CN104650649A - Acid-proof ink for protecting integrated touch screen and preparation method of acid-proof ink - Google Patents
Acid-proof ink for protecting integrated touch screen and preparation method of acid-proof ink Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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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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- Wood Science & Technology (AREA)
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- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract
The invention discloses acid-proof ink for protecting an integrated touch screen and a preparation method of the acid-proof ink. The acid-proof ink comprises components A to F. The component A contains polystyrene-polyurethane-unsaturated polyester resin; the polystyrene-polyurethane-unsaturated polyester resin is synthesized by virtue of a molecular design, and a controllable design of the structure and properties of a material is realized. A three-dimensional network structure is formed by virtue of chemical reaction between the film-forming components A and B, so that the acid resistance and the high temperature resistance of the ink, and the strippability of a film can be improved, and the protection effect of the ink to a substrate can be enhanced; (2) the acid corrosion resistance of the ink is further improved. The protective ink is excellent in acid resistance, excellent in film-forming property and excellent in film adhesion, and can be stripped completely after use; besides, the ink is excellent in high temperature resistance.
Description
Technical field
The present invention relates to OGS ink, especially relate to a kind of acid-proof ink for the protection of integrated touch-control touch-screen and preparation method thereof.
Background technology
Touch-screen cover-plate glass, as a kind of high strength, damage resistant glass, is widely used in the fields such as high-end smartphones, panel computer, flat panel TV and industrial business touch-screen.OGS is one of touch-screen industry future thrust.Integration touch-control (OneGlassSolution, OGS) technology refers to the technology directly forming ITO conducting film and sensor on protective glass, and one block of glass plays the dual function of protective glass and touch sensor simultaneously.Glass after OGS technical finesse obtains OGS touch screen after cutting.The G/G touch technology that OGS technology is more traditional has a lot of advantage, e.g., can economize a slice glass substrate, production process can save one bonding process, thus is conducive to reducing production cost, improving product yield.And the OGS touch screen obtained has the features such as light, thin, light transmission is good.But glass, after cutting, easily produces slight crack in cut place, and then causes OGS touch screen product mechanical resistance pressure drop.Usually need through follow-up secondary hardening process to overcome the problems referred to above.
The mode of the secondary hardening of OGS touch screen has physics mode and chemical mode.With regard to chemical mode; normally protect on two surfaces up and down through cutting the OGS touch screen obtained; then the OGS touch screen after protection is put into acidic solution; the cut surface of the glass utilizing acid solution process not protected by antiacid film; carry out secondary hardening; repair the slight crack of glass cutting place, thus reach the object of the physical strength improving OGS touch screen.
OGS is one of touch-screen industry future thrust, its complex process, needs to carry out cutting, finishing impression, the operation such as printing, and glass is easily scratched and pollutes; Particularly in plated film, silver-plated sizing process, because processing temperature is high, need a kind of high temperature resistant rippability protecting glue not needing plated film, the part of silver-plated slurry protects.Three kinds of protected mode: UV are had to protect ink, peelable glue and PET pad pasting in the market.
WO2005012434A1 discloses a kind of releasable composition, it contains peelable release particle (3) in specific film-forming material (2), peelable release particle (3) has the 1st peelable release resin and the 2nd peelable release resin, wherein, 1st peelable release resin formation core material (5), the 2nd peelable release resin formation coating material (4).And with described 2nd peelable release resin-phase ratio, the easy extent of exfoliation of the 1st peelable release resin is relatively high.The surface tension of the such as the 1st peelable release resin is 0.01N/m ~ 0.025N/m, and the surface tension of the 2nd peelable release resin is 0.026N/m ~ 0.05N/m.
Chinese patent CN201010184900.8 discloses a kind of elastic peelable glue and carries out the method for parcel plating protection, and described elastic peelable glue comprises following component: styrene analog thermoplastic elastomer 15 ~ 50 weight part, mineral oil 20 ~ 60 weight part, tackifying resin 10 ~ 30 weight part, oxidation inhibitor 0 ~ 2 weight part.The method of carrying out parcel plating protection with described elastic peelable glue is: first put in the heating container of temperature controllable by elastic peelable glue; can use after heat fused; temperature controls between 140 ~ 180 DEG C; then electroplated workpiece is immersed in the protecting glue of fusing; to be impregnated completely after workpiece is proposed, put into cold water cooling and can carry out follow-up electroplating work procedure in 5 ~ 15 minutes.
