CN108003699A - A kind of acid etch glass process protection ink and its preparation method and application - Google Patents

A kind of acid etch glass process protection ink and its preparation method and application Download PDF

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Publication number
CN108003699A
CN108003699A CN201810027200.4A CN201810027200A CN108003699A CN 108003699 A CN108003699 A CN 108003699A CN 201810027200 A CN201810027200 A CN 201810027200A CN 108003699 A CN108003699 A CN 108003699A
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protection ink
parts
glass
epoxy resin
weight
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CN108003699B (en
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包亚群
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Guangzhou Long Electronics Co Ltd
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Guangzhou Long Electronics Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

The present invention relates to the protection ink in a kind of acid etch glass process,In parts by weight,The resin Composition of the protection ink includes 45~60 parts of adjacent alkyl phenolic epoxy acrylic resin,5~10 parts of photo polymerization monomer,3~8 parts of Photoepolymerizationinitiater initiater and 3~5 parts of epoxy resin,The present invention is by selecting adjacent alkyl phenolic epoxy acrylic resin to be used as main component,Obtained ink has excellent hydrofluoric acid corrosion resistance performance after glass surface film-forming,Compared with traditional glass protection ink,Its hydrofluoric acid resistant performance improves at least more than one times,Its adhesive force is 0 grade,Hardness is moderate,It is more suitable for preparing the 3D glass with AG effects compared to traditional protection ink,And,Alkali soluble excellent performance of the protection ink after glass surface film-forming prepared by the present invention,Soak to demould completely within 60s in sodium hydroxide solution and do not remain,Be conducive to improve production efficiency,Save post processing man-hour.

Description

A kind of acid etch glass process protection ink and its preparation method and application
Technical field
The present invention relates to print field, more particularly to a kind of acid etch glass process with protection ink and preparation method thereof and Purposes.
Background technology
In recent years, with the continuous development and popularization of 3D Curved screens smart mobile phone and mobile equipment, there is anti-dazzle frosting Also consumer pursues gradually for the mobile phone screen or rear cover of effect (AG effects), especially has pattern effect and AG effects at the same time Glass screen be particularly subject to consumer welcome, in order to realize AG effects, it is necessary to use the hydrofluoric acid of high concentration to glass surface Perform etching, this just need a kind of glass protection ink with protective effect glass screen process to glass surface into Row protection.
Glass protection ink is coated with usually using the figure that the mode of silk-screen printing is printed as required in the prior art In glass surface, glass surface remainder is performed etching afterwards, then washes away protection ink and obtains tool of the surface through over etching There is the glass material of AG effects, however, since silk-screen printing is only applicable to the material that surface is plane, use the painting of silk-screen printing Mode for cloth is also only applicable to glass protection ink being coated on the flat glass that screen main body is 2D or 2.5D, is for surface The 3D glass of curved surface does not apply to simultaneously, and by further research, the prior art provides another method using spraying by glass Glass protection ink is uniformly coated on the scheme of 3D glass surfaces, however, spraying process cannot be as silk screen print method in glass table Face obtains specific pattern, is only capable of integrally being coated glass surface, as that need to obtain specific pattern, it is necessary to take specific The glass protection ink photocuring of selection area is formed pattern by the method for regional exposure, that is, optics transfer printing, utilizes development afterwards Liquid washes away uncured ink, is performed etching using hydrofluoric acid, reuses lye afterwards and cured ink is dissolved or degraded To the 3D glass materials with AG effects.
