CN108003699B - Protective printing ink for glass acid etching process and preparation method and application thereof - Google Patents
Protective printing ink for glass acid etching process and preparation method and application thereof Download PDFInfo
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- CN108003699B CN108003699B CN201810027200.4A CN201810027200A CN108003699B CN 108003699 B CN108003699 B CN 108003699B CN 201810027200 A CN201810027200 A CN 201810027200A CN 108003699 B CN108003699 B CN 108003699B
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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
- 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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- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
The invention relates to protective ink for an acid etching glass process, which comprises, by weight, 45-60 parts of o-alkyl novolac epoxy acrylic resin, 5-10 parts of photopolymerization monomer, 3-8 parts of photopolymerization initiator and 3-5 parts of epoxy resin, wherein the o-alkyl novolac epoxy acrylic resin is used as a main component, the obtained ink has excellent hydrofluoric acid corrosion resistance after being cured and formed into a film on the surface of glass, compared with the traditional glass protective ink, the hydrofluoric acid corrosion resistance is improved by at least more than one time, the adhesive force is 0 grade, the hardness is moderate, compared with the traditional protective ink, the ink is more suitable for preparing 3D glass with AG effect, the alkali solubility of the prepared protective ink after being cured and formed into a film on the surface of glass is excellent, and the protective ink can be completely demoulded without residue after being soaked in a sodium hydroxide solution for 60s, is beneficial to improving the production efficiency and saving the post-processing working hours.
Description
Technical Field
The invention relates to the field of printing, in particular to protective ink for a glass acid etching process, and a preparation method and application thereof.
Background
In recent years, with the continuous development and popularization of 3D curved-surface-screen smart phones and mobile devices, mobile phone screens or back covers with anti-glare frosting effect (AG effect) are gradually sought after by consumers, especially glass screens with pattern effect and AG effect are popular with consumers, and in order to achieve the AG effect, high-concentration hydrofluoric acid is required to etch the glass surface, so that a glass protection ink with protection effect is required to protect the glass surface in the glass screen processing process.
In the prior art, a screen printing method is generally used for coating glass protection ink on a glass surface according to a pattern to be printed, then the rest part of the glass surface is etched, and then the protection ink is washed off to obtain a glass material with an AG effect, wherein the surface of the glass material is etched, however, the screen printing method is only suitable for a material with a plane surface, the coating method using the screen printing method is also only suitable for coating the glass protection ink on a plane glass with a 2D or 2.5D screen body, the screen printing method is not suitable for a 3D glass with a curved surface, through further research, the prior art provides another scheme for uniformly coating the glass protection ink on the 3D glass surface by using a spraying method, however, the spraying method cannot obtain a specific pattern on the glass surface like the screen printing method, and only can coat the whole glass surface, if a specific pattern needs to be obtained, the method of exposing in a specific area, namely an optical transfer method, is adopted to carry out photocuring on the glass protection ink in a selected area to form a pattern, then an uncured ink is washed away by utilizing a developing solution, etching is carried out by using hydrofluoric acid, and then the cured ink is dissolved or degraded by using an alkali solution to obtain the 3D glass material with the AG effect.
