CN104673140A - Peelable mask and preparation method thereof - Google Patents
Peelable mask and preparation method thereof Download PDFInfo
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- CN104673140A CN104673140A CN201510105535.XA CN201510105535A CN104673140A CN 104673140 A CN104673140 A CN 104673140A CN 201510105535 A CN201510105535 A CN 201510105535A CN 104673140 A CN104673140 A CN 104673140A
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Abstract
The invention provides a peelable mask and a preparation method thereof. The peelable mask has properties of adhesion, elasticity, peeling strength, high-temperature resistance and the like, the film forming condition is simple, a film has properties of high adhesion, elasticity, peeling strength, high-temperature resistance and the like, quick and integral peeling can be realized, no residue exists after peeling, and the peelable mask is significant in high-temperature resistance, non-sticky, anti-fogging and high in chemical reagent resistance. The peelable mask takes a chlorinated polypropylene-ethylene random copolymer, a vinyl chloride-vinyl acetate-acrylate terpolymer, polystyrene-polyurethane-unsaturated polyester resin as well as organosilicone modified acrylate rubber as main film forming matters and takes epoxy resin, cellulose acetate butyrate and blocked polyurethane as auxiliary film forming matters.
Description
Technical field
The present invention relates to a kind of peelable glue and preparation method thereof, belong to functional high polymer material field.
Background technology
Along with the development of touch screen technology, touch-screen mobile phone and panel computer become the main flow of mass consumption just gradually.In production touch-screen process, need the protection ITO layer of touch-screen being carried out to high temperature resistance and acid and alkali corrosion in specific operation, after this operation, need protective membrane to peel off to carry out subsequent processing.Therefore, in today that touch-screen demand is growing, commute printing, sticking power is good and be easy to peel off, and the demand with the peelable protective film of excellent mechanical performances becomes more urgent.
Peelable glue, except having suitable sticking power and rippability to protection basal plane, also requires that film has good high thermal resistance, elasticity, intensity and chemical proofing etc. simultaneously.
CN103627313A peelable protecting materials disclosing a kind of ultraviolet light polymerization and its preparation method and application.This peelable protecting materials comprises the component of following parts by weight: polyurethane-modified polyacrylate 50 ~ 90%, esters of acrylic acid reactive thinner 5 ~ 35%, light trigger 1 ~ 8%, filler 1 ~ 15% and auxiliary agent 0 ~ 10%.The peelable protecting materials of ultraviolet light polymerization of the present invention adopts UV-light to cause chain polymerization, and set time is short, and general set time is 1 ~ 5 second, and production efficiency is high; Do not discharge organic gas completely, more environmental protection; Use operating procedure is easy, because of crossing thermofixation, can not impact, be peeling the phenomenon that rear appearance is vaporific to material surface; Have and better peel off integrity, and adhesion, not haze, be applicable to the surface protection of the materials such as ito glass, ito film and PET film sheet.
CN103031053A discloses a kind of touch-screen temporary protection UV and solidifies peelable protection ink and preparation method thereof, UV solidifies peelable protection ink formulations and consists of: modified acrylic ester resin 50 ~ 70 parts, acrylate monomer 20 ~ 30 parts, light curing agent 1.0-5.0 part, thixotropic agent 0.1-1.0 part, auxiliary agent 0.1-5.0 part, pigment 0.1-1.0 part; Described preparation method is: accurately take various raw material by formula rate, first modified acrylic ester resin, acrylate monomer, light curing agent, auxiliary agent, pigment are added in reactor successively and stir, to be mixed evenly after, add thixotropic agent, discharging after being uniformly dispersed.UV of the present invention solidifies peelable protection ink and is non-solvent and does not contain phthalate substance system, more safety and environmental protection.
CN102807785A discloses high temperature resistant peelable protection ink of a kind of non-solvent and preparation method thereof; it comprises and being prepared from by the raw material of following weight proportion: vinyl chloride-vinyl acetate resin 55 ~ 65 parts; 35 ~ 45 parts, softening agent; epoxy resin 0.2 ~ 0.5 part; thermo-stabilizer 0.5 ~ 1 part, aerosil 1 ~ 2 part, toner 0.3 ~ 0.5 part; flow agent 0.6 ~ 1 part, defoamer 0.6 ~ 1 part and 0.6 ~ 1 part, tensio-active agent.This ink adopts solventless formulation, and printing and paint having no volatile substances in film process, be non-reactive ink, filming condition is simple, the excellent property of film body.
But in prior art generally there is following problem in peelable glue: the peelable glue of UV curing system due to cross-linking density too high, paint film is really up to the mark, causes sticking power to be deteriorated, easily comes off; Need in the peelable glue of non-solvent to use softening agent in a large number, when high temperature film forming, softening agent easily migrates to paint film both sides, causes the variation such as sticking power, thermotolerance, do not have the effect of protection, and softening agent is unfriendly to human body.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the problems of the prior art, peelable glue of a kind of excellent combination property and preparation method thereof is provided, it is simple containing softening agent, filming condition, and film body has good rippability, moderate sticking power, the performance such as high temperature resistant.Peelable glue snappiness prepared by the present invention and good springiness, sticking power is moderate, can realize quick monoblock and peel off, and without any residual after stripping, and resistance to elevated temperatures is remarkable, and adhesion, does not haze, and chemical-resistant reagent ability is strong.