However, by spraying process prepare the 3D glass with AG effects need to use it is a kind of with strong hydrofluoric acid resistant performance Curing glass protects ink, just can guarantee that the stable structure that ink is protected in the hydrofluoric acid corrosion process after optics transfer, Because appearance is decomposed transfer will not be caused to fail, in the prior art as described in the technical solution disclosed in CN101126902B, made What light-curable ink was obtained using bisphenol A type epoxy resin and the compound containing acrylic acid structure by esterification more Alkali soluble resin is equipped with solvent, pigment, photoinitiator and photo polymerization monomer and obtains glass protection ink as main component, this Kind glass protection ink hydrofluoric acid corrosion resistance poor performance, is not suitable for preparing the 3D glass with AG effects, other can to alkali Molten resin component has done certain prior art for improving or adding new additive and has improved protection ink to a certain extent The ability of hydrofluoric acid resistant, as in CN104497944B by with epoxidized soybean oil acrylic resin, polyurethane modified epoxy resin Deng modified epoxy and also pass through modified crylic acid ester mixture as matrix resin, be aided with acrylate, activated monomer, Photoinitiator, filler, auxiliary agent etc., obtain a kind of hydrofluoric acid resistant Protection glue, after being coated on glass surface film-forming, at 30 DEG C Under 40wt% concentration hf etchings, the difference of the glass surface through overprotection and the glass surface etching depth without protection is 1.1mm, which has certain hydrofluoric acid corrosion resistance performance, but dissolving demoulding time is longer in alkaline conditions, 30 ~70min or so, moreover, not being suitable for preparing the 3D glass with AG effects, still needs to further improve.
Those skilled in the art needs further to the photocuring oil for glass protection on the basis of existing technology Ink is studied, and research and development have more high adhesion force, more excellent hydrofluoric acid resistant performance and alkali-soluble glass protection ink material.
The content of the invention
It is an object of the present invention to provide the protection ink in a kind of acid etch glass process, it is characterised in that In parts by weight, the resin Composition of the protection ink includes following components：
Wherein, the parts by weight of adjacent alkyl phenolic epoxy acrylic resin can be 46 parts, 49 parts, 52 parts, 55 parts, 58 Part, 59 parts etc., the parts by weight of photo polymerization monomer can be 6 parts, 7 parts, 8 parts, 9 parts etc., the parts by weight of Photoepolymerizationinitiater initiater It can be 4 parts, 5 parts, 6 parts, 7 parts etc., the parts by weight of epoxy resin can be 3.2 parts, 3.6 parts, 4 parts, 4.4 parts, 4.8 parts Deng.
Protection ink of the present invention substitutes traditional glass protection by using adjacent alkyl phenolic epoxy acrylic resin Other epoxy acrylates used in ink, the avtive spot on phenyl ring is secured using adjacent alkyl substituent, reduces work The quantity in property site, can effectively prevent the ink after photocured cross-linked contacted with hydrofluoric acid after the reaction such as substitution reaction Occur, and make its favorable solubility in aqueous slkali, meanwhile, adjacent alkyl introduces the degree of polymerization for causing resin and density more Height, increases the hydrophobicity of ink after curing, reduces infiltration rate of the hydrofluoric acid in cured printing ink, further prevents hydrogen fluorine Corrosion of the acid for the protected glassy layer of needs.
Epoxy resin is also introduced in protection ink of the present invention as main component, those skilled in the art according to The professional knowledge and actual needs that oneself is grasped can select any one or at least two epoxy resin, the introducing of epoxy resin The dissolubility between each component can be improved, and the epoxide group of epoxy resin can be with adjacent alkyl phenolic epoxy acrylic tree Ester exchange reaction is carried out between fat, the part after curing as tridimensional network is introduced into, and is had between other each components Have cooperative effect, it is possible to increase after curing protection ink chemical resistance, humidity resistance and heat resistance, enhancing protection ink with The adhesive force of protected glass interface, ensures to protect ink layer with glass surface will not occur during hf etching Depart from, photocuring can be carried out with the resolution ratio of higher.
Photo polymerization monomer and Photoepolymerizationinitiater initiater are further included in protection ink of the present invention, above two component is to use In the necessary component of glass protection ink, those skilled in the art can be according to the professional knowledge or actual needs oneself grasped Select any one photo polymerization monomer and Photoepolymerizationinitiater initiater.
Preferably, the solid content of the adjacent alkyl phenolic epoxy acrylic resin be 30%~70%, such as 31%, 35%th, 40%, 45%, 50%, 55%, 60%, 65%, 69% etc..
Preferably, the weight average molecular weight of the adjacent alkyl phenolic epoxy acrylic resin is 4000~50000, such as 4100th, 4500,6000,8000,14000,20000,25000,30000,35000,40000,48000 etc., more preferably 8000~30000, it is most preferably 10000~20000.