However, the preparation of the 3D glass with AG effect by the spray coating method requires a photo-curable glass protective ink with strong hydrofluoric acid resistance to ensure the stable structure of the protective ink in the hydrofluoric acid corrosion process after optical transfer, and no transfer failure due to decomposition, in the prior art, as described in the technical scheme disclosed in CN101126902B, the used photo-curable ink mostly uses alkali-soluble resin obtained by esterification of bisphenol a epoxy resin and a compound containing an acrylic acid structure as a main component, and is matched with a solvent, a pigment, a photoinitiator and a photopolymerization monomer to obtain the glass protective ink, which has poor hydrofluoric acid corrosion resistance, and is not suitable for preparing the 3D glass with AG effect, and the other prior art that the alkali-soluble resin component is improved or a new additive is added improves the hydrofluoric acid resistance of the protective ink to a certain extent, for example, in CN104497944B, modified epoxy resins such as epoxy soybean oil acrylic resin, polyurethane modified epoxy resin, etc. are mixed with the same modified acrylate as a main resin, and acrylate, active monomer, photoinitiator, filler, auxiliary agent, etc. are used as auxiliary materials to obtain a hydrofluoric acid resistant protective adhesive, after the protective adhesive is coated on the surface of glass and cured to form a film, the difference between the etching depth of the protected glass surface and the unprotected glass surface is 1.1mm under the etching of 40 wt% hydrofluoric acid at 30 ℃, the protective adhesive has a certain hydrofluoric acid corrosion resistance, but the dissolution and demolding time under alkaline conditions is longer, about 30-70 min, and the protective adhesive is not suitable for preparing 3D glass with AG effect, and needs further improvement.
Those skilled in the art need to further research the photo-curable ink for glass protection based on the prior art and develop a glass protection ink material with higher adhesion, more excellent hydrofluoric acid resistance and alkali solubility.
Disclosure of Invention
One purpose of the invention is to provide protective ink used in a glass acid etching process, which is characterized in that resin components of the protective ink comprise the following components in parts by weight:
the weight parts of the o-alkyl novolac epoxy acrylic resin can be 46 parts, 49 parts, 52 parts, 55 parts, 58 parts, 59 parts and the like, the weight parts of the photopolymerization monomer can be 6 parts, 7 parts, 8 parts, 9 parts and the like, the weight parts of the photopolymerization initiator can be 4 parts, 5 parts, 6 parts, 7 parts and the like, and the weight parts of the epoxy resin can be 3.2 parts, 3.6 parts, 4 parts, 4.4 parts, 4.8 parts and the like.
According to the protective ink, the o-alkyl novolac epoxy acrylic resin is adopted to replace other epoxy acrylate used in the traditional glass protective ink, the o-alkyl substituent is utilized to fix active sites on a benzene ring, the number of the active sites is reduced, the occurrence of reactions such as substitution reaction and the like after the ink subjected to photocuring crosslinking is contacted with hydrofluoric acid can be effectively prevented, the ink is good in solubility in an alkali solution, meanwhile, the introduction of the o-alkyl enables the polymerization degree and density of the resin to be higher, the hydrophobicity of the cured ink to be increased, the permeation rate of the hydrofluoric acid in the cured ink to be reduced, and the corrosion of the hydrofluoric acid to a glass layer to be protected is further prevented.
The protective ink of the invention also introduces epoxy resin as a main component, and a person skilled in the art can select any one or at least two epoxy resins according to professional knowledge and actual needs mastered by the person, wherein the introduction of the epoxy resin can improve the solubility of the components, and the epoxy group of the epoxy resin can perform ester exchange reaction with the o-alkyl novolac epoxy acrylic resin, and the epoxy group of the epoxy resin is introduced as a part of a three-dimensional network structure after being cured, and has synergistic effect with other components, so that the chemical resistance, the humidity resistance and the heat resistance of the cured protective ink can be improved, the adhesive force of the protective ink and a protected glass interface is enhanced, the protective ink layer can not be separated from the glass surface in the hydrofluoric acid etching process, and photocuring can be performed with higher resolution.
The protective ink also comprises a photopolymerization monomer and a photopolymerization initiator, wherein the two components are necessary components for the glass protective ink, and any one of the photopolymerization monomer and the photopolymerization initiator can be selected by a person skilled in the art according to the professional knowledge or actual needs mastered by the person.
Preferably, the ortho-alkyl novolac epoxy acrylic resin has a solid content of 30% to 70%, such as 31%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 69%, and the like.
Preferably, the weight average molecular weight of the ortho-alkyl novolac epoxy acrylic resin is 4000 to 50000, such as 4100, 4500, 6000, 8000, 14000, 20000, 25000, 30000, 35000, 40000, 48000, etc., more preferably 8000 to 30000, and most preferably 10000 to 20000.