The shortcoming of peelable glue in the market: all can remain when (1) peels off, there is cull, need to use solvent wiping.(2) UV needs after protecting ink to process to remove with alkaline soak, can destroy sensor part.(3) high thermal resistance is poor, particularly particularly outstanding in OGS processing, because peelable glue heat resistance is poor, causes the yield step-down adopting OGS technique related products.(4) ink acid resistance is in the market poor, not easily moves back film, and cleaning needs to use buck, can destroy sensor part.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of acid-proof ink for the protection of integrated touch-control touch-screen and preparation method thereof is provided.
Described ink consisting of by mass percentage:
Wherein, the consisting of of film-forming components A:
Polystyrene-poly ammonia ester-unsaturated polyester resin 40-60 part; Chlorinatedpolyolefins 10-30 part of modified by maleic acid anhydride graft; Carboxy-modified chlorine vinegar terpolymer 30-50 part; Organic-silicon-modified terpolymer EP rubber 30-40 part;
Film-forming components B consists of: cellulose acetate butyrate, 20-35 part; Epoxy resin, 5-15 part, blocked polyurethane, 15-25 part;
The C of resistance to acid constituents is N-(2-amino-ethyl)-APTES, 3-isocyanate group propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane is the mixture of 1: 1-1.5: 1-3 according to mass ratio;
The D of resistance to acid constituents is nano aluminium oxide;
Auxiliary agent E is acetyl acetone salt;
Described solvent F is the organic solvent that this area is commonly used; Ester system, ketone system, chlorine system, alcohol system, ether system, hydrocarbon system, ether-ether system etc. can be enumerated.Include, for example as ethylcarbitol acetate, butyl cellosolve acetic ester, propylene-glycol monoalky lether acetic ester, N-Methyl pyrrolidone (NMP), propylene glycol monomethyl ether (PGMEA), pimelinketone, methyl ethyl ketone (MEK), methyl isopropyl Ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether ethyl acetate, methylethylketone, methyl iso-butyl ketone (MIBK), monomethyl ether glycol ester, gamma-butyrolactone, propionic acid-3-ether ethyl ester, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, diethylene glycol ethyl ether acetic ester, ethoxyl ethyl propionate, hexanaphthene, one or more in dimethylbenzene and Virahol.
The polymerization process of described polystyrene-poly ammonia ester-unsaturated polyester resin is:
Step (1): the synthesis of the unsaturated polyester containing terminal hydroxy group
In the four mouthfuls of reaction vessels being with stirring and condensation, drop into 70-100 part monounsaturated dicarboxylic acid, 10-70 part unsaturated dibasic acid and/or 10-40 part unsaturated dicarboxylic acid anhydride, 80-160 part polyvalent alcohol, 0.1-3 part catalyzer, 100-200 part solvent successively, logical nitrogen also stirs, slowly be warming up to 120-140 DEG C, heat up gradually again after maintaining 2-3h 150 ~ 190 DEG C and continue reaction 1-4h, until acid number is close or reach 40mgKOH/g, continue to add polyvalent alcohol, reaction 0.5-2h, stretched system acid number is less than 10mgKOH/g, and is reaction end when aquifer yield is unchanged; Vacuumize; Washing; Dry; Obtain the unsaturated polyester containing terminal hydroxy group; In this step, the consumption of-OH is relative to the many 0.5-10.5mol% of the consumption of-COOH (molar percentage);
Step (2): the synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing unsaturated polyester 50-120 part of terminal hydroxy group, polyisocyanates 60-160 part, catalyzer 0.1-3 part, solvent 100-300 part, temperature reaction 2-4h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Wherein, the consumption of-NCO is relative to the many 1-5mol% of the consumption of-OH (molar percentage);
Add (methyl) dihydroxypropyl dodecyl ester 30-90 part, add catalyzer 0.1-3 part, stopper 0.1-3 part simultaneously, continue reaction, to system, NCO exhausts, stopped reaction; Vacuumize; Washing; Dry; Obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy;
Step (3): the synthesis of polystyrene-poly ammonia ester-unsaturated polyester ester copolymer
The end group getting second step synthesis is urethane unsaturated polyester ester copolymer 50-100 part of acryloxy, vinylbenzene, initiator 0.5-2 part, solvent 50-300 part, reacting by heating 1-4h, continue temperature reaction 0.5-2 hour, stopped reaction, vacuumize, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin.
