, the ink composite and included acid-proof ink and ultra-fine rubber
The quality of powder, average grain diameter≤0.04mm of the ultra-fine rubber powder, and the rubber powder account for the acid-proof ink quality 5~
20%.The screen printing method includes：Step A, acid-proof ink mixed with curing agent, be charged with diluent and ultra-fine rubber powder
Obtain a kind of silk-screen protection ink composite；Step B, using silk-screen ink composite and silk-screen half tone is protected to carry out silk to glass
Wire mark brush.Although the technical side can produce the product of glass surface privileged site effect containing frosting, acid-proof ink enters
Row is improved, and there is certain deficiency.
The content of the invention
The technological deficiency existed for outer addition type frosting effect ink, the present invention provides raw type frosting effect glass in a kind of
Glass ink, good fluidity, printing is good, and waste water, waste gas are not produced, obtains frosting effect by UV solidifications, frosting effect is true to nature,
And, damage resistant, adhesive force, water resistance, resistance to acids and bases excellent feature high with hardness.
A kind of ink of interior raw type frosting effect, gross mass part is made up of based on 100 parts the component of following mass parts：
Preferably, the ink of described interior raw type frosting effect, gross mass part is based on 100 parts, by following mass parts
Component is constituted：
Further preferably, the ink of described interior raw type frosting effect, gross mass part is based on 100 parts, by following mass parts
Component composition：
In the present invention, ink belongs to the ink that interior raw type UV solidifies frosting effect.The ink printing of interior raw type frosting effect
Surface and frosting effect is not directly formed afterwards, because chemically reacting during ultraviolet light, microgel is generated, so that shape
Into frosting effect surface.
Described photosensitive oligomer is urethane acrylate, polyester acrylate, epoxy acrylate, aminoacrylic acid
Ester, aromatic acid acrylate half ester, one kind in organosilicon (phosphorus) modification acrylate or its mixture.Photosensitive oligomer should be controlled
In the range of 30-85 parts, preferably 40-80 parts.The degree of functionality of photosensitive oligomer is higher, and curing of coatings film hardness is higher, in formula
The content increase of high functionality oligomer, solidification film hardness increase, but shrinkage factor can also increase, adhesive force reduction.Described light
The number-average molecular weight of quick oligomer is 500~15000.
During using aromatic acid acrylate half ester, performance is relatively undesirable, is used as further preferred, described photosensitive oligomer
For urethane acrylate, polyester acrylate, epoxy acrylate, amino acrylates, organosilicon (phosphorus) modified acroleic acid
One kind or its mixture in ester.
Described urethane acrylate, such as Taiwan Changxing chemistry 6148J-75,6170,6196,6195-100, the U.S. are husky
Duo Ma companies CN984, CN968, CN977, CN968, CN9006, Bayer Bitterfeld GmbH chemistry U400, U200, U100, Taiwan double bond
5290,5812 learned, Qing Te companies of the U.S. EB270, EB8254, EB1290, two to ten functional groups such as Zhong Shan sections field 3620,3910
Aliphatic or aromatic urethane acrylate.
Described polyester acrylate, such as U.S. Qing Te companies EB741, EB450, EB811, EB870, Taiwan Changxing chemistry
6312-100,6311-100,6336-100, DR-E509, two to 18 officials such as Taiwan double bond chemical industry 220,2288,245,2015
Can base polyester acrylate.
Described epoxy acrylate, such as Taiwan Changxing chemistry DR-G908,625C-45, Sartomer of the U.S.
CN2202, the wood company 6104-80,6105-80 of Jiangsu three etc..
Described amino acrylates, such as wood of Jiangsu three public affairs 6117,6115,6113, etc..
Described aromatic acid acrylate half ester, such as Sartomer of U.S. SB400, SB401, SB500E50.
Described organosilicon (phosphorus) modification acrylate, such as double bond chemical industry 347-1, upper Hypon profit chemical industry PAC7210,
PAC7389 etc..