The acid value of the o-alkyl novolac epoxy acrylic resin is preferably 30 to 150mgKOH/g, for example, 31mgKOH/g, 40mgKOH/g, 50mgKOH/g, 60mgKOH/g, 80mgKOH/g, 100mgKOH/g, 120mgKOH/g, 140mgKOH/g, 145mgKOH/g, etc., and more preferably 50 to 100 mgKOH/g.
The hydrofluoric acid resistance and alkali solubility of the protective inks of the present invention can be further improved by optimizing the solids content, molecular weight, and acid number of the appropriate ortho-alkyl novolac epoxy acrylic resin.
Preferably, the ortho-alkyl novolac epoxy acrylic resin is represented by the structural formula
Is obtained by the esterification reaction of the compound (A) and acrylic acid and/or methacrylic acid after being dissolved in an organic solvent, wherein R is1Is an alkane group having 1 to 10 carbon atoms, n is not less than 20An integer number.
Preferably, said R is1Is methyl or ethyl.
Preferably, the epoxy resin comprises any one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, novolac epoxy resin and o-methyl novolac epoxy resin or a mixture of at least two of the two, and more preferably any one of JER828 type epoxy resin, JER834 type epoxy resin, JER1001 type epoxy resin, JER1004 type epoxy resin, JER type epoxy resin, NPES-901 type epoxy resin and NPES-904 type epoxy resin which are produced by Taiwan south Asia.
Preferably, the photopolymerizable monomer includes any one of pentaerythritol tri (methacrylate), pentaerythritol tetra (methacrylate), dipentaerythritol hexa (methacrylate), dipentaerythritol penta (methacrylate), dipentaerythritol tetra (methacrylate), caprolactone-modified dipentaerythritol hexa (methacrylate), caprolactone-modified dipentaerythritol penta (methacrylate), and a mixture of at least two thereof, and further preferably dipentaerythritol hexa (methacrylate).
Preferably, the photopolymerization initiator includes any one or a mixture of at least two of a phosphine oxide initiator, a peroxide initiator, a benzoin initiator, an anthraquinone initiator, an acetophenone initiator, an aminoacetone initiator, a ketal initiator, a benzophenone initiator, a phosphine oxide initiator, a thioxanthone initiator, and a benzoin alkyl ether initiator, and is more preferably acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, Any one or a mixture of at least two of 2, 4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzil dimethyl ketal, benzophenone, (2, 6-dimethoxybenzoyl) -2,4, 4-pentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, and ethyl 2,4, 6-trimethylbenzoyl diphenylphosphinate.
Preferably, the protective ink further comprises 1-1.5 parts by weight (e.g., 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, etc.) of a coupling agent, which can be any one selected by those skilled in the art according to their own professional knowledge and practical situation, for increasing the crosslinking density and enhancing the hydrofluoric acid resistance.
Preferably, the coupling agent is a silane coupling agent, more preferably any coupling agent containing gamma-glycidoxypropyltrimethoxysilane, and most preferably any one of a Z-6040 type coupling agent manufactured by Dow Corning and a KBM-403 type coupling agent manufactured by shin-Etsu chemical company.
Preferably, the protective ink further comprises 5 to 10 parts by weight (e.g., 6 parts, 7 parts, 8 parts, 9 parts, etc.) of a solvent, wherein the solvent can be any one selected by those skilled in the art according to their own expertise and practical situation, and the addition of the solvent can enhance the coating performance of the protective ink of the present invention.
Preferably, the solvent comprises any one or a mixture of at least two of ester, fatty alcohol, ketone, amide and polyether organic solvents, more preferably any one or a mixture of at least two of ester organic solvents and ketone organic solvents, and most preferably butanone, propylene glycol dimethyl ether acetate or a mixture obtained by mixing the two in any proportion.