More preferably following preparation method:
Step (1): the synthesis of the unsaturated polyester containing terminal hydroxy group
In the four mouthfuls of reaction vessels being with stirring and condensation, drop into 30 parts of tetrachlorophthalic acids successively, 30 parts of tetrabromophthalate, 35 parts of octadecane diacids, 45 parts of methylfumaric acid, 15 parts of MALEIC ANHYDRIDE, 15 parts of chlordene endo-methylene group Tetra hydro Phthalic anhydrides, 60 parts of neopentyl glycols, 55 parts of 2-ethyl-2-butyl-1, ammediol, 0.3 part of catalyzer, 150 parts of solvents, logical nitrogen also stirs, slowly be warming up to 125 DEG C, heat up gradually 165 DEG C again after maintaining 2h and continue reaction 3h, until acid number is close or reach 40mgKOH/g, continue to add 2-ethyl-2-butyl-1, ammediol, reaction 1h, stretched system acid number is less than 10mgKOH/g, and aquifer yield unchanged time be reaction end, vacuumize, washing, dry, obtain the unsaturated polyester containing terminal hydroxy group, in this step, the consumption of-OH is relative to the many 1.5mol% of the consumption of-COOH,
Step (2): the synthesis of urethane unsaturated polyester ester copolymer
Get the unsaturated polyester 80 parts, 4 containing terminal hydroxy group of the first step synthesis, 4 '-diphenylmethanediisocyanate 120 parts, catalyzer 0.1 part, solvent 200 parts add in reaction vessel, temperature reaction 2h, when-NCO% stablizes, obtains the urethane unsaturated polyester ester copolymer that end group is-NCO; Wherein, the consumption of-NCO is relative to the many 1.5mol% of the consumption of-OH (molar percentage);
Add the dihydroxypropyl dodecyl ester of accurate-metering, add catalyzer 0.3 part, stopper 0.3 part simultaneously, continue reaction, to system, NCO exhausts, stopped reaction; Vacuumize; Washing; Dry; Obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy; In this step, the consumption of dihydroxypropyl dodecyl ester has just reacted-the NCO in system;
Step (3): the synthesis of polystyrene-poly ammonia ester-unsaturated polyester ester copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00 part, vinylbenzene 150 parts, initiator 0.5 part, the solvent 300 parts of acryloxy, reacting by heating 4h, continue temperature reaction 0.5 hour, stopped reaction, vacuumize, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin.
In the method for the described polystyrene-poly ammonia ester-unsaturated polyester resin of synthesis, the organic solvent that described solvent selects this area conventional; Ester system, ketone system, chlorine system, alcohol system, ether system, hydrocarbon system, ether-ether system etc. can be enumerated.Include, for example as ethylcarbitol acetate, butyl cellosolve acetic ester, propylene glycol alkyl ether acetic acid ester, N-Methyl pyrrolidone (NMP), methyl proxitol acetate, pimelinketone, methyl ethyl ketone (MEK), methyl isopropyl Ketone, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, glycol propyl ether, butyl glycol ether, diethylene glycol diethyl ether ethyl acetate, methylethylketone, methyl iso-butyl ketone (MIBK), monomethyl ether glycol ester, gamma-butyrolactone, propionic acid-3-ether ethyl ester, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic ester, methyl proxitol, 1-Methoxy-2-propyl acetate, diethylene glycol ethyl ether acetic ester, ethoxyl ethyl propionate, hexanaphthene, one or more in dimethylbenzene.Preferred described solvent is the mixed solvent according to following proportioning, NMP: hexanaphthene: MEK=50: 30: 20
Described carboxy-modified chlorine vinegar terpolymer; Preferably, the content of vinylchlorid (VC) is 70-85wt%, and the content of vinyl acetate is 10-20wt%.Available example as:
e 15/45M;
Wherein, the chlorinatedpolyolefins of described modified by maleic acid anhydride graft is the ethylene chloride/propylene/octene random terpolymer of modified by maleic acid anhydride graft; Preferably, ethylene content is 3-5mol%; Octene content is 1-3mol%; Cl content is 12-16 % by weight; The content of maleic anhydride is 5 ~ 9 % by weight; Its number-average molecular weight is 9000-100.000.
