CN104673140B - A kind of peelable glue and preparation method thereof - Google Patents
A kind of peelable glue and preparation method thereof Download PDFInfo
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- CN104673140B CN104673140B CN201510105535.XA CN201510105535A CN104673140B CN 104673140 B CN104673140 B CN 104673140B CN 201510105535 A CN201510105535 A CN 201510105535A CN 104673140 B CN104673140 B CN 104673140B
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Abstract
The present invention provides a kind of peelable glue and preparation method thereof, it takes into account the performances such as adhesive force, elasticity, peel strength, high temperature resistant simultaneously, its membrance casting condition is simple, film body has the performances such as good adhesive force, elasticity, peel strength, high temperature resistant, it can realize that quick monoblock is peeled off, without any residual after stripping, and resistance to elevated temperatures is notable, and adhesion, do not haze, chemical-resistant reagent ability is strong.Chlorinated polypropylene ethylene atactic copolymer, vinyl chloride vinyl acetate acrylic acid ester terpolymer, polystyrene polyurethane unsaturated polyester resin and the organosilicon-modified acrylate rubber that the peelable glue uses are as main film forming matter；Using epoxy resin, acetylbutyrylcellulose, blocked polyurethane peelable glue film forming subsidiary material.
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
With the continuous development of touch screen technology, touch-screen mobile phone is increasingly becoming the main flow of mass consumption with tablet personal computer.
The guarantor of high temperature resistance and acid and alkali corrosion is carried out to the ITO layer of touch-screen during touch-screen is produced, it is necessary in specific process
Shield, need to peel off diaphragm after the process to carry out subsequent processing.Therefore, in touch-screen demand growing today,
To easily printing, adhesive force is good and is easily peeled off, and the demand with the peelable protective film of excellent mechanical performances becomes more to step up
Compel.
Peelable glue also requires that film has preferably in addition to having suitable adhesive force and rippability to protection basal plane
Heat-resisting quantity, elasticity, intensity and chemical proofing etc..
CN103627313A discloses a kind of peelable protection materials of ultraviolet light solidification and its preparation method and application.Should
Peelable protection materials include the component of following parts by weight meter：Polyurethane-modified polyacrylate 50~90%, esters of acrylic acid are lived
Property diluent 5~35%, light trigger 1~8%, filler 1~15% and auxiliary agent 0~10%.The ultraviolet light solidification of the present invention
Peelable protection materials use ultraviolet light-initiated chain polymerization, and hardening time is short, and general hardening time is 1~5 second, production efficiency
It is high；Organic gas is not discharged completely, it is more environmentally-friendly；It is easy using operating procedure, material surface will not be made because of heat cure is crossed
Into influence, occurs vaporific phenomenon after being peeling；Integrality is peeled off with more preferable, and adhesion, is not hazed, and is applied to
The surface protection of the materials such as ito glass, ito film and PET film piece.
CN103031053A discloses a kind of peelable protection ink of the interim protection UV solidifications of touch-screen and its preparation side
Method, the peelable protection ink formulations composition of UV solidifications are：50~70 parts of modified acrylic ester resin, acrylate monomer 20~30
Part, light curing agent 1.0-5.0 parts, thixotropic agent 0.1-1.0 parts, auxiliary agent 0.1-5.0 parts, pigment 0.1-1.0 parts；The preparation method
For：Various raw materials are accurately weighed by formula rate, first by modified acrylic ester resin, acrylate monomer, light curing agent, help
Agent, pigment are sequentially added in reactor and stirred, it is to be mixed uniformly after, add thixotropic agent, discharged after being uniformly dispersed.The UV of the present invention
Solidify peelable protection ink to be non-solvent and be free of phthalate substance system, more safety and environmental protection.