Preferably, the acid number of the adjacent alkyl phenolic epoxy acrylic resin is 30~150mgKOH/g, such as 31mgKOH/g、40mgKOH/g、50mgKOH/g、60mgKOH/g、80mgKOH/g、100mgKOH/g、120mgKOH/g、 140mgKOH/g, 145mgKOH/g etc., more preferably 50~100mgKOH/g.
Can be further by solid content, molecular weight and the acid number of preferably suitable adjacent alkyl phenolic epoxy acrylic resin Improve the hydrofluoric acid resistant performance and alkali solubility of protection ink of the present invention.
Preferably, the adjacent alkyl phenolic epoxy acrylic resin is by structural formula Compound be dissolved in acrylic acid and/or methacrylic acid after organic solvent and react to obtain through over-churning, wherein, R1For carbon atom The alkane group of number 1~10, n are >=20 positive integer.
Preferably, the R1For methyl or ethyl.
Preferably, the epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, aliphatic epoxy tree In fat, novolac epoxy resin, o-cresol formaldehyde epoxy resin any one or at least two mixture, more preferably JER828 types epoxy resin, JER834 types epoxy resin, the JER1001 type ring oxygen trees of Mitsubishi Chemical Co., Ltd. production Fat, JER1004 types epoxy resin, NPES-901 types epoxy resin, the NPES-904 type epoxy resin of the production of Taiwan South Asia company In any one.
Preferably, the photo polymerization monomer includes pentaerythrite three (methacrylic acid) ester, four (metering system of pentaerythrite Acid) ester, dipentaerythritol six (methacrylic acid) ester, dipentaerythritol five (methacrylic acid) ester, four (methyl of dipentaerythritol Acrylic acid) ester, caprolactone modification dipentaerythritol six (methacrylic acid) ester, caprolactone modification five (first of dipentaerythritol Base acrylic acid) in ester any one or at least two mixture, more preferably six (metering system of dipentaerythritol Acid) ester.
Preferably, the Photoepolymerizationinitiater initiater draws including phosphinoxides initiator, peroxide type initiators, benzoin class Hair agent, Anthraquinones initiator, acetophenones initiator, aminoacetophenone class initiator, ketal class initiator, benzophenone draw Send out any one in agent, phosphinoxides initiator, thioxanthene ketone class initiator, benzoin alkyl ethers initiator or at least two Mixture, more preferably acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl benzene second Ketone, 1,1- dichloroacetophenones, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl groups anthraquinone, 1- chloroanthraquinones, 2,4- dimethyl thioxanthenes Ketone, 2,4- diethyl thioxanthones, 2-chlorothioxanthone, 2,4- diisopropylthioxanthones, acetophenone dimethyl ketal, benzil diformazan Base ketal, benzophenone, (2,6- Dimethoxybenzoyls) -2,4,4- amyl groups phosphine oxide, double (2,4,6- trimethylbenzoyls Base)-phenyl phosphine oxide, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 2,4,6- trimethyl benzoyl diphenyls bases In phosphinic acid ethyl ester any one or at least two mixture.
Preferably, the protection ink further includes 1~1.5 parts by weight (such as 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts etc.) Coupling agent, the coupling agent can be those skilled in the art according to selected by the professional knowledge and actual conditions that oneself is grasped Any one coupling agent selected, for improving crosslink density, strengthens hydrofluoric acid resistant performance.
Preferably, the coupling agent is silane coupling agent, and more preferably any one contains γ-glycidyl ether oxygen The coupling agent of propyl trimethoxy silicane, is most preferably Z-6040 types coupling agent, the chemical company of SHIN-ETSU HANTOTAI of Dow Corning Corporation's production Any one in the KBM-403 type coupling agents of production.
Preferably, the protection ink further includes the solvent of 5~10 parts by weight (such as 6 parts, 7 parts, 8 parts, 9 parts etc.), institute State solvent can be those skilled in the art according to the professional knowledge and actual conditions oneself grasped it is selected any one Solvent, the addition of solvent can strengthen the coating performance of protection ink of the present invention.