End-blocking isocyanate group contained in described blocked polyurethane is that isocyanate group is protected by reacting with end-capping reagent, thus by the group of temporary transient passivation.When being heated to specified temperature, this end-capping reagent dissociates, and generates isocyanate group.Blocked polyurethane can select Sumidule BL-3175, BL-4165, BL-1100, BL-1265, DesmoduleTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm 2265, coronate 2512, coronate 2513, coronate 2520, B-830, B-815, B-846, B-870, B-874, B-88, TPA-B80E, 17B-60PX, E402-B80T etc. one or more.
Described epoxy resin is epoxidized polybutadiene, and it has polyhutadiene main chain and epoxy group(ing) concurrently, can select EPOLEAD PB3600, EPOFRIEND CT310, EPOFRIENDAT501, Ricon 657, DENAREXR-45EPT etc. one or more.
The preparation method of the described acid-proof ink for the protection of integrated touch-control touch-screen, comprises the following steps:
1) according to recipe configuration film-forming components A, B;
2) take component A-F by metering, mix under normal temperature, after stirring, grinding, namely obtains described acid-proof ink.
In step 2) in, the condition of described grinding can be grinds 0.5-2 hour on three-roll grinder.
Advantage of the present invention and technique effect as follows:
1) by the chemical reaction of official between film-forming components A, B, form three-dimensional net structure, improve the acid resistance of ink, resistance to elevated temperatures, and the rippability of paint film, improve the protection of ink to base material.
2) by the synergy of the C of resistance to acid constituents, D, the performance of the antiacid corrosion of ink is further increased.
3) by molecular designing synthetic polystyrene-urethane-unsaturated polyester resin, select best polymerization single polymerization monomer to balance the over-all properties of peelable material, realize the controlled design of material structure, performance.Select tetrachlorophthalic acid, tetrabromophthalate, chlordene endo-methylene group Tetra hydro Phthalic anhydride, add the consistency commonly using film forming matter vinyl chloride-vinyl acetate resin with peelable material, make prepared polystyrene-poly ammonia ester-unsaturated polyester resin and vinyl chloride-vinyl acetate resin have good consistency; Select the long chain molecule such as neopentyl glycol, octadecane diacid, (methyl) dihydroxypropyl dodecyl ester, polymer molecular chain can be rotated freely, then take into account sticking power and the flexibility of peelable material very well; Add 2-ethyl-2-butyl-1,3-PD, make polymer molecule backbone have long-chain side base, form dendritic structure, improve strippability, and reduce polymkeric substance viscosity in a solvent, be conducive to coating; Vinylbenzene, 4,4 '-diphenylmethanediisocyanate further increases acid resistance, the high thermal resistance of ink.
Embodiment
The present invention is described in detail for following examples.