Preferably, the weight of the protective ink further includes 25 to 35 parts by weight (for example, 26 parts, 27 parts, 28 parts, 30 parts, 32 parts, 34 parts, etc.) of a filler, the filler may be any one selected by those skilled in the art according to their own professional knowledge and practical situation, and the addition of the filler can enhance the hydrofluoric acid resistance of the protective ink of the present invention.
Preferably, the filler comprises talc and/or alumina.
Preferably, the protective ink further comprises 0.5 parts by weight of a leveling agent, and the leveling agent can be any one selected by a person skilled in the art according to his own professional knowledge and practical situations for improving the dispersibility.
Preferably, the leveling agent is a BYK-333 type leveling agent produced by BYK company of germany.
Preferably, the protective ink further comprises 0.1 weight part of polymerization inhibitor, and the polymerization inhibitor can be any preparation which is selected by a person skilled in the art according to the professional knowledge and actual conditions of the person skilled in the art and is beneficial to storage of the protective ink.
The polymerization inhibitor is preferably any one of those containing tris (N-nitroso-N-phenylhydroxylamine) aluminum salt, and more preferably IHT-IN510 type polymerization inhibitor produced by Beijing Englic corporation.
Preferably, the protective ink further comprises 0.3 weight part of pigment, and the pigment can be any pigment for ink hyperchromia selected by the person skilled in the art according to his own professional knowledge and practical conditions.
Preferably, the pigment is a phthalocyanine blue and/or ultramarine blue pigment.
The second purpose of the invention is to provide a preparation method of the protective ink, which comprises the following steps:
the ortho-alkyl novolac epoxy acrylic resin, the photopolymerization monomer, the photopolymerization initiator, the epoxy resin and other components in the formula amount are uniformly mixed, and then are ground for at least 3 times (for example, 4 times, 5 times, 8 times, 10 times, 15 times and the like) to ensure that the fineness of the components existing in a solid state is less than or equal to 8 mu m.
The other components comprise a coupling agent, a solvent and a filler, and any 1 or at least 2 of optional leveling agent, polymerization inhibitor and pigment.
Preferably, the grinding is effected by a three-roll mill or a sand mill.
The invention also aims to provide a preparation method of the glass material with the AG effect, which is characterized by comprising the following steps:
step (1), coating the protective printing ink on the surface of glass to form a film layer;
step (2), exposing the film layer according to a preset pattern by using an LED parallel light source;
step (3), after exposure is finished, using a developer to dissolve an unexposed part, and after being cleaned by ultrapure water, baking to obtain glass with a part of surface protected;
and (4) placing the glass with the partially protected surface in an etching tank, etching by using a hydrofluoric acid aqueous solution, soaking in a sodium hydroxide solution after etching, demolding, and washing to remove alkali liquor to obtain the glass material with the AG effect.
Preferably, the light intensity of the exposure in the step (2) is 10-4000J/m2E.g. 11J/m2、50J/m2、100J/m2、500J/m2、1100J/m2、2500J/m2、3500J/m2、3800J/m2、3950J/m2And the like.
Preferably, the developer in step (3) is 0.8 to 1.2 wt% (e.g., 0.9 wt%, 1 wt%, 1.1 wt%, 1.15 wt%, etc.) of sodium carbonate solution.
Preferably, the demolding treatment time in the step (4) is 30 to 60s, such as 31s, 35s, 45s, 55s, 58s, etc., and the temperature is 80 to 100 ℃, such as 81 ℃, 85 ℃, 90 ℃, 95 ℃, 98 ℃, etc.
Preferably, the concentration of the aqueous solution of sodium hydroxide in step (4) is 5 to 10 wt%, such as 6 wt%, 7 wt%, 8 wt%, 9 wt%, etc.