The technical solution adopted in the present invention is:
A kind of peelable glue, its main film forming substance: polystyrene-poly ammonia ester-unsaturated polyester resin 25-30 part; Chlorinated Polypropylene III-ethylene atactic copolymer 20-40 part; Vinyl chloride-vinyl acetate-acrylate terpolymer 20-30 part; Organosilicon-modified acrylate rubber 30-40 part;
Described polystyrene-poly ammonia ester-unsaturated polyester resin has the sticking power of the chemical-resistant of polystyrene, the snappiness of urethane and unsaturated polyester resin concurrently.In the composition by adding the multipolymer containing this three block, except playing the characteristic of polystyrene, urethane, unsaturated polyester, also create good synergy, it gives paint film good rippability, and its result of use is much better than polystyrene, urethane, unsaturated polyester to add in composition as independent component; And described polystyrene-poly ammonia ester-unsaturated polyester resin contains the residue of (methyl) acryloxy, by molecular designing, described polystyrene-poly ammonia ester-unsaturated polyester resin is made to have the characteristic of acrylic polymer.
The preparation method of described polystyrene-poly ammonia ester-unsaturated polyester resin can adopt the preparation method of this area routine.Polymerization process can be: the first step, be polymerized with excessive polyol condensating the unsaturated polyester obtained containing hydroxyl by binary unsaturated carboxylic acid or acid anhydrides, then reacting with polyisocyanates, by controlling the consumption of isocyanic ester, obtaining the urethane-unsaturated polyester resin containing-NCO end group; And then add (methyl) acrylic acid hydroxy alkyl ester, by controlling the consumption of (methyl) acrylic acid hydroxy alkyl ester, end group is changed into (methyl) acryloxy; Finally add vinylbenzene, by the copolymerization of vinylbenzene and acryloxy, obtain polystyrene-poly ammonia ester-unsaturated polyester resin.
Preferably described polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer number-average molecular weight is 5000 ~ 150000; Molecular weight distribution is at 1.5-3.
Described polystyrene-poly ammonia ester-unsaturated polyester ester copolymer, preferably its synthesis the steps include:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
20-50 part behenic acid, 10-50 part fumaric acid, 20-50 part maleic anhydride, 5-20 part Tetra hydro Phthalic anhydride, 60-100 part ethylene glycol, 100-120 part tetramethylolmethane, 20-40 part glycerine, 80-200 part pimelinketone, 1-50 part vitriol oil are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 10-100 part propylene glycol (be-OH to make the end group of polycondensate), reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, cools, for subsequent use.
(2) synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing unsaturated polyester 50-80 part of terminal hydroxy group, isophorone diisocyanate IPDI 100-160 part, polyether glycol (Mn=6000) 20-50 part, dibutyl tin laurate 0.2-5 part, 50-100 part pimelinketone, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 60-100 part, add dibutyl tin laurate 0.1-3 part and phenolic inhibitor 0.1-5 part continuation reaction, to system, NCO exhausts, stopped reaction simultaneously, vacuumize, obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy.
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00-250 part of acryloxy, vinylbenzene 80-140 part, AIBN 1-5 part, 80-180 part pimelinketone; 80 DEG C are heated under protection of inert gas; react 2 hours; continue to be warming up to 115 DEG C; react 1 hour; underpressure distillation desolvation, namely obtains described polystyrene-poly ammonia ester-unsaturated polyester resin.
Preferably, the preparation method of described polystyrene-poly ammonia ester-unsaturated polyester ester copolymer is:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of Tetra hydro Phthalic anhydrides, 80 parts of ethylene glycol, 100 parts of tetramethylolmethanes, 20 parts of glycerine, 100 parts of pimelinketone, 2.6 parts of vitriol oils are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 20 parts of propylene glycol, reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, and cooling is for subsequent use.
(2) synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing the unsaturated polyester 60 parts of terminal hydroxy group, isophorone diisocyanate IPDI 150 parts, polyether glycol 20 parts, dibutyl tin laurate 0.5 part, 80 parts of pimelinketone, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 90 parts, add dibutyl tin laurate 0.3 part and phenolic inhibitor 0.5 part continuation reaction, to system, NCO exhausts, and stopped reaction vacuumizes, and obtains the urethane unsaturated polyester ester copolymer that end group is acryloxy simultaneously.
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester ester copolymer 200 parts, vinylbenzene 120 parts, AIBN 1.5 parts, 150 parts of pimelinketone of acryloxy; 80 DEG C are heated under protection of inert gas; react 2 hours; continue to be warming up to 115 DEG C; react 1 hour; underpressure distillation desolvation, namely obtains described polystyrene-poly ammonia ester-unsaturated polyester resin.