Preparation example 1
Prepare polystyrene-poly ammonia ester-unsaturated polyester resin, preparation method is as follows:
Step (1): the synthesis of the unsaturated polyester containing terminal hydroxy group
In the four mouthfuls of reaction vessels being with stirring and condensation, drop into 30 parts of tetrachlorophthalic acids successively, 30 parts of tetrabromophthalate, 35 parts of octadecane diacids, 45 parts of methylfumaric acid, 15 parts of MALEIC ANHYDRIDE, 15 parts of chlordene endo-methylene group Tetra hydro Phthalic anhydrides, 60 parts of neopentyl glycols, 55 parts of 2-ethyl-2-butyl-1, ammediol, 0.3 part of catalyzer, 150 parts of solvents, logical nitrogen also stirs, slowly be warming up to 125 DEG C, heat up gradually 165 DEG C again after maintaining 2h and continue reaction 3h, until acid number is close or reach 40mgKOH/g, continue to add 2-ethyl-2-butyl-1, ammediol, reaction 1h, stretched system acid number is less than 10mgKOH/g, and aquifer yield unchanged time be reaction end, vacuumize, washing, dry, obtain the unsaturated polyester containing terminal hydroxy group, in this step, the consumption of-OH is relative to the many 1.5mol% of the consumption of-COOH,
Step (2): the synthesis of urethane unsaturated polyester ester copolymer
Get the unsaturated polyester 80 parts, 4 containing terminal hydroxy group of the first step synthesis, 4 '-diphenylmethanediisocyanate 120 parts, catalyzer 0.1 part, solvent 200 parts add in reaction vessel, temperature reaction 2h, when-NCO% stablizes, obtains the urethane unsaturated polyester ester copolymer that end group is-NCO; Wherein, the consumption of-NCO is relative to the many 1.5mol% of the consumption of-OH (molar percentage);
Add the dihydroxypropyl dodecyl ester of accurate-metering, add catalyzer 0.3 part, stopper 0.3 part simultaneously, continue reaction, to system, NCO exhausts, stopped reaction; Vacuumize; Washing; Dry; Obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy; In this step, the consumption of dihydroxypropyl dodecyl ester has just reacted-the NCO in system;
Step (3): the synthesis of polystyrene-poly ammonia ester-unsaturated polyester ester copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00 part, vinylbenzene 150 parts, initiator 0.5 part, the solvent 300 parts of acryloxy, reacting by heating 4h, continue temperature reaction 0.5 hour, stopped reaction, vacuumize, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin
Embodiment 1
For the protection of an acid-proof ink for integrated touch-control touch-screen, it is made up of the component of following mass percent:
Wherein, the consisting of of film-forming components A:
Polystyrene-poly ammonia ester-unsaturated polyester resin 60 parts; The chlorinatedpolyolefins of modified by maleic acid anhydride graft 15 parts; Carboxy-modified chlorine vinegar terpolymer 35 parts; Organic-silicon-modified terpolymer EP rubber 40 parts;
Film-forming components B consists of: cellulose acetate butyrate, 20 parts; Epoxy resin, 5 parts, blocked polyurethane, 25 parts;
The C of resistance to acid constituents is N-(2-amino-ethyl)-APTES, 3-isocyanate group propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane is the mixture of 1: 1: 1 according to mass ratio;
The D of resistance to acid constituents is nano aluminium oxide;
Auxiliary agent E is ferric acetyl acetonade;
Described solvent F is the mixture (mass ratio is 3: 1) of NMP and MEK
Its preparation method, comprises the following steps:
1) according to recipe configuration film-forming components A, B;
2) take component A-F by metering, grind 2 hours on three-roll grinder after mixing under normal temperature, stirring, namely obtain described acid-proof ink.
Embodiment 2
For the protection of an acid-proof ink for integrated touch-control touch-screen, it is made up of the component of following mass percent:
Wherein, the consisting of of film-forming components A:
Polystyrene-poly ammonia ester-unsaturated polyester resin 50 parts; The chlorinatedpolyolefins of modified by maleic acid anhydride graft 20 parts; Carboxy-modified chlorine vinegar terpolymer 35 parts; Organic-silicon-modified terpolymer EP rubber 30 parts;
Film-forming components B consists of: cellulose acetate butyrate, 25 parts; Epoxy resin, 10 parts, blocked polyurethane, 20 parts;
The C of resistance to acid constituents is N-(2-amino-ethyl)-APTES, 3-isocyanate group propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane is the mixture of 1: 1.5: 2 according to mass ratio;
The D of resistance to acid constituents is nano aluminium oxide;
Auxiliary agent E is acetylacetonate nickel;
Described solvent F is the mixture (mass ratio is 1: 1) of NMP and MEK
Its preparation method, comprises the following steps:
1) according to recipe configuration film-forming components A, B;
2) take component A-F by metering, grind 1.5 hours on three-roll grinder after mixing under normal temperature, stirring, namely obtain described acid-proof ink.
Comparative example 1
Except film-forming components A is not containing except polystyrene-poly ammonia ester-unsaturated polyester resin, all the other components are identical with embodiment 1.
Comparative example 2
Except not containing except the C of resistance to acid constituents, the D of resistance to acid constituents, all the other components are identical with embodiment 2.