The fourth purpose of the invention is to provide a glass material with AG effect, which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the protective ink prepared by the invention, the ortho-alkyl novolac epoxy acrylic resin is used as a main component, the protective ink has excellent hydrofluoric acid corrosion resistance after being cured and formed into a film on the surface of glass, can resist the corrosion of a mixed acid solution of 40 wt% hydrofluoric acid and sulfuric acid for more than 15 minutes without falling off, and compared with the traditional glass protective ink taking acrylic resin or novolac epoxy acrylic resin as a main component, the hydrofluoric acid resistance of the protective ink is improved by at least one time.
(2) The protective ink prepared by the invention has the adhesion of 0 grade after the surface of the glass is cured into a film, has moderate hardness, is convenient for forming patterns on the surface of the 3D glass by utilizing a spraying coating mode and an optical transfer printing pattern mode of exposure and development, has the fineness superior to that of a traditional screen printing mode, and is more suitable for preparing the 3D glass with the AG effect compared with the traditional protective ink.
(3) The protective ink prepared by the invention has excellent alkali solubility after being cured and formed into a film on the glass surface, can be completely demoulded without residue after being soaked in a sodium hydroxide solution for less than 60s, is beneficial to improving the production efficiency and saving the post-treatment working hours.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Protective ink 1 was prepared by the following steps:
50g of WDS-1161 type o-methyl novolac epoxy acrylic resin (with a solid content of 68%, a weight-average molecular weight of 10000 and an acid value of 80mgKOH/g) produced by Wuxi Victoria electronic materials Co., Ltd, 5g of photopolymerized monomer dipentaerythritol hexa (methacrylic acid) ester, 3g of photopolymerization initiator 2,4, 6-trimethylbenzoyl diphenylphosphine oxide, 3g of NPES-904 type epoxy resin produced by Taiwan southern Asia, 1g of Z-6040 type coupling agent produced by Dow Corning, 10g of a solvent prepared by butanone and propylene glycol dimethyl ether acetate IN a volume ratio of 1:1, 30g of filler talc, 0.5g of BYK-333 type leveling agent produced by Germany BYK, 0.1g of IHT-IN510 type polymerization inhibitor produced by Beijing Yili company, and 0.3g of pigment phthalocyanine blue are uniformly mixed and ground by a three-roll grinder for 10 times, the fineness of the components present therein in solid form is less than or equal to 8 μm.
Example 1 protective ink 1 was obtained.
Example 2
Protective ink 2 was prepared by the following steps:
the difference from example 1 is that the amount of the orthomethylnovolac epoxy acrylic resin added is 45g, wherein the solid content of the orthomethylnovolac epoxy acrylic resin is 30%, the weight average molecular weight is 20000, and the acid value is 100 mgKOH/g.
Example 2 protective ink 2 was obtained.
Example 3
Protective ink 3 was prepared by the following steps:
the difference from example 1 is that 60g of an o-cresol novolac epoxy acrylic resin was added, wherein the o-cresol novolac epoxy acrylic resin had a solid content of 70% and an acid value of 50 mgKOH/g.
Example 3 protective ink 3 was obtained.
Example 4
Protective ink 4 was prepared by the following steps:
the only difference from example 1 was that the amount of the photopolymerizable monomer added was 10g and the amount of the photopolymerization initiator added was 8 g.
Example 4 protective ink 4 was obtained.
Example 5
Protective ink 5 was prepared by the following steps:
the only difference from example 1 is that the amount of epoxy resin added is 5 g.
Example 5 protected ink 5 was obtained.
Example 6
Protective ink 6 was prepared by the following steps:
the only difference from example 1 was that the amount of the coupling agent added was 1.5g and the amount of the solvent added was 5 g.
Example 6 a protective ink 6 was obtained.
Comparative example 1
The difference from example 1 is that the o-cresol novolac epoxy acrylic resin is replaced by acrylic resin with the same molecular weight, acid value and solid content.
Comparative example 1 gave a protective ink 7.
Comparative example 2
The difference from example 1 is that the o-methyl novolac epoxy acrylic resin is replaced by novolac epoxy acrylic resin with the same molecular weight, acid value and solid content.