Described activated monomer be many (more than three) functional monomers, bifunctional monomer, one kind in monofunctional monomer or its
Mixture.Activated monomer is mainly used in regulation ink viscosity and crosslink density, and its consumption should be controlled in the range of 3-30 parts, preferably
5-18 parts.
Described polyfunctional monomer is dipentaerythritol acrylate (DPHA), tetramethylol methane tetraacrylate
(PETA), two-trimethylolpropane tetra-acrylate (DiTMP4A), pentaerythritol triacrylate (PET3A), trihydroxy methyl
Propane triacrylate (TMPTA), three (2- ethoxys) isocyanurate triacrylates (THEICTA), tripropoxyization three
It is more than one or both of hydroxymethyl-propane triacrylate (TMP3POTA).
Described bifunctional monomer is tripropylene glycol diacrylate (TPGDA), 1,6 hexanediyl ester
(HDDA), neopentylglycol diacrylate (NPGDA), Ethoxylated bisphenol A acrylate (BPA4EODA), propoxylation new penta
It is more than one or both of omega-diol diacrylate (NPG2PODA), methacrylate hydroxyl ethyl ester phosphate (PM-2).
Described monofunctional monomer such as hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA), different ice
Piece acrylate (IBOA), isoborneol methacrylate (IBOMA), HEMA phosphate (HEMAP),
It is more than one or both of ethoxylation phenoxy group acrylate (PH3EOA).
Described sensitising agent is 1- hydroxy cyclohexyl phenylketones (184), 2- hydroxy-2-methyl -1- phenyl -1- acetone
(1173), benzoin dimethylether (651), 2.4.6- trimethyl benzoyl diphenyl base phosphine oxides (TPO), isopropyl thioxanthone
(ITX), 2,4- diethyl thioxanthones (DETX), benzophenone (BP), 4- phenyl benzophenones (PBZ), 4- (N, N- diformazan ammonia
Base) ethyl benzoate (EDAB), one kind in 4- benzoyls -4 '-methyl-diphenyl sulfide (BMS) or its mixture.In ink
During sensitising agent large usage quantity, curing rate is fast, but Storage period shortens, and when sensitising agent consumption is less, curing rate is slow.UV glass is covered
Sand total ink is in terms of 100 parts, and photosensitive agent content should be controlled in the range of 0-10 parts, preferably 0-5 parts, more preferably 0-3 parts.
Described filler is talcum powder, calcium carbonate, silica, silicon powder, white carbon, organobentonite, three oxidations two
One kind or its mixture in aluminium.Change the filer content in ink, regulating oil black viscosity, rheological characteristic and cured film are transparent
Property, UV glass frostings total ink is in terms of 100 parts, and filer content should be controlled in the range of 1-20 parts, preferably 1-10 parts.
In the present invention, levelling agent and defoamer can use prior art, can use commercially available prod.
Described polymerization inhibitor is in hydroquinones, MEHQ, three (N- nitroso-N-phenylhydroxylamines azanol) aluminium salt etc.
One or more kinds of (including two kinds).
Described adhesion promoter is sour modification acrylate or coupling agent, and it can improve UV coatings to glass substrate
Attachment fastness and water resistance.Sour modification acrylate such as U.S. Zhan Xin chemical companies EB168, Guangzhou Boxing science and technology B-55, Taiwan
Changxing chemistry 3500A, 648-1, the special chemical industry SC1400 in U.S. of South Korea source, Japanese chemical drug chemical industry PM-2, Hangzhou Jesse's card chemical industry
JSC-7300 modified phosphates etc..Coupling agent such as aluminate coupling agent, titanium aluminate coupling agent, silane coupler etc..Above-mentioned
In coupling agent, two (ethyl acetoacetate) aluminic acid diisopropyl esters (HY-1804), the oleic acid acyl-oxygen titanate esters (HY- of isopropyl three
105), isopropyl three (DBSA) titanate esters (HY-109), gamma-amino triethyl group TMOS (KH-550), Ν-
β (aminoethyl)-γ-aminopropyl dimethoxy silane (KH-602), γ-methacryloxypropyl trimethoxy silane (KH-
570) it is etc. ideal, only it need to add a small amount of coupling agent, you can obtain preferable effect.