Preferably, Chlorinated Polypropylene III-ethylene atactic copolymer 25-30 part; Vinyl chloride-vinyl acetate-acrylate terpolymer 25-30 part; Organosilicon-modified acrylate rubber 35-40 part; Polystyrene-poly ammonia ester-unsaturated polyester resin 25-30 part;
Wherein, in preferred described Chlorinated Polypropylene III-ethylene atactic copolymer, cl content is 15wt%-25wt%; The weight average number-average molecular weight of polymkeric substance is 400.000-800.000; Number average molecular weight distribution is less than 3; Applicant finds, in the system of the application, in the situation of cl content lower than 15wt%, paint film adhesion is deteriorated; Its cl content is higher than 25 % by weight, and the strippability of paint film declines.
Preferably, the weight average number-average molecular weight of vinyl chloride-vinyl acetate-acrylate terpolymer is 40.000-80.000;
Preferably, silicone content described in organosilicon-modified acrylate rubber is 5-10wt%, weight average number-average molecular weight is 50.000-600.000, described acrylate monomer can be one or more of following material: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) i-butyl base ester, (methyl) vinylformic acid amyl group ester, (methyl) vinylformic acid polyhexamethylene, (methyl) vinylformic acid octyl group ester, (methyl) nonylphenol acrylate ester, (methyl) lauryl acrylate, (methyl) trimethylcyclohexylacrylate, (methyl) isobutyl acrylate, (methyl) t-butylcyclohexyl base ester.Organosilane monomer can be one or more of following material: γ-acryloxypropyl Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl three (2-methoxy ethoxy) silane, vinyltrimethoxy silane, vinyltriethoxysilane and vinyl three (2-methoxy ethoxy) silane, acryloxy silane, methacryloxypropyl silane, vinyl alkoxysilicone, vinyl methyl diacetoxy silane, propylene acid group closes propyl group triacetoxysilane, (methyl) propylene acid group closes propyl group triacetoxysilane.
Applicant surprisingly finds, not by theory restriction of the prior art, four kinds of polymkeric substance of above-mentioned consumption are in film process, except playing respective characteristic, cooperatively interact between component, learn from other's strong points to offset one's weaknesses, can produce good synergy, its effect is much better than one or both resins be used alone wherein; Adopt four kinds of polymkeric substance of above-mentioned consumption as film forming matter, paint film can balance sticking power and strippability very well; Especially described polystyrene-poly ammonia ester-unsaturated polyester resin, it, while giving the good strippability of paint film very well, significantly improves the high thermal resistance of ink.
The more unexpected discovery of applicant, adds the film forming subsidiary material matter of following consumption in above-mentioned formula, and decapacitation balances outside sticking power and strippability further, can also improve the high thermal resistance of paint film, and produces Self-leveling effect, without the need to adding other flow agent.Described film forming subsidiary material matter consists of: cellulose acetate butyrate, 10-15 part; Epoxy resin, 10-15 part, blocked polyurethane, 10-15 part; Preferably, film forming subsidiary material matter also contains: organic tin catalyzer, 1-2 part.
Because epoxy resin is the known material of prior art, do not repeat them here.Preferred epoxy to be oxirane value be 0.8 ~ 1.2 epoxy resin; Epoxy resin is commonly used in suitable epoxy resin this area, as used one or more in glycidyl ether compound, cycloaliphatic epoxy, epoxy resin E-39, epoxy resin E-44, epoxy resin E-51, the epoxy resin E-56D such as polyoxyethylene glycol, polypropylene glycol, hexylene glycol, TriMethylolPropane(TMP), glycerine, tetramethylolmethane, Sorbitol Powder;
Based on reactive behavior, stability, color inhibition etc., in preferred blocked polyurethane ,-NCO content is at 6-9wt%, minimum solidification value being greater than 120 DEG C, as B1370B.
Any one in the preferred dibutyl tin dilaurate of organotin, Butyl Tin Trilaurate or sulfydryl oleic acid methyl tin;
Preferably, described peelable ink also contains pigment, thixotropic agent, defoamer, oxidation inhibitor, solvent etc.;
Preferred content is pigment 1-3 part; Thixotropic agent 0.1-0.5 part; Defoamer, 0.1-0.5 part; Oxidation inhibitor, 0.1-0.5 part; Solvent 20-60 part.
This area common pigments commonly used by described pigment, as the mixture of one or more in barba hispanica, ultramarine blue, cobalt blue or phthalocyanine blue;
The preferred fumed silica of described thixotropic agent;
Described defoamer is silicone antifoam agent, and its effect reduces the bubble manufacturing and produce in use procedure.
Described oxidation inhibitor is selected from the mixture of one or more in alkylation of hindered phenol, diphenyl phosphite, triphenyl phosphite, thioester, alkylation of hindered amine or hydroxybenzotriazole; Preferred alkyl Hinered phenols material four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (Irganox1010) or tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester (Irganox168).
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 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 viscosity of described peelable glue 25 DEG C time is preferably 2000 ~ 60,000cps, and preferably 20,000 ~ 30,000cps.
The preparation method of described peelable glue, the method that its preparation method adopts this area conventional, as: by as described in raw material carry out peelable glue as described in dispersed rear formation.
Preferred preparation method comprises the steps:
1) the various raw material of precise;
2) main film forming matter and solvent dispersion is even, obtain mixing solutions 1;
3) then add pigment, defoamer, oxidation inhibitor (if needs, and adding time film forming matter), three-roll grinder grinds, and obtains mixing solutions 2;
4) then add thixotropic agent, be uniformly dispersed discharging.