Comparative example 2 gave a protective ink 8.
Comparative example 3
The only difference from example 1 is that no epoxy resin component was added.
Comparative example 3 gave a protective ink 9.
Selecting 3D glass to prepare glass materials 1-9 with AG effect according to the following steps:
step (1), spraying 1-9 of the protective printing ink in the embodiment and the comparative example on the surface of 3D glass, and prebaking to form a film layer with the thickness of 0.5 mm;
step (2), exposing the film layer by using an LED parallel light source according to a stripe pattern with the width of 2cm and the interval of 2cm, wherein the light intensity of exposure is 1000J/m2The exposure dominant wavelength is 365 nm;
step (3), after exposure, using a sodium carbonate solution with the concentration of 1 wt% to dissolve the unexposed part, and after being cleaned by ultrapure water, baking to obtain glass with a part of surface protected;
and (4) putting part of the glass with the protected surface into an etching tank, soaking and etching the glass for 20min at 45 ℃ by using a mixed acid solution containing 20 wt% of hydrofluoric acid and 20 wt% of sulfuric acid, soaking the glass in a 10 wt% sodium hydroxide solution at 80 ℃ after etching is finished, demolding, separating the residual cured ink layer from the surface of the glass, and washing with water to remove alkali liquor to obtain the glass material 1-9 with the AG effect.
The protective inks described in the above examples and comparative examples were characterized by the following test methods, the results of which are given in table 1:
(1) test of film removal Performance
The film fading performance of the protective ink 1-9 after curing and crosslinking is represented by measuring the time required by demolding treatment, and the shorter the time required by demolding treatment is, the better the film fading performance is when the ink after curing and crosslinking swells in an alkali solution and the film fading is faster.
(2) Adhesion test
The adhesion of the ink 1-9 to the glass surface after curing and film forming is tested according to the test method described in GB/T9286-1998 test for marking out paint films of colored paint and varnish, wherein the tested adhesion is classified into 6 grades from 0 grade to 5 grade, the 0 grade is the optimal adhesion, and the 5 grade is the worst adhesion.
(3) Paint film hardness test
The hardness of the ink after curing and film forming is tested according to the test method described in GB/T6739-2006 determination of paint film hardness by paint and varnish pencil method, wherein the measured hardness is divided into 18 grades according to the hardness of a pencil, wherein the 9B grade is the softest, and the 9H grade is the hardest, and the 6B grade is the 6B-5B-4B-3B-2B-H-2H-3H-4H-5H-6H-7H-8H-9H.
(4) Hydrofluoric acid resistance test
Spraying the protective printing ink 1-9 described in the above examples and comparative examples on the surface of 3D glass, prebaking to form a film layer with the thickness of 0.5mm, and exposing and curing the film layer for the same time by using an LED parallel light source, wherein the light intensity of exposure is 1000J/m2And the exposure dominant wavelength is 365nm, then soaking the cured film layer in a mixed acid solution containing 20 wt% of hydrofluoric acid and 20 wt% of sulfuric acid at 45 ℃, measuring the adhesive force of the cured film layer at regular intervals according to the method in the adhesive force test, and recording the soaking time if the adhesive force is lower than level 2, namely the hydrofluoric acid resistance of the protective ink 1-9.
TABLE 1 comparison of the Properties of the protective inks in the examples and comparative examples
According to the test results, the protective ink prepared by the invention has excellent hydrofluoric acid corrosion resistance after being cured and formed into a film on the glass surface by selecting the o-alkyl novolac epoxy acrylic resin as a main component, can resist the corrosion of a mixed acid solution of 40 wt% hydrofluoric acid and sulfuric acid for more than 15 minutes without falling, is more than one time higher in hydrofluoric acid resistance compared with the traditional protective ink, has 0-grade adhesive force and moderate hardness, is more suitable for preparing 3D glass with AG effect compared with the traditional protective ink, has excellent alkali solubility after being cured and formed into a film, can be completely demoulded after being soaked in a sodium hydroxide solution for less than 60 seconds, is beneficial to improving the production efficiency and saving the post-treatment working hour.