CN102807785A discloses peelable protection ink of a kind of non-solvent high temperature resistant and preparation method thereof, and it includes
It is prepared by the raw material of following weight proportion：55~65 parts of vinyl chloride-vinyl acetate resin, 35~45 parts of plasticizer, epoxy resin 0.2~0.5
Part, 0.5~1 part of heat stabilizer, 1~2 part of aerosil, 0.3~0.5 part of toner, 0.6~1 part of levelling agent, defoamer
0.6~1 part and 0.6~1 part of surfactant.The ink uses solventless formulation, printing and non-volatility thing in film forming procedure
Matter, it is non-reactive ink, membrance casting condition is simple, the function admirable of film body.
But peelable glue generally there are problems with the prior art：The peelable glue of UV curing systems is due to crosslink density
Too high, paint film is really up to the mark, causes adhesive force to be deteriorated, and easily comes off；Need largely to use plasticizer in the peelable glue of non-solvent,
Plasticizer is easily migrated to paint film both sides during high temperature film forming, is caused adhesive force, heat resistance etc. to be deteriorated, is not had the effect of protection,
And plasticizer is unfriendly to human body.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the problems of the prior art, there is provided a kind of combination property is excellent
Different peelable glue and preparation method thereof, it is not contained, and plasticizer, membrance casting condition are simple, and film body has good rippability, fitted
In adhesive force, the performance such as high temperature resistant.Peelable glue pliability and elasticity prepared by the present invention is good, and adhesive force is moderate, can realize fast
Fast monoblock is peeled off, and without any residual after stripping, and resistance to elevated temperatures is notable, and adhesion, is not hazed, chemical-resistant reagent ability
By force.
The technical solution adopted in the present invention is：
A kind of peelable glue, its main film forming substance：Polystyrene-poly urethane-unsaturated polyester resin 25-30 parts；Chlorination
Polypropylene-ethylene random copolymer 20-40 parts；Vinyl chloride-vinyl acetate-acrylate terpolymer 20-30 parts；Organosilicon
Modification acrylate rubber 30-40 parts；
Polystyrene-poly urethane-the unsaturated polyester resin have concurrently the chemical-resistant of polystyrene, polyurethane it is soft
The adhesive force of toughness and unsaturated polyester resin.In the composition by adding the copolymer containing the three block, except performance
Polystyrene, polyurethane, unsaturated polyester (UP) characteristic outside, also create good synergy, its assign paint film it is good can
Fissility, its using effect are much better than as independent component to add polystyrene, polyurethane, unsaturated polyester (UP) in composition；
Moreover, the polystyrene-poly urethane-unsaturated polyester resin contains the residue of (methyl) acryloxy, set by molecule
Meter, makes described polystyrene-poly urethane-unsaturated polyester resin have the characteristic of acrylic polymer.
The preparation method of the polystyrene-poly urethane-unsaturated polyester resin can use the conventional preparation in this area
Method.Polymerization can be：The first step, it is polymerize by binary unsaturated carboxylic acid or acid anhydrides with the polyol condensating of excess and is contained
There is the unsaturated polyester (UP) of hydroxyl, then reacted with polyisocyanates, by controlling the dosage of isocyanates, contained-NCO
Polyurethane-unsaturated polyester resin of end group；Then (methyl) acrylic acid hydroxy alkyl ester is added, by controlling (methyl) propylene
The dosage of sour hydroxy alkyl ester, end group is changed into (methyl) acryloxy；Styrene is eventually adding, passes through styrene and propylene
The copolymerization of acyloxy, obtain polystyrene-poly urethane-unsaturated polyester resin.
It is preferred that described polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer number-average molecular weight be 5000~
150000；Molecular weight distribution is in 1.5-3.