Preferably, the solvent includes any one in esters, aliphatic alcohols, ketone, amide-type, polyethers organic solvent Kind or at least two mixture, more preferably any one in based organic solvent and organic solvent of ketone or at least Two kinds of mixture, is most preferably butanone, Propylene Glycol Dimethyl Ether acetic acid esters or the two mixture being mixed to get with arbitrary proportion.
Preferably, it is described protection ink by weight further include 25~35 parts by weight (such as 26 parts, 27 parts, 28 parts, 30 parts, 32 Part, 34 parts etc.) filler, the filler can be those skilled in the art according to the professional knowledge oneself grasped and actual feelings Any one selected filler of condition, the addition of filler can strengthen the hydrofluoric acid resistant performance of protection ink of the present invention.
Preferably, the filler includes talcum powder and/or alundum (Al2O3).
Preferably, the protection ink further includes the levelling agent of 0.5 parts by weight, and the levelling agent can be the skill of this area Any one selected levelling agent for being used to improve dispersiveness of professional knowledge and actual conditions that art personnel grasp according to oneself.
Preferably, the levelling agent is the BYK-333 type levelling agents of BYK companies of Germany production.
Preferably, the protection ink further includes the polymerization inhibitor of 0.1 parts by weight, and the polymerization inhibitor can be the skill of this area Art personnel according to the professional knowledge and actual conditions oneself grasped it is selected any one be beneficial to it is described protection ink store Preparation.
Preferably, the polymerization inhibitor contains the polymerization inhibitor of three (N- nitrosos-N-Phenylhydroxylamine) aluminium salts for any one, into One step is preferably the 510 type polymerization inhibitors of IHT-IN of Beijing Ying Li companies production.
Preferably, the protection ink further includes the pigment of 0.3 parts by weight, and the pigment can be those skilled in the art Member is according to any one selected pigment hyperchromic for ink of the professional knowledge and actual conditions oneself grasped.
Preferably, the pigment is phthalocyanine blue and/or ultramarine blue pigment.
The second object of the present invention is to provide a kind of preparation method of the protection ink, and the preparation method is：
By the adjacent alkyl phenolic epoxy acrylic resin of formula ratio, photo polymerization monomer, Photoepolymerizationinitiater initiater, epoxy resin and Other components after mixing, grinding at least 3 times (such as 4 times, 5 times, 8 times, 10 times, it is 15 inferior), make wherein with solid forms Fineness≤8 μm of existing component.
The other components include appointing in coupling agent, solvent and filler, and optional levelling agent, polymerization inhibitor, pigment The combination of a kind or at least two kinds of of meaning.
Preferably, the grinding is realized by three-roll grinder or sand mill.
The third object of the present invention is to provide a kind of preparation method of the glass material with AG effects, its feature exists In described method includes following steps：
Step (1), is coated with the protection ink on the glass surface, forms film layer；
Step (2), is exposed the film layer by predetermined pattern using LED sources of parallel light；
Step (3), using developer dissolving unexposed portion after end exposure, after ultra-pure water cleaning, baking, obtains part The protected glass in surface；
Step (4), is placed in etching groove by the protected glass of part surface, is performed etching using hydrofluoric acid aqueous solution, is carved Soak the demoulding in sodium hydroxide solution after erosion to handle, washing obtains the glass material with AG effects after removing lye.
Preferably, the luminous intensity exposed described in step (2) is 10~4000J/m2, such as 11J/m2、50J/m2、100J/ m2、500J/m2、1100J/m2、2500J/m2、3500J/m2、3800J/m2、3950J/m2Deng.
Preferably, developer described in step (3) for 0.8~1.2wt% (such as 0.9wt%, 1wt%, 1.1wt%, 1.15wt% etc.) sodium carbonate liquor.
Preferably, the demoulding processing time described in step (4) is 30~60s, such as 31s, 35s, 45s, 55s, 58s It is 80~100 DEG C Deng, temperature, such as 81 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 98 DEG C etc..
Preferably, the concentration of the sodium hydrate aqueous solution described in step (4) is 5~10wt%, such as 6wt%, 7wt%, 8wt%, 9wt% etc..
The fourth object of the present invention is to provide a kind of glass material with AG effects, the glass with AG effects Material is prepared by above-mentioned preparation method.