Following performance test experiment is carried out to the protection ink prepared in above-described embodiment:
1) film forming properties and sticking power detect
The glass board material printed and PET film are taken out after toasting 10min under 130 DEG C, 140 DEG C and 150 DEG C of conditions, observe film forming situation, include without shrinkage cavity, with or without ftracture and protective membrane surface whether dry.
◎ shows that film forming is all right, × show have problem to occur.
Protective membrane sheet material being carried out water and drench test, is continue 1h under the flow velocity of 3.5L/min in discharge, observes protective membrane and whether has foaming, the situation of stripping or cracking occurs.
◎ shows that film sticking power is good, × show have problem to occur.
2) acid resistance detects
Prepare the glass board material with ITO layer and each 2 pieces of PET film, before printing, measure the resistance value of each sheet material ITO layer in advance, using the criterion to protective value after protective membrane stripping.
Ink is printed in after on ready sheet material by 250 object silk-screen half tones, after toasting 10min film forming under 140 DEG C of conditions, is immersed in by sheet material in the hydrochloric acid soln of 35%, envrionment temperature 25 DEG C, soak time 30min.
Sheet material taking-up after soaking is dried, observes protective membrane with or without the vestige be corroded, measure ITO layer resistance value after protective membrane of tearing and contrast with the front resistance of immersion.If resistance change scope is within 5%, then show that the acid resistance of protective membrane is good.
◎ shows that resistance change is within 2%, and zero shows that resistance change is in 2-5%, × show that resistance change is greater than 5%.
3) resistance to elevated temperatures test
Prepare the glass board material with ITO layer and each 1 piece of PET film, before printing, measure the resistance value of each sheet material ITO layer in advance, using the criterion to protective value after protective membrane stripping.
Ink is printed in after on ready sheet material by 250 object silk-screen half tones; after toasting 10min film forming under 140 DEG C of conditions; take out after sheet material is continued to toast 1h under the condition of 150 DEG C; protective membrane is peeled off and measures ITO layer resistance and contrast with the front resistance of baking; if change in resistance is within 5%, then show that the resistance to elevated temperatures of protective membrane is good.
◎ shows that resistance change is within 2%, and zero shows that resistance change is in 2-5%, × show that resistance change is greater than 5%.Ink test result prepared by the present invention is as follows:
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Film-forming properties | ◎ | ◎ | × | × |
| Sticking power | ◎ | ◎ | × | × |
| Acid resistance | ◎ | ◎ | × | × |
| High temperature resistant | ◎ | ◎ | × | ○ |
As can be seen from the above table: protection ink acid resistance prepared by the present invention is excellent, and film forming is all right, film sticking power is good, can peel off completely after using; Resistance to elevated temperatures is good.Therefore the excellent property of film body is described.
Each raw material cited by the present invention, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.This explanatory note adopts embodiment openly to comprise the present invention of optimal mode, and makes any those skilled in the art implement and utilize the present invention.Patentable scope of the present invention is defined by the claims, and can comprise other feasible for a person skilled in the art embodiment.Other embodiment this, as they have not different with the word language of claim textural element, if or they comprise the result key element with the word language of claim significant difference useless, then should be within the scope of the claims.
Claims (10)
1. for the protection of an acid-proof ink for integrated touch-control touch-screen, it is characterized in that, described ink forms by the component of following mass percent:
Wherein, the consisting of of film-forming components A:
Polystyrene-poly ammonia ester-unsaturated polyester resin 40-60 part; Chlorinatedpolyolefins 10-30 part of modified by maleic acid anhydride graft; Carboxy-modified chlorine vinegar terpolymer 30-50 part; Organic-silicon-modified terpolymer EP rubber 30-40 part; Wherein, the chlorinatedpolyolefins of described modified by maleic acid anhydride graft is the ethylene chloride/propylene/octene random terpolymer of modified by maleic acid anhydride graft;
Film-forming components B consists of: cellulose acetate butyrate, 20-35 part; Epoxy resin, 5-15 part, blocked polyurethane, 15-25 part;
The C of resistance to acid constituents is N-(2-amino-ethyl)-APTES, 3-isocyanate group propyl-triethoxysilicane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane is the mixture of 1: 1-1.5: 1-3 according to mass ratio;
The D of resistance to acid constituents is nano aluminium oxide;
Auxiliary agent E is acetyl acetone salt.