Polystyrene-poly urethane-unsaturated polyester (UP) the copolymer, preferable its synthesize its step and are：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 20-50 parts behenic acid, 10-50 parts fumaric acid, 20-50 parts maleic anhydride, 5-20 parts phthalic anhydride, 60-
100 parts of ethylene glycol, 100-120 parts pentaerythrite, 20-40 parts glycerine, 80-200 parts cyclohexanone, 1-50 part concentrated sulfuric acids sequentially add
In the reaction vessel heated equipped with electric stirring, water knockout drum, thermometer, electric jacket, heat, stirring, be warming up to 140 DEG C, reaction
2.5 hour；It is warming up to 155 DEG C to react 0.5 hour, is cooled to 100 DEG C and adds 10-100 parts propane diols (so that the end group of condensation polymer
For-OH), 1h is reacted, vacuumizes, obtains the unsaturated polyester (UP) containing terminal hydroxy group, is cooled down, it is standby.
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
Take unsaturated polyester (UP) 50-80 parts containing terminal hydroxy group, the IPDI IPDI of first step synthesis
100-160 parts, PPG (Mn=6000) 20-50 parts, dibutyl tin laurate 0.2-5 parts, 50-100 part cyclohexanone
Add in reaction vessel, be warming up to 100 DEG C of reaction 2h, when-NCO% is stable, it is unsaturated to obtain the polyurethane that end group is-NCO
Polyester copolymer；Hydroxy propyl methacrylate 60-100 parts are added, while add dibutyl tin laurate 0.1-3 parts and phenols
Polymerization inhibitor 0.1-5 parts continue to react, and into system, NCO exhausts, and stop reaction, vacuumize, and obtain end group as acryloxy
Polyurethane unsaturated polyester (UP) copolymer.
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
The end group for taking second step to synthesize is polyurethane unsaturated polyester (UP) copolymer 1 00-250 parts of acryloxy, benzene second
Alkene 80-140 parts, AIBN 1-5 parts, 80-180 part cyclohexanone, 80 DEG C are heated under inert gas shielding, reacted 2 hours, after
It is continuous to be warming up to 115 DEG C, react 1 hour, be evaporated under reduced pressure desolvation, that is, it is poly- to obtain described polystyrene-poly urethane-unsaturation
Ester resin.
It is preferred that the preparation method of the polystyrene-poly urethane-unsaturated polyester (UP) copolymer is：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of phthalic anhydrides, 80 parts of ethylene glycol, 100
Part pentaerythrite, 20 parts of glycerine, 100 parts of cyclohexanone, 2.6 parts of concentrated sulfuric acids are sequentially added equipped with electric stirring, water knockout drum, temperature
In the reaction vessel that meter, electric jacket heat, heat, stirring, be warming up to 140 DEG C, react 2.5 hours；It is warming up to 155 DEG C of reactions
0.5 hour, it is cooled to 100 DEG C and adds 20 parts of propane diols, react 1h, vacuumize, obtain the unsaturated polyester (UP) containing terminal hydroxy group, it is cold
But, it is standby.
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
60 parts of unsaturated polyester (UP), the IPDI IPDI 150 containing terminal hydroxy group for taking the first step to synthesize
0.5 part, 80 parts part, 20 parts of PPG, dibutyl tin laurate cyclohexanone are added in reaction vessel, are warming up to 100 DEG C
2h is reacted, when-NCO% is stable, obtains the polyurethane unsaturated polyester (UP) copolymer that end group is-NCO；Add hydroxyethyl methacrylate
90 parts of propyl ester, while add 0.3 part of dibutyl tin laurate and continue to react with 0.5 part of phenolic inhibitor, into system, NCO consumes
To the greatest extent, stop reaction, vacuumize, obtain the polyurethane unsaturated polyester (UP) copolymer that end group is acryloxy.
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
The end group for taking second step to synthesize is 200 parts of polyurethane unsaturated polyester (UP) copolymer, the styrene 120 of acryloxy
1.5 parts, 150 parts part, AIBN cyclohexanone, 80 DEG C are heated under inert gas shielding, react 2 hours, be continuously heating to 115
DEG C, react 1 hour, be evaporated under reduced pressure desolvation, that is, obtain described polystyrene-poly urethane-unsaturated polyester resin.