Compared with prior art, the invention has the advantages that：
(1) the preparation-obtained protection ink of the present invention is by selecting adjacent alkyl phenolic epoxy acrylic resin to be used as mainly Component, has excellent hydrofluoric acid corrosion resistance performance after glass surface film-forming, is resistant to more than 15 minutes The mixed acid solution of 40wt% hydrofluoric acid and sulfuric acid corrodes and does not fall off, with traditional with acrylic resin or epoxy novolac acrylic acid Resin is compared for the glass protection ink of main component, its hydrofluoric acid resistant performance improves at least more than one times.
(2) the preparation-obtained protection ink of present invention adhesive force after glass surface film-forming is 0 grade, and hardness is fitted In, easy to form pattern in 3D glass surfaces using the coating method of spraying and the optics transfer graphic mode of exposure imaging, The fineness of pattern is better than traditional silk-screen mode, is more suitable for preparing the 3D glass with AG effects compared to traditional protection ink Glass.
(3) alkali soluble excellent performance of the protection ink prepared by the present invention after glass surface film-forming, in hydroxide Soak to demould completely within 60s in sodium solution and do not remain, be conducive to improve production efficiency, save post processing man-hour.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair Bright concrete restriction.
Embodiment 1
Protection ink 1 is made by the steps：
By the WDS-1161 type o-cresol aldehyde epoxy acrylic trees of 50g Wuxis dimension all this Electron Material Co., Ltd production Fat (solid content 68%, weight average molecular weight 10000, acid number 80mgKOH/g), 5g photo polymerization monomers dipentaerythritol six (methacrylic acid) ester, 3g Photoepolymerizationinitiater initiater 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 3g Taiwan South Asia company NPES-904 types epoxy resin, Z-6040 types coupling agent, 10g butanone and the propane diols diformazan of the production of 1g Dow Corning Corporations of production Ether acetic acid ester by volume 1:1 prepares obtained solvent, 30g fillers talcum powder, the BYK-333 of BYK companies of 0.5g Germany production Type levelling agent, the 510 type polymerization inhibitors of IHT-IN of 0.1g Beijing Ying Li companies production, 0.3g monastral blues are blue uniformly mixed, pass through Three-roll grinder is ground 10 times, is made wherein with fineness≤8 μm of component existing for solid forms.
Embodiment 1 obtains protection ink 1.
Embodiment 2
Protection ink 2 is made by the steps：
Difference from Example 1 is that the addition of o-cresol aldehyde epoxy acrylic resin is 45g, wherein adjacent first The solid content of base epoxy novolac acrylic resin is 30%, weight average molecular weight 20000, acid number 100mgKOH/g.
Embodiment 2 obtains protection ink 2.
Embodiment 3
Protection ink 3 is made by the steps：
Difference from Example 1 is that the addition of o-cresol aldehyde epoxy acrylic resin is 60g, wherein adjacent first The solid content of base epoxy novolac acrylic resin is 70%, acid number 50mgKOH/g.
Embodiment 3 obtains protection ink 3.
Embodiment 4
Protection ink 4 is made by the steps：
Difference from Example 1 is only that, the addition of photo polymerization monomer is 10g, the addition of Photoepolymerizationinitiater initiater For 8g.
Embodiment 4 obtains protection ink 4.
Embodiment 5
Protection ink 5 is made by the steps：
Difference from Example 1 is only that the addition of epoxy resin is 5g.
Embodiment 5 obtains protection ink 5.
Embodiment 6
Protection ink 6 is made by the steps：
Difference from Example 1 is only that the addition of coupling agent is 1.5g, and the addition of solvent is 5g.
Embodiment 6 obtains protection ink 6.
Comparative example 1
It is with the difference of embodiment 1, o-cresol aldehyde epoxy acrylic resin is substituted for identical molecular weight, acid Value, the acrylic resin of solid content.
Comparative example 1 obtains protection ink 7.
Comparative example 2
It is with the difference of embodiment 1, o-cresol aldehyde epoxy acrylic resin is substituted for identical molecular weight, acid Value, the phenolic epoxy acrylic resin of solid content.
Comparative example 2 obtains protection ink 8.