The preparation of the ink of raw type frosting effect, can be prepared by by the mixing of each component in the present invention.
Present invention also offers a kind of method of the Printing ink producing frosting effect product using interior raw type frosting effect, use
Two sections of UV curings, i.e., with the certain thickness ink coating of silk-screen printing, first issue biochemical anti-in low-intensity UV light irradiations
Should, microgel is generated, so as to form rough frosting effect surface.Now the surface of ink is not fully cured, in advance
Solidify coating is fully cured under higher-strength UV light irradiations again, ultimately forms the high rigidity UV cured films of glass frosting effect.
The interior raw type frosting effect ink of the present invention generates microgel during ultraviolet light because occurring chemical reaction,
So as to form frosting effect.The present invention disobeys outer addition solid packing formation frosting surface.
Coating surface smooth after the interior raw type frosting effect ink printing of the present invention, not directly forms frosting effect,
Only after the ultraviolet light of some strength, coating could form rough frosting effect glass surface.
A kind of method of Printing ink producing frosting effect product using interior raw type frosting effect, comprises the following steps：
The ink of raw type frosting effect in being coated with base material, using two sections of ultraviolet (UV) curing process, including low energy
Ultraviolet (UV) light irradiation and high energy UV (UV) light irradiation two procedures are measured, frosting effect product is obtained.
The intensity of described low energy ultraviolet light irradiation is 3-200mw/cm2；
The intensity of described high energy UV light irradiation is 201-350mw/cm2。
Described base material is this hair more than one or both of glass, metal base, plastic basis material etc. (including two kinds)
The ink of Ming Neisheng type frosting effects is not only suitable for printed glass, also can print various metals and plastic basis material.
The UV frosting effects glass of the present invention is using two sections of UV curing process, including low energy UV light irradiations and high-energy UV
Light irradiation two procedures, i.e., ink (the UV oil of the certain thickness interior raw type frosting effect of silk-screen printing on the base materials such as glass
Ink), first with low energy ultraviolet light coating surface, form frosting effect, after make coating complete with stronger ultraviolet light again
All solidstate, had so both taken into account the frosting effect on surface, production efficiency can be improved again.Raw type frosting effect in being coated with base material
Ink thickness be 10~50 microns, thickness general control is appropriate at 10-50 microns, and more than 50 microns solidifications are slower, together
When waste ink, less than 10 microns layer of ink are too thin, and frosting effect is poor.
Regulation lamp is away from can change UV luminous intensities；UV lamp spacing, can adjust the distribution of UV luminous intensities before and after changing.
It is high-pressure sodium lamp, medium pressure mercury lamp, metal halid lamp, Non-polarized lamp etc., height to produce ultraviolet lamp used in ultraviolet
Pressure mercury lamp is because cheap, and UV energy is uniform, using ideal.
When ultraviolet ray intensity is less than 3mw/cm2When, even if illumination is for a long time, ink coating is also difficult to form frosting effect
Really.When luminous intensity is more than 230mw/cm2When, coating rapid curing, surface thoroughly solidifies, it is impossible to forms frosting effect, and produces
Local dead skin (local frosting, local one kind without frosting phenomenon are commonly called as), the frosting surface resulted in is uneven, cured film compared with
Crisp, shrinkage factor is big, poor to substrate adhesion, even without adhesive force.
Low energy ultraviolet light strength control is in 3-200mw/cm2In the range of be suitable, preferably 30-200mw/cm2。
Ultraviolet light intensity can be adjusted by changing the spacing (lamp away from) of uviol lamp and ground.Lamp is away from bigger, light
Intensity is weaker, and lamp is away from smaller, and light is stronger.