It is preferred that chlorinated polypropylene-ethylene atactic copolymer 25-30 parts；Vinyl chloride-vinyl acetate-acrylic ester ternary is common
Polymers 25-30 parts；Organosilicon-modified acrylate rubber 35-40 parts；Polystyrene-poly urethane-unsaturated polyester resin 25-30
Part；
Wherein, chlorinity is 15wt%-25wt% in preferably described chlorinated polypropylene-ethylene atactic copolymer；Polymer
The equal number-average molecular weight of weight be 400.000-800.000；Number average molecular weight distribution is less than 3；It has been found that the application's
In system, it is less than 15wt% situation in chlorinity, paint film adhesion is deteriorated；Its chlorinity is higher than 25 weight %, paint film can
Stripping property declines.
It is preferred that the equal number-average molecular weight of the weight of vinyl chloride-vinyl acetate-acrylate terpolymer is 40.000-
80.000；
It is preferred that silicone content described in organosilicon-modified acrylate rubber is 5-10wt%；The equal number-average molecular weight of weight
For 50.000-600.000；The acrylate monomer can be the one or more of following material：(methyl) methyl acrylate,
(methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) i-butyl base ester, (first
Base) acrylic acid amyl group ester, (methyl) acrylic acid hexyl ester, (methyl) acrylic acid octyl group ester, (methyl) nonylphenol acrylate ester, (first
Base) lauryl acrylate, (methyl) trimethylcyclohexylacrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid uncle
Butylcyclohexyl acetate.Organic silicon monomer can be the one or more of following material：γ-acryloxypropyl trimethoxy silicon
Alkane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl three (2- methoxy ethoxies)
Silane, vinyltrimethoxy silane, VTES and vinyl three (2- methoxy ethoxies) silane, propylene
Acyloxy silane, methacryloxypropyl silane, vinyl alkoxysilicone, vinyl methyl diacetoxy silane, third
Olefin(e) acid root closes propyl group triacetoxysilane, and (methyl) propylene acid group closes propyl group triacetoxysilane.
Applicant has been surprisingly found that, not by theoretical restriction of the prior art, four kinds of polymer of above-mentioned dosage are in film forming mistake
Cheng Zhong, in addition to respective characteristic is played, cooperate, learn from other's strong points to offset one's weaknesses between component, good synergy, its effect can be produced
It is much better than one or two kinds of resins therein are used alone；Using four kinds of polymer of above-mentioned dosage as film forming matter, paint film energy
Balance adhesive force and strippable property very well；Especially described polystyrene-poly urethane-unsaturated polyester resin, it is being assigned very well
While giving paint film good strippable property, the heat-resisting quantity of ink is significantly improved.
Applicant is more had been surprisingly found that, the subsidiary film forming matter of following dosage is added in above-mentioned formula, except can further put down
Weigh outside adhesive force and strippable property, moreover it is possible to improve the heat-resisting quantity of paint film, and be produced from levelling effect, without adding other levellings
Agent.Described subsidiary film forming matter forms：Acetylbutyrylcellulose, 10-15 parts；Epoxy resin, 10-15 parts, enclosed type are gathered
Urethane, 10-15 parts；It is preferred that subsidiary film forming matter also contains：Organic tin catalyst, 1-2 parts.
Because epoxy resin is material known in the art, will not be repeated here.Preferred epoxy is that epoxide number is
0.8~1.2 epoxy resin；Suitable epoxy resin epoxy resin commonly used in the art, such as using polyethylene glycol, polypropylene glycol,
The glycidol ether such as hexylene glycol, trimethylolpropane, glycerine, pentaerythrite, D-sorbite compound, cycloaliphatic epoxy,
One or more in epoxy resin E-39, epoxy resin E-44, epoxy resin E-51, epoxy resin E-56D；
Based on reactivity, stability, color inhibition etc., preferably in blocked polyurethane-NCO content in 6-9wt%, it is minimum
Solidification temperature is more than 120 DEG C, such as B1370B.