The application method of described peelable glue, described ink is printed on ito glass or PET film base material by silk-screen printing technique, and screen printing net plate order number is 250 orders or 300 orders, keeps scraper to be 45° angle, ink is evenly coated on base material.Through overbaking film forming after finishing printing, this film is fully peeled off from base material.
Relative to prior art, the advantage of the application:
1), in prior art, adopt vinyl chloride-vinyl acetate resin, epoxy resin, acrylate resin as the main film forming substance of peelable glue more.But, vinyl chloride-vinyl acetate resin is as conventional film forming matter, its over-all properties is bad, and conventional acrylate resin is (as (methyl) methacrylate resin, PMMA) not there is good elasticity, the sticking power of epoxy resin is not good, causes such peelable glue in use usually can not take into account sticking power and the strippability of film simultaneously, peel off time can not monoblock peel off or sticking power too poor.Applicant finds that the Chlorinated Polypropylene III-ethylene atactic copolymer of above-mentioned consumption, vinyl chloride-vinyl acetate-acrylate terpolymer, organosilicon-modified acrylate rubber, polystyrene-poly ammonia ester-unsaturated polyester resin are in film process, except playing respective characteristic, cooperatively interact between component, learn from other's strong points to offset one's weaknesses, good synergy can be produced, can balance sticking power and the strippability of paint film very well, and resistance to elevated temperatures is excellent.
2) in above-mentioned main film-forming components, add a certain amount of cellulose acetate butyrate, epoxy resin, blocked polyurethane of adding as the film forming subsidiary material of peelable glue, its effect is more excellent simultaneously.Cellulose acetate butyrate is commonly used for the auxiliary agent of ink, applicant surprisingly finds cellulose acetate butyrate as film forming matter, composite as film forming subsidiary material with epoxy resin, blocked polyurethane, by the chemical reaction between epoxy resin, blocked polyurethane, cellulose acetate butyrate (it contains hydroxyl, carboxyl etc.), three is formed micro-crosslinked in film process, form the tridimensional network of microcosmic, when not weakening other performances of paint film, improve the performances such as strippability, high temperature resistant, chemical-resistant resistance further.And the primary and secondary film forming matter described in the application, in ink film process, create good synergy, the performance of paint film is significantly promoted.
3) in peelable ink described in the application, without the need to adding flow agent, it has Self-leveling effect; And without the need to adding softening agent, more environmental protection.
4) adopt polystyrene-poly ammonia ester-unsaturated polyester resin except playing the characteristic of polystyrene, urethane, unsaturated polyester, the high thermal resistance of ink can also be significantly improved, and solving polystyrene, urethane, unsaturated polyester resin compatibility problem in the composition, its effect is much better than to add polystyrene, urethane, unsaturated polyester respectively.And polystyrene-poly ammonia ester-unsaturated polyester resin and all the other components create good synergy, improve the over-all properties of material.
Test event
Film-forming properties is tested
The ito glass substrate printing peelable glue of the present invention is placed under 145-160 DEG C of condition and takes out after baking 20 ~ 30min, observe film forming situation, comprise edge contracting ink, shrinkage cavity, whether film chaps, finger touches film forming dry and comfortable.If film forming does not have above-mentioned any one situation, be designated as "○"; If film forming has above-mentioned any one situation, be designated as "×".
Adhesion strippability is tested
By peelable glue silk-screen of the present invention in ito glass substrate 25mm*20cm, and 20-30min film forming is toasted under 145-160 DEG C of condition, then, stretch along 180 ° of directions (inverse approach) by peeling rate 300mm/min, start peel off masterpiece be peeling force, unit " gf/inch ".When peeling force is at 10-30gf/inch, monoblock is peeled off noresidue then to adhere to strippability best, is designated as " 00 "; When peeling force is at 10-30gf/inch, monoblock is peeled off but to have minimal residue (revolution mark is less than 5%) then to adhere to strippability good, is designated as "○"; The peelable noresidue when peeling force is less than 10gf/inch but adhesivity is poor, is designated as " △ "; When peeling force is greater than 30gf/inch, then the good difficulty stripping of adhesivity has residual, is designated as "×".
High temperature resistant test
By peelable glue silk-screen of the present invention in glass substrate, and toast 20-30min film forming under 145-160 DEG C of condition, be then placed on heat baking 250 DEG C × 2 hours, observe the phenomenons such as whether film shrinks, chaps, yellowing; If any not having above-mentioned phenomenon to show that thermotolerance is best, be designated as " 00 "; If have a small amount of yellowing, be full of cracks or trace to shrink show good heat resistance, be designated as "○"; If above-mentioned three kinds of phenomenons exist show that thermotolerance is poor simultaneously, be designated as "×".
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Preparation example 1
Prepare polystyrene-poly ammonia ester-unsaturated polyester ester copolymer, its synthesis the steps include:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of Tetra hydro Phthalic anhydrides, 80 parts of ethylene glycol, 100 parts of tetramethylolmethanes, 20 parts of glycerine, 100 parts of pimelinketone, 2.6 parts of vitriol oils are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 20 parts of propylene glycol (be-OH to make the end group of polycondensate), reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, cools, for subsequent use.