The quality of frosting effect, it is both relevant with ultraviolet lighting intensity and relevant with the light irradiation time.
High-energy UV light irradiations, which refer to use, is not less than 200mw/cm2The UV light irradiation ink coatings of intensity, use up coating
It is fully cured soon, improves production efficiency.When ultraviolet ray intensity is less than 200mw/cm2When, the curing of coatings time is longer, or even can not
Solidification, low production efficiency；When ultraviolet ray intensity is more than 350mw/cm2When, quickly, but shrinkage factor is larger, adhesive force for curing of coatings
Difference.
The luminous intensity of high-energy ultraviolet light is controlled in 201-350mw/cm2In the range of be suitable, preferably 210-300mw/
cm2。
Using only the low energy UV light irradiations frosting ink coating, it can equally make ink solidification, simply hardening time
It is very long, it is less efficient.
Compared with prior art, the invention has the advantages that：
The interior raw type frosting effect ink of the present invention has good mobility and printing, with environmental protection, energy-conservation and height
The advantages such as effect.Coating through the production of two sections of UV curing process, frosting uniform in effect, fine and closely woven, hardness is high, adhesive force, water resistance, resistance to
Acid-base property, solvent resistance are superior to addition type frosting ink, cut in glass, be not in edging procedure come off, embrittlement etc.
Bad phenomenon.Frosting effect product, such as mat glass are obtained by UV solidifications, frosting effect is true to nature, and high with hardness, scratch-resistant
The advantage such as wound, adhesive force, water resistance, resistance to acids and bases be excellent, is conducive to market-oriented utilization and extention, has broad application prospects.
Brief description of the drawings
Fig. 1 solidifies the schematic diagram of mat glass for existing outer addition type UV, and wherein a is that before UV solidifies, b is that UV solidifies
Afterwards；
Fig. 2 is raw type frosting effect ink produces the schematic diagram of frosting effect, wherein c in the UV solidifications present invention on glass
Before UV solidifications, d is after UV solidifies.
Embodiment
Embodiment 1
57 parts of urethane acrylate (U.S. Sartomer CN9006), epoxy acrylate (Taiwan Changxing chemistry DR-
G908) 17 parts, 8 parts of trimethylolpropane trimethacrylate (TMPTA), 5 parts of tripropylene glycol diacrylate (TPGDA), methyl
3 parts of hydroxypropyl acrylate (HPMA), 1 part of 1- hydroxycyclohexyl phenyl ketones (UV-184), 1 part of 4- phenyl benzophenones (PBZ),
5 parts of talcum powder, 0.5 part of defoamer (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor (MEHQ), adhesive force
2 parts of accelerator (sour modification acrylate, U.S. Zhan Xin chemical company EB168), levelling agent (German Bi Ke chemistry BYK-354) 1
Part, the mixing of above-mentioned each component be can be prepared by into interior raw type frosting effect ink.
Condition of cure：It is first 50mw/cm with intensity2UV light irradiations coating 50 seconds, then use 280mw/cm2High-energy UV light
Irradiation 3 seconds.
Embodiment 2
SB40015 parts of aromatic acid acrylate half ester, 6336-10035 parts of polyester acrylate, amino acrylates 611715
Part, 8 parts of dipentaerythritol acrylate (DPHA), 7 parts of neopentylglycol diacrylate (NPGDA), methacrylic acid hydroxypropyl
6 parts of ester (HPMA), (184) 0.5 parts of 1- hydroxy cyclohexyl phenylketones, 0.5 part of isopropyl thioxanthone (ITX), 9 parts of white carbon,
0.5 part of defoamer (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor (MEHQ), adhesion promoter (γ-
Amino triethyl group TMOS KH-550) 2 parts, 1 part of levelling agent (German Bi Ke chemistry BYK-354), by the mixed of above-mentioned each component
Conjunction can be prepared by interior raw type frosting effect ink.