It is any one in the preferred dibutyl tin dilaurate of organotin, Butyl Tin Trilaurate or sulfydryl oleic acid methyl tin
Kind；
It is preferred that the peelable ink also contains pigment, thixotropic agent, defoamer, antioxidant, solvent etc.；
Preferable content is pigment 1-3 parts；Thixotropic agent 0.1-0.5 parts；Defoamer, 0.1-0.5 parts；Antioxidant, 0.1-0.5
Part；Solvent 20-60 parts.
The pigment commonly uses pigment commonly used in the art, as one or both of barba hispanica, ultramarine blue, cobalt blue or phthalocyanine blue with
On mixture；
The preferred fumed silica of thixotropic agent；
The defoamer is organic silicon defoamer, and it is to reduce caused bubble during manufacture and use that it, which is acted on,.
Described antioxidant is selected from alkylation of hindered phenol, diphenyl phosphite, triphenyl phosphite, thioester, alkyl
Change one or more of mixtures in hindered amine or hydroxybenzotriazole；It is preferred that (the β-(3,5- of alkylated hindered phenolic material four
Di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (Irganox1010) or phosphorous acid three (2,4- di-tert-butyl-phenyl)
Ester (Irganox168).
The solvent selects organic solvent commonly used in the art；Can enumerate ester system, ketone system, chlorine system, alcohol system, ether system, hydrocarbon system,
Ether-ether system etc..Such as can be enumerated as ethylcarbitol acetate, butyl cellosolve acetic acid esters, propylene-glycol monoalky lether acetic acid esters,
1-METHYLPYRROLIDONE (NMP), propylene glycol monomethyl ether (PGMEA), cyclohexanone, methyl ethyl ketone (MEK), methyl are different
Propyl group ketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether acetic acid
Ethyl ester, MEK, methyl iso-butyl ketone (MIBK), monomethyl ether glycol ester, gamma-butyrolacton, propionic acid -3- ether ethyl ester, butyl card must
Alcohol, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, diethylene glycol ether acetate, ethoxy-c
One or more in acetoacetic ester, hexamethylene, dimethylbenzene and isopropanol.
Viscosity of the peelable glue at 25 DEG C is preferably 2000~60,000cps, preferably 20,000~30,000cps.
The preparation method of the peelable glue, its preparation method use method commonly used in the art, such as：The raw material is carried out
The peelable glue is formed after dispersed.
It is preferred that preparation method comprises the following steps：
1) the various raw materials of precise；
2) main film forming matter is uniformly dispersed with solvent, obtains mixed solution 1；
3) and then pigment, defoamer, antioxidant (if desired, and addition time film forming matter) are added, three-roll grinder is ground
Mill, obtains mixed solution 2；
4) and then thixotropic agent is added, be uniformly dispersed discharging.
The application process of the peelable glue, the ink are printed in ito glass or PET film base by silk-screen printing technique
On material, screen printing net plate mesh number is 250 mesh or 300 mesh, and it is in 45° angle to keep scraper, ink is evenly applied on base material.Print
Through overbaking film forming after finishing, the film is fully peeled off from base material.
Relative to prior art, the advantages of the application：
1) in the prior art, more using the main film forming of vinyl chloride-vinyl acetate resin, epoxy resin, acrylate as peelable glue
Material.However, vinyl chloride-vinyl acetate resin, as conventional film forming matter, its combination property is bad, and conventional acrylate (such as (first
Base) methacrylate resin, PMMA) do not have good elasticity, the adhesive force of epoxy resin is bad, causes such peelable glue to exist
The adhesive force and strippable property of film generally can not be taken into account in use simultaneously, monoblock stripping is unable to when peeling off or adhesive force is too poor.Shen
Ask someone to find chlorinated polypropylene-ethylene atactic copolymer, the vinyl chloride-vinyl acetate-acrylic ester ternary polymerization of above-mentioned dosage
Thing, organosilicon-modified acrylate rubber, polystyrene-poly urethane-unsaturated polyester resin are each except playing in film forming procedure
From characteristic outside, cooperate, learn from other's strong points to offset one's weaknesses between component, good synergy can be produced, the attached of paint film can be balanced very well
Put forth effort and strippable property, and resistance to elevated temperatures is excellent.