(2) synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing the unsaturated polyester 60 parts of terminal hydroxy group, isophorone diisocyanate IPDI 150 parts, polyether glycol (Mn=6000) 20 parts, dibutyl tin laurate 0.5 part, 80 parts of pimelinketone, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 90 parts, add dibutyl tin laurate 0.3 part and phenolic inhibitor 0.5 part continuation reaction, to system, NCO exhausts, and stopped reaction vacuumizes, and obtains the urethane unsaturated polyester ester copolymer that end group is acryloxy simultaneously.
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester ester copolymer 200 parts, vinylbenzene 120 parts, AIBN 1.5 parts, 150 parts of pimelinketone of acryloxy; 80 DEG C are heated under protection of inert gas; react 2 hours; continue to be warming up to 115 DEG C; react 1 hour; underpressure distillation desolvation, namely obtain described polystyrene-poly ammonia ester-unsaturated polyester resin, its number-average molecular weight is 50000.
Embodiment 1
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 28 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 25 parts; Organosilicon-modified acrylate rubber 37 parts; Polystyrene-poly ammonia ester-unsaturated polyester resin 30 parts; Pigment 2 parts; Thixotropic agent 0.2 part; Defoamer, 0.3 part; Oxidation inhibitor, 0.5 part; Solvent 40 parts.
Its preparation method is:
1) the various raw material of precise;
2) main film forming matter and solvent (mass ratio, NMP: PGMEA: MEK=60: 20: 20) are uniformly dispersed, obtain mixing solutions 1;
3) then add pigment, defoamer, oxidation inhibitor, three-roll grinder grinds, and obtains mixing solutions 2;
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 2
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 30 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 30 parts; Organosilicon-modified acrylate rubber 35 parts; Polystyrene-poly ammonia ester-unsaturated polyester resin 25 parts; Cellulose acetate butyrate, 10 parts; Epoxy resin, 10 parts, blocked polyurethane, 15 parts; Organotin, 1 part; Pigment 3 parts; Thixotropic agent 0.4 part; Defoamer, 0.5 part; Oxidation inhibitor, 0.4 part; Solvent 20 parts.
Its preparation method is:
1) the various raw material of precise;
2) main film forming matter and solvent dispersion is even, obtain mixing solutions 1;
3) then add pigment, defoamer, oxidation inhibitor, secondary film forming matter, three-roll grinder grinds, and obtains mixing solutions 2;
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 3
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 35 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 25 parts; Organosilicon-modified acrylate rubber 30 parts; Polystyrene-poly ammonia ester-unsaturated polyester resin 30 parts; Cellulose acetate butyrate, 11 parts; Epoxy resin, 12 parts, blocked polyurethane, 10 parts; Organotin, 2 parts; Pigment 2 parts; Thixotropic agent 0.3 part; Defoamer, 0.5 part; Oxidation inhibitor, 0.4 part; Solvent 30 parts.
Its preparation method is:
1) the various raw material of precise;
2) main film forming matter and solvent dispersion is even, obtain mixing solutions 1;
3) then add pigment, defoamer, oxidation inhibitor, secondary film forming matter, three-roll grinder grinds, and obtains mixing solutions 2;
4) then add thixotropic agent, be uniformly dispersed discharging.
Embodiment 4
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 28 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 25 parts; Organosilicon-modified acrylate rubber 37 parts; Polystyrene-poly ammonia ester-unsaturated polyester resin 30 parts; Cellulose acetate butyrate, 12 parts; Epoxy resin, 12 parts, blocked polyurethane, 15 parts; Organotin, 1.5 parts; Pigment 2 parts; Thixotropic agent 0.3 part; Defoamer, 0.5 part; Oxidation inhibitor, 0.4 part; Solvent 30 parts.
Its preparation method is:
1) the various raw material of precise;
2) main film forming matter and solvent dispersion is even, obtain mixing solutions 1;
3) then add pigment, defoamer, oxidation inhibitor, secondary film forming matter, three-roll grinder grinds, and obtains mixing solutions 2;
4) then add thixotropic agent, be uniformly dispersed discharging.
Comparative example 1
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 80 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 20 parts; Organosilicon-modified acrylate rubber 20 parts; Polystyrene-poly ammonia ester-unsaturated polyester resin 5 parts; Pigment 2 parts; Thixotropic agent 0.2 part; Defoamer, 0.3 part; Oxidation inhibitor, 0.5 part; Solvent 40 parts.
Its preparation method is with embodiment 1.
Comparative example 2
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 50 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 40 parts; Organosilicon-modified acrylate rubber 30 parts; Pigment 2 parts; Thixotropic agent 0.2 part; Defoamer, 0.3 part; Oxidation inhibitor, 0.5 part; Solvent 40 parts.
Its preparation method is with embodiment 1.