2. an acid-proof ink as claimed in claim 1, is characterized in that, described polystyrene-poly ammonia ester-unsaturated polyester resin is prepared as follows:
Step (1): the synthesis of the unsaturated polyester containing terminal hydroxy group
In the four mouthfuls of reaction vessels being with stirring and condensation, drop into 70-100 part monounsaturated dicarboxylic acid, 10-70 part unsaturated dibasic acid and/or 10-40 part unsaturated dicarboxylic acid anhydride, 80-160 part polyvalent alcohol, 0.1-3 part catalyzer, 100-200 part solvent successively, logical nitrogen also stirs, slowly be warming up to 120-140 DEG C, heat up gradually again after maintaining 2-3h 150 ~ 190 DEG C and continue reaction 1-4h, until acid number is close or reach 40mgKOH/g, continue to add polyvalent alcohol, reaction 0.5-2h, stretched system acid number is less than 10mgKOH/g, and is reaction end when aquifer yield is unchanged; Vacuumize; Washing; Dry; Obtain the unsaturated polyester containing terminal hydroxy group; In this step, the consumption of-OH is relative to the many 0.5-10.5mol% of the consumption of-COOH (molar percentage);
Step (2): the synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing unsaturated polyester 50-120 part of terminal hydroxy group, polyisocyanates 60-160 part, catalyzer 0.1-3 part, solvent 100-300 part, temperature reaction 2-4h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Wherein, the consumption of-NCO is relative to the many 1-5mol% of the consumption of-OH (molar percentage);
Add (methyl) dihydroxypropyl dodecyl ester 30-90 part, add catalyzer 0.1-3 part, stopper 0.1-3 part simultaneously, continue reaction, to system, NCO exhausts, stopped reaction; Vacuumize; Washing; Dry; Obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy;
Step (3): the synthesis of polystyrene-poly ammonia ester-unsaturated polyester ester copolymer
The end group getting second step synthesis is urethane unsaturated polyester ester copolymer 50-100 part of acryloxy, vinylbenzene, initiator 0.5-2 part, solvent 50-300 part, reacting by heating 1-4h, continue temperature reaction 0.5-2 hour, stopped reaction, vacuumize, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin.
3. an acid-proof ink as claimed in claim 1, is characterized in that, described polystyrene-poly ammonia ester-unsaturated polyester resin is prepared as follows:
Step (1): the synthesis of the unsaturated polyester containing terminal hydroxy group
In the four mouthfuls of reaction vessels being with stirring and condensation, drop into 30 parts of tetrachlorophthalic acids successively, 30 parts of tetrabromophthalate, 35 parts of octadecane diacids, 45 parts of methylfumaric acid, 15 parts of MALEIC ANHYDRIDE, 15 parts of chlordene endo-methylene group Tetra hydro Phthalic anhydrides, 60 parts of neopentyl glycols, 55 parts of 2-ethyl-2-butyl-1, ammediol, 0.3 part of catalyzer, 150 parts of solvents, logical nitrogen also stirs, slowly be warming up to 125 DEG C, heat up gradually 165 DEG C again after maintaining 2h and continue reaction 3h, until acid number is close or reach 40mgKOH/g, continue to add 2-ethyl-2-butyl-1, ammediol, reaction 1h, stretched system acid number is less than 10mgKOH/g, and aquifer yield unchanged time be reaction end, vacuumize, washing, dry, obtain the unsaturated polyester containing terminal hydroxy group, in this step, the consumption of-OH is relative to the many 1.5mol% of the consumption of-COOH,
Step (2): the synthesis of urethane unsaturated polyester ester copolymer
Get the unsaturated polyester 80 parts, 4 containing terminal hydroxy group of the first step synthesis, 4 '-diphenylmethanediisocyanate 120 parts, catalyzer 0.1 part, solvent 200 parts add in reaction vessel, temperature reaction 2h, when-NCO% stablizes, obtains the urethane unsaturated polyester ester copolymer that end group is-NCO; Wherein, the consumption of-NCO is relative to the many 1.5mol% of the consumption of-OH (molar percentage);
Add the dihydroxypropyl dodecyl ester of accurate-metering, add catalyzer 0.3 part, stopper 0.3 part simultaneously, continue reaction, to system, NCO exhausts, stopped reaction; Vacuumize; Washing; Dry; Obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy; In this step, the consumption of dihydroxypropyl dodecyl ester has just reacted-the NCO in system;
Step (3): the synthesis of polystyrene-poly ammonia ester-unsaturated polyester ester copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00 part, vinylbenzene 150 parts, initiator 0.5 part, the solvent 300 parts of acryloxy, reacting by heating 4h, continue temperature reaction 0.5 hour, stopped reaction, vacuumize, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin.