Condition of cure：It is first 70mw/cm with intensity2UV light irradiations coating 45 seconds, then use 250mw/cm2High-energy UV light
Irradiation 5 seconds.
Embodiment 3
59 parts of urethane acrylate (U.S. Sartomer CN968), polyester acrylate (Taiwan Changxing chemistry
6196) 9 parts, DR-G9085 parts of epoxy acrylate, 7 parts of dipentaerythritol acrylate (DPHA), the propylene of tripropylene glycol two
5 parts of acid esters (TPGDA), 2 parts of hydroxy propyl methacrylate (HPMA), 2 parts of benzophenone (BP), benzoin dimethylether (651) 1
Part, 6 parts of organobentonite, 0.5 part of defoamer (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor (MEHQ),
2 parts of adhesion promoter (sour modification acrylate, U.S. Zhan Xin chemical company EB168), levelling agent (German Bi Ke chemistry BYK-
354) 1 part, the mixing of above-mentioned each component be can be prepared by into interior raw type frosting effect ink.
Condition of cure：It is first 80mw/cm with intensity2UV light irradiations coating 40 seconds, then use 250mw/cm2High-energy UV light
Irradiation 4 seconds.
Embodiment 4
362045 parts of urethane acrylate, CN900621 parts of urethane acrylate, organosilicon-modified acrylate
347-15 parts, three 5 parts of (2- ethoxys) isocyanurate triacrylates (THEICTA), neopentylglycol diacrylate NPGDA
5 parts, 6 parts of hydroxyethyl methacrylate (HEMA), (184) 1 parts of 1- hydroxy cyclohexyl phenylketones, 4- phenyl benzophenones (PBZ) 2
Part, 5.5 parts of silica, 0.2 part of defoamer (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor (MEHQ),
2 parts of adhesion promoter (sour modification acrylate, U.S. Zhan Xin chemical company EB168), levelling agent (German Bi Ke chemistry BYK-
354) 1.8 parts, the mixing of above-mentioned each component be can be prepared by into interior raw type frosting effect ink.
Condition of cure：It is first 100mw/cm with intensity2UV light irradiations coating 25 seconds, then use 230mw/cm2High-energy UV light
Irradiation 5 seconds.
Embodiment 5
611727 parts of amino acrylates, 529035 parts of urethane acrylate, two-trimethylolpropane tetra-acrylate
(DiTMP4A) 13 parts, three 7 parts of (2- ethoxys) isocyanurate triacrylates, tripropylene glycol diacrylate (TPGDA) 5
Part, 5 parts of hydroxy propyl methacrylate (HPMA), 0.5 part of 2- hydroxy-2-methyl -1- phenyl -1- acetone, 0.5 part of benzophenone,
4 parts of talcum powder, 0.5 part of defoamer (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor, adhesion promoter (acid modified third
Olefin(e) acid ester, U.S. Zhan Xin chemical company EB168) 1 part, 1 part of levelling agent (German Bi Ke chemistry BYK-354), by above-mentioned each component
Mixing can be prepared by interior raw type frosting effect ink.
Condition of cure：It is first 140mw/cm with intensity2UV light irradiations coating 20 seconds, then with 230mw/cm high-energy UV light
Irradiation 5 seconds.
Embodiment 6
529045 parts of urethane acrylate, 6115J-8010 parts of urethane acrylate, aromatic acid acrylate half ester
SB40122 parts, 7 parts of tripropoxy trimethylolpropane trimethacrylate (TMP3POTA), hydroxy propyl methacrylate
(HPMA) 5 parts, (184) 1 parts of 1- hydroxy cyclohexyl phenylketones, 1 part of 4- phenyl benzophenones (PBZ), 6 parts of calcium carbonate, defoamer
0.5 part of (German Bi Ke chemistry BYK-1790), 0.5 part of polymerization inhibitor (hydroquinones), adhesion promoter (sour modified acroleic acid
Ester, U.S. Zhan Xin chemical company EB168) 1 part, 1 part of levelling agent (German Bi Ke chemistry BYK-354), by the mixed of above-mentioned each component
Conjunction can be prepared by interior raw type frosting effect ink.