Comparative example 3
Described peelable glue is containing, for example lower raw material:
Chlorinated Polypropylene III-ethylene atactic copolymer 28 parts; Vinyl chloride-vinyl acetate-acrylate terpolymer 25 parts; Organosilicon-modified acrylate rubber 37 parts; Polystyrene, 10 parts; Urethane, 10 parts; Unsaturated polyester resin, 10 parts; Cellulose acetate butyrate, 12 parts; Epoxy resin, 12 parts, blocked polyurethane, 15 parts; Organotin, 1.5 parts; Pigment 2 parts; Thixotropic agent 0.3 part; Defoamer, 0.5 part; Oxidation inhibitor, 0.4 part; Solvent 30 parts.
Its preparation method is with embodiment 1.
Comparative example 4
The peelable glue of prior art, containing following component: vinyl chloride-vinyl acetate resin, 40 parts; MMA resin, 15 parts; Epoxy resin, 10 parts; Octyl adipate, 23 parts; Epoxy soybean oil, 10 parts
Adopt identical technique, by the peelable glue of embodiment, comparative example by the even coating glass substrate of silk-screen printing technique, test.
Test result is as described in Table 1
Table 1
| Numbering | Film-forming properties | Adhere to strippability | High temperature resistant | Comprehensive Assessment |
| Embodiment 1 | ○ | ○ | ○ | Good |
| Embodiment 2 | ○○ | ○○ | ○○ | Excellent |
| Embodiment 3 | ○○ | ○○ | ○○ | Excellent |
| Embodiment 4 | ○○ | ○○ | ○○ | Excellent |
| Comparative example 1 | ○ | × | ○ | Difference |
| Comparative example 2 | × | △ | × | Difference |
| Comparative example 3 | × | △ | × | Difference |
| Comparative example 4 | × | × | × | Difference |
From the test result of table 1, peelable glue simultaneously containing the main film forming matter (Chlorinated Polypropylene III-ethylene atactic copolymer, vinyl chloride-vinyl acetate-acrylate terpolymer, organosilicon-modified acrylate rubber, polystyrene-poly ammonia ester-unsaturated polyester resin) in specific amount ranges described in the application takes into account sticking power, stripping strength, elasticity, the performance such as high temperature resistant simultaneously, have unforeseeable technique effect, its performance is much better than the peelable glue adopting vinyl chloride-vinyl acetate resin, (methyl) methacrylate resin, epoxy resin as film forming matter.And as can be seen from experimental data obviously, adopt the peelable glue of Chlorinated Polypropylene III-ethylene atactic copolymer, vinyl chloride-vinyl acetate-acrylate terpolymer, organosilicon-modified acrylate rubber, polystyrene-poly ammonia ester-unsaturated polyester resin simultaneously, its effect is much better than one or more the peelable glue be used alone wherein, has good synergy between these three kinds of polymkeric substance; Adopt epoxy resin, cellulose acetate butyrate, blocked polyurethane as film forming subsidiary material, it adheres to strippability, high thermal resistance is largely increased; Relative to adopting epoxy resin separately, it does not reach the synergy between epoxy resin and cellulose acetate butyrate, blocked polyurethane; Add the high thermal resistance that polystyrene-poly ammonia ester-unsaturated polyester resin can improve peelable glue.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a peelable glue, is characterized in that, the component of its filmogen and consumption are: polystyrene-poly ammonia ester-unsaturated polyester resin 25-30 part; Chlorinated Polypropylene III-ethylene atactic copolymer 20-40 part; Vinyl chloride-vinyl acetate-acrylate terpolymer 20-30 part; Organosilicon-modified acrylate rubber 30-40 part; Wherein, described polystyrene-poly ammonia ester-unsaturated polyester resin contains the residue of (methyl) acryloxy; In described Chlorinated Polypropylene III-ethylene atactic copolymer, cl content is 15wt%-25wt%, and its number-average molecular weight is 400.000-800.000.
2. peelable glue as claimed in claim 1, is characterized in that, except film forming matter described in claim 1, the secondary filmogen of described filmogen also containing following component and content is: cellulose acetate butyrate, 10-15 part; Epoxy resin, 10-15 part, blocked polyurethane, 10-15 part.
3. peelable glue as claimed in claim 1 or 2, is characterized in that, preferably: Chlorinated Polypropylene III-ethylene atactic copolymer 25-30 part; Vinyl chloride-vinyl acetate-acrylate terpolymer 25-30 part; Organosilicon-modified acrylate rubber 35-40 part; Polystyrene-poly ammonia ester-unsaturated polyester resin 25-30 part.
4. peelable glue as claimed in claim 2 or claim 3, it is characterized in that, secondary film forming matter consists of: cellulose acetate butyrate, 10-15 part; Epoxy resin, 10-15 part, blocked polyurethane, 10-15 part; Organic tin catalyzer, 1-2 part.
5. the peelable glue as described in any one of claim 1-4, is characterized in that, in described Chlorinated Polypropylene III-ethylene atactic copolymer, cl content is 15wt%-25wt%; Vinyl chloride-vinyl acetate-acrylate terpolymer content of vinylchloride is 61.0 ± 1.0wt%; Vinyl acetate content 39.0 ± 1.0wt%.