4. the acid-proof ink according to any one of claim 1-3, is characterized in that, described carboxy-modified chlorine vinegar terpolymer, and wherein, the content of vinylchlorid (VC) is 70-85wt%, and the content of vinyl acetate is 10-20wt%.
5. the acid-proof ink according to any one of claim 1-4, is characterized in that, the chlorinatedpolyolefins of described modified by maleic acid anhydride graft is the ethylene chloride/propylene/octene random terpolymer of modified by maleic acid anhydride graft; Wherein, ethylene content is 3-5mol%; Octene content is 1-3mol%; Cl content is 12-16 % by weight; The content of maleic anhydride is 5 ~ 9 % by weight.
6. the acid-proof ink according to any one of claim 1-5, is characterized in that, described epoxy resin is epoxidized polybutadiene, and it has polyhutadiene main chain and epoxy group(ing) concurrently.
7. the acid-proof ink according to any one of claim 1-6, it is characterized in that, described epoxy resin is epoxidized polybutadiene, it has polyhutadiene main chain and epoxy group(ing) concurrently, and it selects one or more in EPOLEAD PB3600, EPOFRIEND CT310, EPOFRIENDAT501, Ricon 657, DENAREXR-45EPT.
8. the acid-proof ink according to any one of claim 1-7, it is characterized in that, described blocked polyurethane select in Sumidule BL-3175, BL-4165, BL-1100, BL-1265, DesmoduleTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm 2265, coronate 2512, coronate 2513, coronate 2520, B-830, B-815, B-846, B-870, B-874, B-88, TPA-B80E, 17B-60PX, E402-B80T one or more.
9. a preparation method for the acid-proof ink for the protection of integrated touch-control touch-screen according to any one of claim 1-8, comprises the following steps:
1) according to recipe configuration film-forming components A, B;
2) take component A-F by metering, mix under normal temperature, after stirring, grinding, namely obtains described acid-proof ink.
In step 2) in, the condition of described grinding for grind 0.5-2 hour on three-roll grinder.
10. the application for the protection of the acid-proof ink of integrated touch-control touch-screen as claimed in any one of claims 1-9 wherein.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109082158A (en) * | 2018-10-31 | 2018-12-25 | 深圳市金达盛化工有限公司 | A kind of touch screen high temperature ink and preparation method thereof |
| CN109370300A (en) * | 2018-10-31 | 2019-02-22 | 深圳市金达盛化工有限公司 | A kind of touch display screen ink |
| CN112759718A (en) * | 2020-12-30 | 2021-05-07 | 上海宝庆通用电工有限公司 | Strippable resin and preparation method thereof |
| CN113174050A (en) * | 2021-05-08 | 2021-07-27 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
| WO2021178285A1 (en) * | 2020-03-03 | 2021-09-10 | Momentive Performance Materials Inc. | Catalyst for use in binder compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109082158A (en) * | 2018-10-31 | 2018-12-25 | 深圳市金达盛化工有限公司 | A kind of touch screen high temperature ink and preparation method thereof |
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| WO2021178285A1 (en) * | 2020-03-03 | 2021-09-10 | Momentive Performance Materials Inc. | Catalyst for use in binder compositions |
| CN112759718A (en) * | 2020-12-30 | 2021-05-07 | 上海宝庆通用电工有限公司 | Strippable resin and preparation method thereof |
| CN113174050A (en) * | 2021-05-08 | 2021-07-27 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
| CN113174050B (en) * | 2021-05-08 | 2022-06-07 | 株洲市九华新材料涂装实业有限公司 | Elastic epoxy resin and application thereof |
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