The applicant states that the present invention is illustrated by the above examples of the process of the present invention, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (36)
1. The protective printing ink used in the process of acid etching of glass is characterized in that the resin component of the protective printing ink comprises the following components in parts by weight:
the o-alkyl novolac epoxy acrylic resin has a solid content of 30-70%, a weight average molecular weight of 4000-50000 and an acid value of 30-150 mgKOH/g, and the epoxy resin comprises any one or a mixture of at least two of bisphenol A epoxy resin, bisphenol F epoxy resin, aliphatic epoxy resin, novolac epoxy resin and o-methyl novolac epoxy resin.
2. The protective ink according to claim 1, wherein the weight average molecular weight of the o-alkyl novolac epoxy acrylic resin is 8000 to 30000.
3. The protective ink according to claim 1, wherein the weight average molecular weight of the ortho-alkyl novolac epoxy acrylic resin is 10000 to 20000.
4. The protective ink according to claim 1, wherein the acid value of the o-alkyl novolac epoxy acrylic resin is 50 to 100 mgKOH/g.
5. The protective ink of claim 1, wherein the ortho-alkyl novolac epoxy acrylic resin has a structural formula
Is obtained by the esterification reaction of the compound (A) and acrylic acid and/or methacrylic acid after being dissolved in an organic solvent, wherein R is1Is an alkane group having 1-10 carbon atoms, and n is a positive integer not less than 20.
6. Protective ink according to claim 5, characterised in that said R is1Is methyl or ethyl.
7. The protective ink according to claim 1, wherein the epoxy resin is any one of JER828 type 828 epoxy resin, JER834 type 834 epoxy resin, JER1001 type 1001 epoxy resin, JER1004 type 1004 epoxy resin, NPES-901 epoxy resin, and NPES-904 epoxy resin.
8. The protective ink according to claim 1, wherein the photopolymerizable monomer comprises any one of pentaerythritol tri (methacrylate), pentaerythritol tetra (methacrylate), dipentaerythritol hexa (methacrylate), dipentaerythritol penta (methacrylate), dipentaerythritol tetra (methacrylate), caprolactone-modified dipentaerythritol hexa (methacrylate), caprolactone-modified dipentaerythritol penta (methacrylate), or a mixture of at least two thereof.
9. The protective ink according to claim 1, wherein the photopolymerizable monomer is dipentaerythritol hexa (methacrylate).
10. The protective ink according to claim 1, wherein the photopolymerization initiator includes any one of a phosphine oxide initiator, a peroxide initiator, a benzoin initiator, an anthraquinone initiator, an acetophenone initiator, an aminophenylacetophenone initiator, a ketal initiator, a benzophenone initiator, a phosphine oxide initiator, a thioxanthone initiator, a benzoin alkyl ether initiator, or a mixture of at least two of them.
11. The protective ink according to claim 1, wherein the photopolymerization initiator is acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone, 2, 4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzildimethylketal, benzophenone, (2, 6-dimethoxybenzoyl) -2,4, 4-pentylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoyldiphenylphosphinate, or a mixture of at least two thereof.
12. The protective ink according to claim 1, further comprising 1 to 1.5 parts by weight of a coupling agent.
13. Protective ink according to claim 12, characterised in that the coupling agent is a silane coupling agent.
14. The protective ink of claim 12, wherein the coupling agent is any coupling agent comprising gamma-glycidoxypropyltrimethoxysilane.
15. The protective ink according to claim 12, wherein the coupling agent is any one of a Z-6040 type coupling agent and a KBM-403 type coupling agent.
16. The protective ink according to claim 1, further comprising 5 to 10 parts by weight of a solvent.
17. The protective ink according to claim 16, wherein the solvent comprises any one of ester, fatty alcohol, ketone, amide and polyether organic solvents or a mixture of at least two of them.