6. the peelable glue as described in any one of claim 1-5, is characterized in that, the polymerization process of described polystyrene-poly ammonia ester-unsaturated polyester resin is:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
20-50 part behenic acid, 10-50 part fumaric acid, 20-50 part maleic anhydride, 5-20 part Tetra hydro Phthalic anhydride, 60-100 part ethylene glycol, 100-120 part tetramethylolmethane, 20-40 part glycerine, 80-200 part pimelinketone, 1-50 part vitriol oil are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 10-100 part propylene glycol, reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, and cooling is for subsequent use;
(2) synthesis of urethane unsaturated polyester ester copolymer
Get unsaturated polyester 50-80 part containing terminal hydroxy group of the first step synthesis, isophorone diisocyanate IPDI 100-160 part, polyether glycol 20-50 part of Mn=6000, dibutyl tin laurate 0.2-5 part, 50-100 part pimelinketone add in reaction vessel, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 60-100 part, add dibutyl tin laurate 0.1-3 part and phenolic inhibitor 0.1-5 part continuation reaction, to system, NCO exhausts, stopped reaction simultaneously, vacuumize, obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy;
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00-250 part of acryloxy, vinylbenzene 80-140 part, AIBN 1-5 part, 80-180 part pimelinketone; 80 DEG C are heated under protection of inert gas; react 2 hours; continue to be warming up to 115 DEG C; react 1 hour; underpressure distillation desolvation, namely obtains described polystyrene-poly ammonia ester-unsaturated polyester resin.
7. the peelable glue as described in any one of claim 1-6, is characterized in that, it also contains: pigment 1-3 part; Thixotropic agent 0.1-0.5 part; Defoamer, 0.1-0.5 part; Oxidation inhibitor, 0.1-0.5 part; Solvent 20-60 part.
8. the peelable glue as described in any one of claim 1-7, is characterized in that, the polymerization process of described polystyrene-poly ammonia ester-unsaturated polyester resin is:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
20-50 part behenic acid, 10-50 part fumaric acid, 20-50 part maleic anhydride, 5-20 part Tetra hydro Phthalic anhydride, 60-100 part ethylene glycol, 100-120 part tetramethylolmethane, 20-40 part glycerine, 80-200 part pimelinketone, 1-50 part vitriol oil are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 10-100 part propylene glycol, reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, and cooling is for subsequent use;
(2) synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing unsaturated polyester 50-80 part of terminal hydroxy group, isophorone diisocyanate IPDI 100-160 part, polyether glycol 20-50 part of Mn=6000, dibutyl tin laurate 0.2-5 part, 50-100 part pimelinketone, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 60-100 part, add dibutyl tin laurate 0.1-3 part and phenolic inhibitor 0.1-5 part continuation reaction, to system, NCO exhausts, stopped reaction simultaneously, vacuumize, obtain the urethane unsaturated polyester ester copolymer that end group is acryloxy;
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester copolymer 1 00-250 part of acryloxy, vinylbenzene 80-140 part, AIBN 1-5 part, 80-180 part pimelinketone, 80 DEG C are heated under protection of inert gas, react 2 hours, continue to be warming up to 115 DEG C, react 1 hour, underpressure distillation desolvation, namely obtains described polystyrene-poly ammonia ester-unsaturated polyester resin;
Preferably described polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer number-average molecular weight is 5000 ~ 150000; Molecular weight distribution is at 1.5-3.
9. a Self-leveling peelable glue, is characterized in that, it is made up of following component and content:
Main film forming matter: Chlorinated Polypropylene III-ethylene atactic copolymer 25-30 part; Vinyl chloride-vinyl acetate-acrylate terpolymer 25-30 part; Organosilicon-modified acrylate rubber 35-40 part; Polystyrene-poly ammonia ester-unsaturated polyester resin 25-30 part;
Film forming subsidiary material matter consists of: cellulose acetate butyrate, 10-15 part; Epoxy resin, 10-15 part, blocked polyurethane, 10-15 part; Organic tin catalyzer, 1-2 part;
Pigment 1-3 part; Thixotropic agent 0.1-0.5 part; Defoamer, 0.1-0.5 part; Oxidation inhibitor, 0.1-0.5 part; Solvent 20-60 part;
The preparation method of described polystyrene-poly ammonia ester-unsaturated polyester resin is:
(1) synthesis of the unsaturated polyester containing terminal hydroxy group
40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of Tetra hydro Phthalic anhydrides, 80 parts of ethylene glycol, 100 parts of tetramethylolmethanes, 20 parts of glycerine, 100 parts of pimelinketone, 2.6 parts of vitriol oils are added in the reaction vessel that electric stirring, water trap, thermometer, electric mantle heating are housed successively, heating, stir, be warming up to 140 DEG C, react 2.5 hours; Be warming up to 155 DEG C of reactions 0.5 hour, be cooled to 100 DEG C and add 20 parts of propylene glycol, reaction 1h, vacuumizes, obtains the unsaturated polyester containing terminal hydroxy group, and cooling is for subsequent use;
(2) synthesis of urethane unsaturated polyester ester copolymer
That gets the first step synthesis adds in reaction vessel containing the unsaturated polyester 60 parts of terminal hydroxy group, isophorone diisocyanate 150 parts, polyether glycol 20 parts, dibutyl tin laurate 0.5 part, 80 parts of pimelinketone, be warming up to 100 DEG C of reaction 2h, when-NCO% stablizes, obtain the urethane unsaturated polyester ester copolymer that end group is-NCO; Add Rocryl 410 90 parts, add dibutyl tin laurate 0.3 part and phenolic inhibitor 0.5 part continuation reaction, to system, NCO exhausts, and stopped reaction vacuumizes, and obtains the urethane unsaturated polyester ester copolymer that end group is acryloxy simultaneously;
(3) synthesis of polystyrene-poly ammonia ester-unsaturated polyester polyurethane copolymer
The end group getting second step synthesis is urethane unsaturated polyester ester copolymer 200 parts, vinylbenzene 120 parts, AIBN 1.5 parts, 150 parts of pimelinketone of acryloxy; 80 DEG C are heated under protection of inert gas; react 2 hours; continue to be warming up to 115 DEG C; react 1 hour; underpressure distillation desolvation, namely obtains described polystyrene-poly ammonia ester-unsaturated polyester resin.