2) a certain amount of addition acetylbutyrylcellulose, epoxy resin, closing are added simultaneously in above-mentioned main film-forming components
Film forming subsidiary material of the type polyurethane as peelable glue, its effect are more excellent.Acetylbutyrylcellulose is commonly used for the auxiliary agent of ink, application
People is had been surprisingly found that using acetylbutyrylcellulose as film forming matter, and secondary film forming is used as with epoxy resin, blocked polyurethane compounding
Thing, by the chemical reaction between epoxy resin, blocked polyurethane, acetylbutyrylcellulose (it contains hydroxyl, carboxyl etc.),
Three forms micro- crosslinking in film forming procedure, forms microcosmic tridimensional network, is not weakening the situation of other performances of paint film
Under, further improve the performances such as strippable property, high temperature resistant, chemical-resistant resistance.And primary and secondary film forming matter described herein, in ink
Good synergy is generated in film forming procedure so that the performance of paint film is significantly lifted.
3) in herein described peelable ink, without adding levelling agent, it has Self-leveling effect；And increase without adding
Agent is moulded, it is more environmentally friendly.
4) using polystyrene-poly urethane-unsaturated polyester resin except performance polystyrene, polyurethane, unsaturated polyester (UP)
Characteristic outside, moreover it is possible to significantly improve the heat-resisting quantity of ink, and solve polystyrene, polyurethane, unsaturated polyester resin and exist
Consistency problem in composition, its effect are much better than to be separately added into polystyrene, polyurethane, unsaturated polyester (UP).Moreover, polyphenyl
Ethene-polyurethane-unsaturated polyester resin generates good synergy with remaining component, improves the combination property of material.
Test event
Film forming is tested
After 20~30min being toasted under the conditions of the ito glass substrate for printing peelable glue of the present invention is placed in into 145-160 DEG C
Take out, observe film forming situation, including whether edge contracting ink, shrinkage cavity, film cracking, the tactile film forming of finger are dry and comfortable.If film forming is not above-mentioned
Any situation, is designated as "○"；If film forming has a kind of any of the above described situation, "×" is designated as.
Adhere to strippable property test
By peelable glue silk-screen of the present invention in ito glass substrate 25mm*20cm, and 20- is toasted under the conditions of 145-160 DEG C
30min film forming, then, stretched by peeling rate 300mm/min along 180 ° of directions (inverse approach), be stripping the masterpiece for starting to peel off
From power, unit " gf/inch ".When peeling force is in 10-30gf/inch, monoblock peels off noresidue best, the note that then adheres to strippable property
For " 00 "；When peeling force is in 10-30gf/inch, monoblock is peeled off but has minimal residue (revolution mark is less than 5%) then to adhere to
Strippable property is good, is designated as "○"；The peelable noresidue but adhesiveness is poor when peeling force is less than 10gf/inch, is designated as " △ "；Work as stripping
Then good difficult peel off of adhesiveness has residual when being more than 30gf/inch from power, is designated as "×".
High temperature resistant is tested
By peelable glue silk-screen of the present invention in glass substrate, and 20-30min film forming is toasted under the conditions of 145-160 DEG C, then
Be placed on heat baking 250 DEG C × 2 hours, observation film whether shrink, be cracked, yellowing phenomena such as；Such as either with or without above-mentioned phenomenon table
Bright heat resistance is best, is designated as " 00 "；If a small amount of yellowing, cracking or micro contraction show heat-resist, "○" is designated as；Such as
The above-mentioned three kinds of phenomenons of fruit exist simultaneously shows that heat resistance is poor, is designated as "×".