Condition of cure：It is first 150mw/cm with intensity2When UV light irradiations coating 18 seconds, then use 210mw/cm2High-energy UV
Light irradiation 10 seconds.
Comparative example 1
It is formulated, condition of cure identical with example 4：It is first 10mw/cm with intensity2UV light irradiations coating 20 minutes, then use
270mw/cm2High-energy UV light irradiations 10 seconds.
Comparative example 2
It is formulated, condition of cure identical with example 5：It is first 250mw/cm with intensity2When UV light irradiations coating 16 seconds, then use
270mw/cm2High-energy UV light irradiations 4 seconds.
Comparative example 3
Outer addition type UV glass frosting ink formulations：20 parts of epoxy acrylate, 14 parts of urethane acrylate, 3 the third two
15 parts of alcohol diacrylate (TPGDA), 15 parts of hydroxy propyl methacrylate (HPMA), 1- hydroxy cyclohexyl phenylketones (184) 4
Part, (1173) 5 parts of 2- hydroxy-2-methyl -1- phenyl -1- acetone, 2 parts of organobentonite, 13 parts of wax powder, 10 parts of matt powder, phosphorus
1.5 parts of acid esters (PM-2), 0.5 part of 201 methyl-silicone oil.
Condition of cure：It is 250mw/cm with luminous intensity2UV light irradiations coating one time 15 seconds, be allowed to be fully cured.
Glass frosting curing membrane performance is evaluated
First, ocular estimate
With visual method, cured film frosting outward appearance is evaluated.
It is excellent：Translucent, frosting particle is uniform, fine and closely woven, surface slip, bubble-free, shrinkage cavity, dead skin and printing reticulate pattern.
It is good：Translucent, frosting particle is uneven, not fine and closely woven, rough surface, there is 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, there is a large amount of shrinkage cavities, booty or reticulate pattern.
2nd, hardening time is evaluated
Hardening time required for cured film can reflect the height of production efficiency, and hardening time is shorter, and production efficiency is higher,
Otherwise production efficiency is lower.
3rd, adhesive force evaluation
Determined by GB4677.7-84 adhesion tests method, adhesive tape stripping method.100% is optimal, and 0% is worst.
4th, case hardness evaluation
Determined by GB6739-1996 hardness of film pencils determination method, numerical value is bigger, and hardness is higher.
5th, water resistance evaluation
Test glass sample is immersed in 25-30 DEG C of running water 24 hours, takes out and is tested after drying.
It is excellent：Adhesive force 100%, case hardness and lustrous surface are unchanged.
It is good：Within adhesive force reduction by 5%, case hardness reduction 1H.
Difference：Adhesive force reduction by more than 5%, matt, case hardness reduction more than 1H.
Acid resistance is evaluated
Test glass sample is soaked 2 hours in 25-30 DEG C, 10% aqueous sulfuric acid, takes out and is tested after drying.
6th, alkali resistance evaluation
Test glass sample is soaked 2 hours in 25-30 DEG C, 5% (wt) sodium hydrate aqueous solution, takes out and is surveyed after drying
Examination.
It is excellent：Adhesive force 100%, case hardness and lustrous surface are unchanged.
It is good：Within adhesive force reduction by 10%, case hardness reduction 1H.
Difference：Adhesive force reduction by more than 10%, matt, case hardness reduction more than 1H.
7th, solvent resistance evaluation
Test glass sample is immersed in corresponding organic solvent (absolute ethyl alcohol, dimethylbenzene, cyclohexanone) 2 hours, taken
Go out after drying and test.
It is excellent：Adhesive force 100%, case hardness and lustrous surface are unchanged.
It is good：Within adhesive force reduction by 10%, case hardness reduction 1H.