10. the application of a peelable glue as described in any one of claim 1-9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176226A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Environmental-friendly reactive peelable blue glue |
| CN105176299A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Low-temperature thermal-curing peelable blue glue |
| CN105176275A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Electric corrosion-resistant peelable blue glue |
| CN105623412A (en) * | 2016-02-24 | 2016-06-01 | 湖南皓志科技股份有限公司 | Temporary protection type high-temperature-resistant peelable glue and preparing method thereof |
| CN109749512A (en) * | 2018-04-13 | 2019-05-14 | 厦门蓝科电子科技有限公司 | A kind of peelable indigo plant glue of environment-friendly type and preparation method thereof being halogen-free |
| CN110330919A (en) * | 2019-07-03 | 2019-10-15 | 昆山博益鑫成高分子材料有限公司 | A kind of UV visbreaking glue |
| CN111139015A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Environment-friendly UV LED (ultraviolet light emitting diode) curing peelable blue glue and preparation method thereof |
| CN113788928A (en) * | 2021-09-07 | 2021-12-14 | 肇庆市宝骏化工有限公司 | High-temperature-resistant and high-elongation polyurethane acrylic resin and application thereof in preparation of ultraviolet-cured peelable glue |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1270210A2 (en) * | 2001-06-26 | 2003-01-02 | Sumitomo Bakelite Company Limited | Cover tape for packaging electronic components |
| CN101072678A (en) * | 2004-12-10 | 2007-11-14 | 三菱瓦斯化学株式会社 | Laminate film |
| CN101255324A (en) * | 2007-02-26 | 2008-09-03 | 北京高盟化工有限公司 | Trans-printing composition and preparation method thereof |
| CN102559078A (en) * | 2011-12-28 | 2012-07-11 | 广州鹿山新材料股份有限公司 | Hot melt adhesive membrane for bonding bi-metallic composite plate and preparing method thereof |
-
2015
- 2015-03-05 CN CN201510105535.XA patent/CN104673140B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1270210A2 (en) * | 2001-06-26 | 2003-01-02 | Sumitomo Bakelite Company Limited | Cover tape for packaging electronic components |
| CN101072678A (en) * | 2004-12-10 | 2007-11-14 | 三菱瓦斯化学株式会社 | Laminate film |
| CN101255324A (en) * | 2007-02-26 | 2008-09-03 | 北京高盟化工有限公司 | Trans-printing composition and preparation method thereof |
| CN102559078A (en) * | 2011-12-28 | 2012-07-11 | 广州鹿山新材料股份有限公司 | Hot melt adhesive membrane for bonding bi-metallic composite plate and preparing method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176226A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Environmental-friendly reactive peelable blue glue |
| CN105176299A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Low-temperature thermal-curing peelable blue glue |
| CN105176275A (en) * | 2015-07-24 | 2015-12-23 | 中山市伯伦克专用化学产品有限公司 | Electric corrosion-resistant peelable blue glue |
| CN105623412A (en) * | 2016-02-24 | 2016-06-01 | 湖南皓志科技股份有限公司 | Temporary protection type high-temperature-resistant peelable glue and preparing method thereof |
| CN105623412B (en) * | 2016-02-24 | 2017-12-19 | 湖南皓志科技股份有限公司 | A kind of interim protection type heat-resisting quantity peelable glue and preparation method thereof |
| CN109749512A (en) * | 2018-04-13 | 2019-05-14 | 厦门蓝科电子科技有限公司 | A kind of peelable indigo plant glue of environment-friendly type and preparation method thereof being halogen-free |
| CN110330919A (en) * | 2019-07-03 | 2019-10-15 | 昆山博益鑫成高分子材料有限公司 | A kind of UV visbreaking glue |
| CN111139015A (en) * | 2019-12-31 | 2020-05-12 | 天津久日新材料股份有限公司 | Environment-friendly UV LED (ultraviolet light emitting diode) curing peelable blue glue and preparation method thereof |
| CN113788928A (en) * | 2021-09-07 | 2021-12-14 | 肇庆市宝骏化工有限公司 | High-temperature-resistant and high-elongation polyurethane acrylic resin and application thereof in preparation of ultraviolet-cured peelable glue |
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