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Preparation example 1
Polystyrene-poly urethane-unsaturated polyester (UP) copolymer is prepared, it synthesizes its step and is：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of phthalic anhydrides, 80 parts of ethylene glycol, 100
Part pentaerythrite, 20 parts of glycerine, 100 parts of cyclohexanone, 2.6 parts of concentrated sulfuric acids are sequentially added equipped with electric stirring, water knockout drum, temperature
In the reaction vessel that meter, electric jacket heat, heat, stirring, be warming up to 140 DEG C, react 2.5 hours；It is warming up to 155 DEG C of reactions
0.5 hour, it is cooled to 100 DEG C and adds 20 parts of propane diols (so that the end group of condensation polymer is-OH), react 1h, vacuumize, contained
There is the unsaturated polyester (UP) of terminal hydroxy group, cool down, it is standby.
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
60 parts of unsaturated polyester (UP), the IPDI IPDI 150 containing terminal hydroxy group for taking the first step to synthesize
0.5 part, 80 parts part, 20 parts of PPG (Mn=6000), dibutyl tin laurate cyclohexanone are added in reaction vessel, are risen
Temperature, when-NCO% is stable, obtains the polyurethane unsaturated polyester (UP) copolymer that end group is-NCO to 100 DEG C of reaction 2h；Add first
90 parts of base hydroxypropyl acrylate, while add 0.3 part of dibutyl tin laurate and continue to react with 0.5 part of phenolic inhibitor, extremely
NCO exhausts in system, stops reaction, vacuumizes, and obtains the polyurethane unsaturated polyester (UP) copolymer that end group is acryloxy.
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
The end group for taking second step to synthesize is 200 parts of polyurethane unsaturated polyester (UP) copolymer, the styrene 120 of acryloxy
1.5 parts, 150 parts part, AIBN cyclohexanone, 80 DEG C are heated under inert gas shielding, react 2 hours, be continuously heating to 115
DEG C, react 1 hour, be evaporated under reduced pressure desolvation, that is, obtain described polystyrene-poly urethane-unsaturated polyester resin, it is counted
Average molecular weight is 50000.
Embodiment 1
The peelable glue contains the following raw material：
28 parts of chlorinated polypropylene-ethylene atactic copolymer；25 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
37 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane -30 parts of unsaturated polyester resin；2 parts of pigment；Thixotropic agent
0.2 part；Defoamer, 0.3 part；Antioxidant, 0.5 part；40 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) by main film forming matter and solvent (mass ratio, NMP: PGMEA: MEK=60: 20: 20) be uniformly dispersed, obtain mixing molten
Liquid 1；
3) and then pigment, defoamer, antioxidant are added, three-roll grinder grinding, obtains mixed solution 2；
4) and then thixotropic agent is added, be uniformly dispersed discharging.
Embodiment 2
The peelable glue contains the following raw material：
30 parts of chlorinated polypropylene-ethylene atactic copolymer；30 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
35 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane -25 parts of unsaturated polyester resin；Acetylbutyrylcellulose,
10 parts；Epoxy resin, 10 parts, blocked polyurethane, 15 parts；Organotin, 1 part；3 parts of pigment；0.4 part of thixotropic agent；Defoamer,
0.5 part；Antioxidant, 0.4 part；20 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter is uniformly dispersed with solvent, obtains mixed solution 1；
3) and then pigment, defoamer, antioxidant, secondary film forming matter are added, three-roll grinder grinding, obtains mixed solution 2；
4) and then thixotropic agent is added, be uniformly dispersed discharging.