Comparative example 3
With the difference is that only for embodiment 1, epoxy resin ingredient is added without.
Comparative example 3 obtains protection ink 9.
3D glass is selected to prepare the glass material 1~9 with AG effects in accordance with the following steps：
Step (1), sprays the protection ink 1~9 described in above-described embodiment and comparative example on 3D glass surfaces, pre-baked Form the film layer that thickness is 0.5mm；
Step (2), exposes the film layer by the striped design that the width of interval 2cm is 2cm using LED sources of parallel light Light, the luminous intensity of exposure is 1000J/m2, exposure dominant wavelength is 365nm；
Step (3), the sodium carbonate liquor that concentration is 1wt% after end exposure dissolve unexposed portion, and process is ultrapure After water cleaning, baking, obtains the protected glass of part surface；
Step (4), etching groove is put into by the protected glass of part surface, using containing 20wt% hydrofluoric acid and 20wt% The mix acid liquor of sulfuric acid soaks etching 20min at 45 DEG C, is immersed in the hydrogen that concentration is 10wt% after etching at 80 DEG C The demoulding is handled in sodium hydroxide solution so that the ink layer after residue cures departs from glass surface, and washing is had after removing lye There is the glass material 1~9 of AG effects.
Characterization test is carried out to the protection ink performance described in above-described embodiment and comparative example by following test method, Test result is listed in table 1：
(1) film properties test is taken off
Film properties are taken off after curing is crosslinked to characterize protection ink 1~9 by the time needed for measurement demoulding processing, are taken off The ink that time shorter explanation needed for mould processing cures after crosslinking is swollen in aqueous slkali, it is faster to take off film, and it is better to take off film.
(2) adhesive force is tested
According to GB/T 9286-1998《The cross cut test of paint and varnish paint film》Described in test method test ink 1 For the adhesive force of glass surface after~9 film-formings, wherein, the adhesive force measured is divided into 0 grade~5 grades totally 6 ranks, 0 grade Optimal for adhesive force, 5 grades worst for adhesive force.
(3) hardness of paint film is tested
According to GB/T 6739-2006《Paint and varnish pencil method measures hardness of paint film》Described in test method test Hardness after 1~9 film-forming of ink, wherein, the hardness measured is divided into 9B-8B-7B-6B-5B-4B- according to the hardness of pencil 3B-2B-B-H-2H-3H-4H-5H-6H-7H-8H-9H totally 18 ranks, 9B grades are most soft, and 9H grade are most hard.
(4) hydrofluoric acid resistant aptitude tests
The protection ink 1~9 described in above-described embodiment and comparative example, pre-baked formation thickness are sprayed on 3D glass surfaces It is the film layer of 0.5mm, the film layer is exposed using LED sources of parallel light and cures the identical time, wherein the light exposed Intensity is 1000J/m2, exposure dominant wavelength is 365nm, is afterwards immersed in the film layer after curing containing 20wt% hydrogen at 45 DEG C In the mix acid liquor of fluoric acid and 20wt% sulfuric acid, every certain period of time according to adhesive force test described in method measure it Adhesive force, if adhesive force is less than 2 grades, records the time of immersion, as protects the hydrofluoric acid resistant ability of ink 1~9.
The performance comparison table of ink is protected in 1 embodiment of table and comparative example
The preparation-obtained protection ink of the present invention can be seen that by selecting adjacent alkyl phenolic by above-mentioned test result Epoxy acrylic resin has excellent hydrofluoric acid corrosion resistance performance, energy as main component after glass surface film-forming Enough it is resistant to the mixed acid solution corrosion of the 40wt% hydrofluoric acid and sulfuric acid of more than 15 minutes and does not fall off, compares traditional protection ink Hydrofluoric acid resistant performance is enhanced about more than once, and adhesive force is 0 grade, and hardness is moderate, is more suitable for making compared to traditional protection ink The standby 3D glass with AG effects, moreover, the alkali soluble excellent performance protected after ink solidification film forming prepared by the present invention, in hydrogen Being soaked in sodium hydroxide solution can demould completely within 60s, be conducive to improve production efficiency, save post processing man-hour.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implement.Technical field Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.