Difference：Adhesive force reduction by more than 10%, matt, case hardness reduction more than 1H.
As shown in table 1, embodiment 1-6 is the formula of different type UV resins composition, and the performance of gained frosting cured film is not
Together；Formula is identical, and illumination program is different, and the performance difference of cured film is also very big, and comparative example 1 is formulated identical with embodiment 4, compares
Example 2 is formulated identical with embodiment 5, but intensity of illumination during its solidification is different.Comparative example 3 is that addition type UV glass frosting ink is matched somebody with somebody
Side.
Table 1
Formula is identical, and UV light irradiations program is different, and gained frosting coating performance difference is very big, the test of UV frostings coating performance
It the results are shown in Table 2.
Table 2
Fig. 1 solidifies the schematic diagram of mat glass for existing outer addition type UV, and Fig. 2 is that UV solidifies in the present invention on glass
Raw type frosting effect ink produces the schematic diagram of frosting effect, it is seen then that applied after interior raw type frosting effect ink printing of the invention
Layer surface smooth, not directly forms frosting effect, only after the ultraviolet light of some strength, and coating could form recessed
Convex uneven frosting effect glass surface.
Claims (3)
1. a kind of method of Printing ink producing frosting effect product using interior raw type frosting effect, it is characterised in that including：
Using the mass parts of urethane acrylate CN968 59 of Sartomer of the U.S., the polyester acrylic of Taiwan Changxing chemistry
The mass parts of ester 6,196 9, the mass parts of epoxy acrylate DR-G908 5, the mass parts of dipentaerythritol acrylate DPHA 7,
The mass parts of tripropylene glycol diacrylate TPGDA 5, the mass parts of hydroxy propyl methacrylate HPMA 2, the mass of benzophenone BP 2
Part, the mass parts of benzoin dimethylether 651 1, the mass parts of organobentonite 6, the defoamer BYK-1790 0.5 of Germany Bi Ke chemistry
Mass parts, the mass parts of polymerization inhibitor MEHQ 0.5, the sour modified acroleic acid of adhesion promoter of Zhan Xin chemical companies of the U.S.
The mass parts of levelling agent BYK-354 1 of the mass parts of ester EB168 2, Germany Bi Ke chemistry, the mixing of above-mentioned each component can be made
Get Nei Sheng type frosting effect inks；
Condition of cure：It is first 80mw/cm with intensity2UV light irradiations coating 40 seconds, then use 250mw/cm2High-energy UV light irradiations 4
Second.
2. a kind of method of Printing ink producing frosting effect product using interior raw type frosting effect, it is characterised in that including：Poly- ammonia
The mass parts of ester acrylate 3,620 45, the mass parts of urethane acrylate CN9006 21, organosilicon-modified acrylate 347-1
5 mass parts, the mass parts of three (2- ethoxys) isocyanurate triacrylate THEICTA 5, neopentylglycol diacrylate
The mass parts of NPGDA 5, the mass parts of hydroxyethyl methacrylate HEMA 6, the mass parts of 1- hydroxy cyclohexyl phenylketones 184 1,4- benzene
The mass parts of base benzophenone PBZ 2, the mass parts of silica 5.5, the mass of defoamer BYK-1790 0.2 of Germany Bi Ke chemistry
Part, the mass parts of polymerization inhibitor MEHQ 0.5, the sour modification acrylate of adhesion promoter of Zhan Xin chemical companies of the U.S.
The mass parts of levelling agent BYK-354 1.8 of the mass parts of EB168 2, Germany Bi Ke chemistry, the mixing of above-mentioned each component can be made
Get Nei Sheng type frosting effect inks；
Condition of cure：It is first 100mw/cm with intensity2UV light irradiations coating 25 seconds, then use 230mw/cm2High-energy UV light irradiations
5 seconds.