18. The protective ink according to claim 16, wherein the solvent is any one of or a mixture of at least two of the organic solvents of the ester type and the ketone type.
19. The protective ink according to claim 16, wherein the solvent is butanone, propylene glycol dimethyl ether acetate or a mixture of two in any ratio.
20. The protective ink of claim 1, further comprising 25 to 35 parts by weight of a filler.
21. Protective ink according to claim 20, characterised in that the filler comprises talc and/or aluminium oxide.
22. The protective ink according to claim 1, further comprising 0.5 parts by weight of a leveling agent.
23. The protective ink according to claim 22, wherein the leveling agent is a BYK-333 type leveling agent.
24. The protective ink according to claim 1, further comprising 0.1 parts by weight of a polymerization inhibitor.
25. The protective ink according to claim 24, wherein the polymerization inhibitor is any one of those containing tris (N-nitroso-N-phenylhydroxylamine) aluminum salt.
26. The protective ink according to claim 24, wherein the polymerization inhibitor is an IHT-IN510 type polymerization inhibitor.
27. The protective ink according to claim 1, characterized in that it further comprises 0.3 parts by weight of a pigment.
28. Protective ink according to claim 27, characterised in that the pigment is a phthalocyanine blue and/or ultramarine blue pigment.
29. A method for preparing a protective ink as claimed in any one of claims 1 to 28, characterized in that the method comprises:
uniformly mixing ortho-alkyl novolac epoxy acrylic resin, a photopolymerization monomer, a photopolymerization initiator, epoxy resin and other components according to the formula amount, and grinding for at least 3 times to ensure that the fineness of the components existing in a solid form is less than or equal to 8 mu m;
the other components comprise a coupling agent, a solvent and a filler, and any 1 or at least 2 of optional leveling agent, polymerization inhibitor and pigment.
30. The method of claim 29, wherein the grinding is accomplished by a three-roll mill or a sand mill.
31. A preparation method of a glass material with AG effect is characterized by comprising the following steps:
a step (1) of coating the protective ink according to any one of claims 1 to 28 on a glass surface;
step (2), exposing the film layer according to a preset pattern by using an LED parallel light source;
step (3), after exposure is finished, using a developer to dissolve an unexposed part, and after being cleaned by ultrapure water, baking to obtain glass with a part of surface protected;
and (4) placing the glass with the partially protected surface in an etching tank, etching by using a hydrofluoric acid aqueous solution, soaking in a sodium hydroxide solution after etching, demolding, and washing to remove alkali liquor to obtain the glass material with the AG effect.
32. The method according to claim 31, wherein the light intensity of the exposure in the step (2) is 10 to 4000J/m2。
33. The method according to claim 31, wherein the developer in the step (3) is a 0.8 to 1.2 wt% sodium carbonate solution.
34. The method according to claim 31, wherein the step (4) comprises a step of subjecting the sheet to the mold release treatment for 30 to 60 seconds at a temperature of 80 to 100 ℃.
35. The method according to claim 31, wherein the concentration of the aqueous sodium hydroxide solution in the step (4) is 5 to 10 wt%.
36. A glass material having an AG effect, characterized in that the material having an AG effect is produced by the production method according to any one of claims 31 to 35.
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| CN201810027200.4A CN108003699B (en) | 2018-01-11 | 2018-01-11 | Protective printing ink for glass acid etching process and preparation method and application thereof |
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| CN108864818B (en) * | 2018-06-27 | 2021-08-24 | 安徽金龙浩光电科技有限公司 | Protective printing ink containing silicon dioxide for 3D LOGO etching of mobile phone |
| 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 |
| CN109541889B (en) | 2018-12-19 | 2020-06-26 | 江苏艾森半导体材料股份有限公司 | Negative photoresist for semiconductor packaging process |
| 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 |
| CN117820895B (en) * | 2024-01-08 | 2024-06-25 | 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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