Claims (10)

  1. A kind of 1. protection ink in acid etch glass process, it is characterised in that in parts by weight, the tree of the protection ink Fat component includes following components：
  2. 2. protection ink according to claim 1, it is characterised in that neighbour's alkyl phenolic epoxy acrylic resin is consolidated Content is 30%~70%；
    Preferably, the weight average molecular weight of the adjacent alkyl phenolic epoxy acrylic resin is 4000~50000, more preferably 8000~30000, it is most preferably 10000~20000；
    Preferably, the acid number of the adjacent alkyl phenolic epoxy acrylic resin is 30~150mgKOH/g, more preferably 50 ~100mgKOH/g；
    Preferably, the adjacent alkyl phenolic epoxy acrylic resin is by structural formula Compound be dissolved in acrylic acid and/or methacrylic acid after organic solvent and react to obtain through over-churning, wherein, R1For carbon atom The alkane group of number 1~10, n are >=20 positive integer；
    Preferably, the R1For methyl or ethyl.
  3. 3. protection ink according to claim 1 or 2, it is characterised in that the epoxy resin includes bisphenol type epoxy tree Any one in fat, bisphenol f type epoxy resin, aliphatic epoxy resin, novolac epoxy resin, o-cresol formaldehyde epoxy resin Or at least two mixture, be preferably JER828 types epoxy resin, JER834 types epoxy resin, JER1001 types epoxy resin, Any one in JER1004 types epoxy resin, NPES-901 types epoxy resin, NPES-904 type epoxy resin.
  4. 4. the protection ink according to one of claims 1 to 3, it is characterised in that the photo polymerization monomer includes Ji Wusi Alcohol three (methacrylic acid) ester, pentaerythrite four (methacrylic acid) ester, dipentaerythritol six (methacrylic acid) ester, two seasons penta Tetrol five (methacrylic acid) ester, dipentaerythritol four (methacrylic acid) ester, the six (methyl of dipentaerythritol of caprolactone modification Acrylic acid) ester, caprolactone modification dipentaerythritol five (methacrylic acid) ester in any one or at least two mixing Thing, is preferably dipentaerythritol six (methacrylic acid) ester；
    Preferably, the Photoepolymerizationinitiater initiater includes phosphinoxides initiator, peroxide type initiators, benzoin class initiation Agent, Anthraquinones initiator, acetophenones initiator, aminoacetophenone class initiator, ketal class initiator, benzophenone trigger Any one in agent, phosphinoxides initiator, thioxanthene ketone class initiator, benzoin alkyl ethers initiator or at least two Mixture, is preferably acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- Dichloroacetophenone, 2-methylanthraquinone, 2- ethyl hydrazine, 2- tert-butyl groups anthraquinone, 1- chloroanthraquinones, 2,4- dimethyl thioxanthones, 2,4- Diethyl thioxanthone, 2-chlorothioxanthone, 2,4- diisopropylthioxanthones, acetophenone dimethyl ketal, benzil dimethyl ketal, Benzophenone, (2,6- Dimethoxybenzoyls) -2,4,4- amyl groups phosphine oxide, double (2,4,6- trimethylbenzoyls)-benzene Base phosphine oxide, 2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, 2,4,6- trimethyl benzoyl diphenyl base phosphinic acids second In ester any one or at least two mixture.
  5. 5. the protection ink according to one of Claims 1 to 4, it is characterised in that the protection ink further includes 1~1.5 The coupling agent of parts by weight；
    Preferably, the coupling agent is silane coupling agent, and more preferably any one contains γ-glycidyl ether oxygen propyl The coupling agent of trimethoxy silane, is most preferably Z-6040 types coupling agent, any one in KBM-403 type coupling agents；
    Preferably, the protection ink further includes 5~10 parts by weight solvent；
    Preferably, the solvent include esters, aliphatic alcohols, ketone, amide-type, in polyethers organic solvent any one or Any one at least two mixture, more preferably based organic solvent and organic solvent of ketone or at least two Mixture, be most preferably butanone, Propylene Glycol Dimethyl Ether acetic acid esters or the two mixture being mixed to get with arbitrary proportion；
    Preferably, the protection ink by weight further includes the filler of 25~35 parts by weight；
    Preferably, the filler includes talcum powder and/or alundum (Al2O3).