3. a kind of method of Printing ink producing frosting effect product using interior raw type frosting effect, it is characterised in that including：Amino
The mass parts of acrylate 6,117 27, the mass parts of urethane acrylate 5,290 35, two-trimethylolpropane tetra-acrylate
The mass parts of DiTMP4A 13, the mass parts of three (2- ethoxys) isocyanurate triacrylate 7, tripropylene glycol diacrylate
The mass parts of TPGDA 5, the mass parts of hydroxy propyl methacrylate HPMA 5, the mass of 2- hydroxy-2-methyl -1- phenyl -1- acetone 0.5
Part, the mass parts of benzophenone 0.5, the mass parts of talcum powder 4, the mass parts of defoamer BYK-1790 0.5 of Germany Bi Ke chemistry, resistance
The poly- mass parts of agent 0.5, the sour mass parts of modification acrylate EB168 1 of adhesion promoter of Zhan Xin chemical companies of the U.S., Germany
The mass parts of levelling agent BYK-354 1 of Bi Ke chemistry, interior raw type frosting effect ink is can be prepared by by the mixing of above-mentioned each component；
Condition of cure：It is first 140mw/cm with intensity2UV light irradiations coating 20 seconds, then use 230mw/cm2High-energy UV light irradiations
5 seconds.
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| KR101997878B1 (en) * | 2015-09-21 | 2019-07-08 | 주식회사 엘지화학 | Uv-curable and infrared ray transmittance ink composition for inkjetting enhanced high temperature heat resistance |
| CN105330167B (en) * | 2015-12-09 | 2018-11-09 | 平湖市华瑞玻璃有限公司 | The manufacture craft of mat glass |
| CN106986549B (en) * | 2017-04-27 | 2020-01-21 | 东莞市银泰玻璃有限公司 | Method for manufacturing noctilucent frosted glass |
| CN107099189B (en) * | 2017-05-18 | 2021-02-02 | 苏州昭奇凯虹精细化工有限公司 | LED curing ink for bottle body surface and preparation and curing methods thereof |
| CN107418154A (en) * | 2017-08-07 | 2017-12-01 | 方碧水 | A kind of environment friendly halogen-free fireproof section bar material and preparation method thereof |
| CN107778956A (en) * | 2017-11-02 | 2018-03-09 | 安徽迈高化工科技有限公司 | A kind of preparation method of high temperature oxidation resisting sand streak agent |
| CN108504184A (en) * | 2018-04-28 | 2018-09-07 | 惠州市惠阳聚晟化工涂料有限公司 | One kind being used for glass shock resistance ink and its application method |
| JP6647497B1 (en) * | 2018-05-07 | 2020-02-14 | ナトコ株式会社 | Method for producing ink-jet printed matter |
| CN108912834A (en) * | 2018-09-11 | 2018-11-30 | 江苏世泰实验器材有限公司 | A kind of glass slide imitative frosting ink and preparation method thereof |
| CN109291697B (en) * | 2018-09-26 | 2021-02-02 | 苏州泛普科技股份有限公司 | Writing board |
| CN110437676B (en) * | 2019-09-16 | 2022-10-25 | 杭州科望特种油墨有限公司 | High-light-transmittance UV (ultraviolet) ink for solar panel |
| CN112898819A (en) * | 2019-12-04 | 2021-06-04 | 北京小米移动软件有限公司 | Two-component heat-curable polyurethane ink and printing method using same |
| CN111073449A (en) * | 2019-12-11 | 2020-04-28 | 江门市壹家美环境工程有限公司 | Seawater corrosion-resistant environment-friendly coating |
| CN111756896B (en) * | 2020-06-02 | 2021-10-01 | Oppo广东移动通信有限公司 | Glass shell assembly, manufacturing method thereof and electronic equipment |
| CN112679105B (en) * | 2020-12-29 | 2022-03-15 | 苏州德达材料科技有限公司 | Water-based glass color jade sand material and preparation method thereof |
| CN116376352B (en) * | 2023-04-28 | 2023-10-24 | 常州市正文印刷有限公司 | UV (ultraviolet) ink and printing process thereof |
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