  6. 6. the protection ink according to one of Claims 1 to 5, it is characterised in that the protection ink further includes 0.5 weight The levelling agent of part；
    Preferably, the levelling agent is BYK-333 type levelling agents；
    Preferably, the protection ink further includes the polymerization inhibitor of 0.1 parts by weight；
    Preferably, the polymerization inhibitor contains the polymerization inhibitor of three (N- nitrosos-N-Phenylhydroxylamine) aluminium salts for any one, further Preferably 510 type polymerization inhibitors of IHT-IN；
    Preferably, the protection ink further includes the pigment of 0.3 parts by weight；
    Preferably, the pigment is phthalocyanine blue and/or ultramarine blue pigment.
  7. A kind of 7. preparation method of protection ink as described in one of claim 1~6, it is characterised in that the preparation method For：
    By the adjacent alkyl phenolic epoxy acrylic resin of formula ratio, photo polymerization monomer, Photoepolymerizationinitiater initiater, epoxy resin and other Component after mixing, is ground at least 3 times, is made wherein with fineness≤8 μm of component existing for solid forms；
    The other components include any a kind in coupling agent, solvent and filler, and optional levelling agent, polymerization inhibitor, pigment Or at least two kinds of combination；
    Preferably, the grinding is realized by three-roll grinder or sand mill.
  8. 8. a kind of preparation method of the glass material with AG effects, it is characterised in that described method includes following steps：
    Step (1), is coated with the protection ink described in one of claim 1~6 on the glass surface；
    Step (2), is exposed the film layer by predetermined pattern using LED sources of parallel light；
    Step (3), using developer dissolving unexposed portion after end exposure, after ultra-pure water cleaning, baking, obtains part surface Protected glass；
    Step (4), is placed in etching groove by the protected glass of part surface, is performed etching, etched using hydrofluoric acid aqueous solution Soak the demoulding in sodium hydroxide solution after finishing to handle, washing obtains the glass material with AG effects after removing lye.
  9. 9. preparation method according to claim 8, it is characterised in that the luminous intensity exposed described in step (2) for 10~ 4000J/m2；
    Preferably, developer described in step (3) is the sodium carbonate liquor of 0.8~1.2wt%；
    Preferably, described in step (4) the demoulding processing time be 30~60s, temperature be 80~100 DEG C；
    Preferably, the concentration of the sodium hydrate aqueous solution described in step (4) is 5~10wt%.
  10. 10. a kind of glass material with AG effects, it is characterised in that the material with AG effects is by claim 8 or 9 The preparation method is prepared.
CN201810027200.4A 2018-01-11 2018-01-11 Protective printing ink for glass acid etching process and preparation method and application thereof Active CN108003699B (en)

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CN108864818A (en) * 2018-06-27 2018-11-23 安徽金龙浩光电科技有限公司 A kind of silica containing protection ink of mobile phone 3D LOGO etching
CN109021672A (en) * 2018-06-27 2018-12-18 安徽金龙浩光电科技有限公司 A kind of mobile phone 3D LOGO etching protection ink
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CN112174539A (en) * 2020-09-29 2021-01-05 台州星星光电科技有限公司 Processing method for avoiding camera position of display panel
CN117820895A (en) * 2024-01-08 2024-04-05 无锡荷雨新能源科技有限公司 Ink composition resistant to hydrofluoric acid etching and capable of being washed by alkali, preparation method and application thereof

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CN108864818A (en) * 2018-06-27 2018-11-23 安徽金龙浩光电科技有限公司 A kind of silica containing protection ink of mobile phone 3D LOGO etching
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CN109021672B (en) * 2018-06-27 2021-08-24 安徽金龙浩光电科技有限公司 Protective printing ink for 3D LOGO etching of mobile phone
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CN112174539A (en) * 2020-09-29 2021-01-05 台州星星光电科技有限公司 Processing method for avoiding camera position of display panel
CN117820895A (en) * 2024-01-08 2024-04-05 无锡荷雨新能源科技有限公司 Ink composition resistant to hydrofluoric acid etching and capable of being washed by alkali, preparation method and application thereof

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