Embodiment 3
The peelable glue contains the following raw material：
35 parts of chlorinated polypropylene-ethylene atactic copolymer；25 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
30 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane -30 parts of unsaturated polyester resin；Acetylbutyrylcellulose,
11 parts；Epoxy resin, 12 parts, blocked polyurethane, 10 parts；Organotin, 2 parts；2 parts of pigment；0.3 part of thixotropic agent；Defoamer,
0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter is uniformly dispersed with solvent, obtains mixed solution 1；
3) and then pigment, defoamer, antioxidant, secondary film forming matter are added, three-roll grinder grinding, obtains mixed solution 2；
4) and then thixotropic agent is added, be uniformly dispersed discharging.
Embodiment 4
The peelable glue contains the following raw material：
28 parts of chlorinated polypropylene-ethylene atactic copolymer；25 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
37 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane -30 parts of unsaturated polyester resin；Acetylbutyrylcellulose,
12 parts；Epoxy resin, 12 parts, blocked polyurethane, 15 parts；Organotin, 1.5 parts；2 parts of pigment；0.3 part of thixotropic agent；Defoamer,
0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method is：
1) the various raw materials of precise；
2) main film forming matter is uniformly dispersed with solvent, obtains mixed solution 1；
3) and then pigment, defoamer, antioxidant, secondary film forming matter are added, three-roll grinder grinding, obtains mixed solution 2；
4) and then thixotropic agent is added, be uniformly dispersed discharging.
Comparative example 1
The peelable glue contains the following raw material：
80 parts of chlorinated polypropylene-ethylene atactic copolymer；20 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
20 parts of organosilicon-modified acrylate rubber；Polystyrene-poly urethane -5 parts of unsaturated polyester resin；2 parts of pigment；Thixotropic agent
0.2 part；Defoamer, 0.3 part；Antioxidant, 0.5 part；40 parts of solvent.
Its preparation method is the same as embodiment 1.
Comparative example 2
The peelable glue contains the following raw material：
50 parts of chlorinated polypropylene-ethylene atactic copolymer；40 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
30 parts of organosilicon-modified acrylate rubber；2 parts of pigment；0.2 part of thixotropic agent；Defoamer, 0.3 part；Antioxidant, 0.5 part；Solvent
40 parts.
Its preparation method is the same as embodiment 1.
Comparative example 3
The peelable glue contains the following raw material：
28 parts of chlorinated polypropylene-ethylene atactic copolymer；25 parts of vinyl chloride-vinyl acetate-acrylate terpolymer；
37 parts of organosilicon-modified acrylate rubber；Polystyrene, 10 parts；Polyurethane, 10 parts；Unsaturated polyester resin, 10 parts；Acetic acid
Cellulose butyrate, 12 parts；Epoxy resin, 12 parts, blocked polyurethane, 15 parts；Organotin, 1.5 parts；2 parts of pigment；Thixotropic agent
0.3 part；Defoamer, 0.5 part；Antioxidant, 0.4 part；30 parts of solvent.
Its preparation method is the same as embodiment 1.
Comparative example 4
The peelable glue of prior art, contains following components：Vinyl chloride-vinyl acetate resin, 40 parts；MMA resins, 15 parts；Epoxy resin, 10
Part；Dioctyl adipate, 23 parts；Epoxidized soybean oil, 10 parts
Using identical technique, the peelable glue of embodiment, comparative example is passed through into the uniform coating glass base of silk-screen printing technique
On material, tested.
Test result is as described in Table 1
Table 1
| Numbering | Film forming | Adhere to strippable property | High temperature resistant | Comprehensive Assessment |
| Embodiment 1 | ○ | ○ | ○ | It is good |
| Embodiment 2 | ○○ | ○○ | ○○ | It is excellent |
| Embodiment 3 | ○○ | ○○ | ○○ | It is excellent |
| Embodiment 4 | ○○ | ○○ | ○○ | It is excellent |
| Comparative example 1 | ○ | × | ○ | Difference |
| Comparative example 2 | × | △ | × | Difference |
| Comparative example 3 | × | △ | × | Difference |
| Comparative example 4 | × | × | × | Difference |
From the test result of table 1, containing the main film forming matter in herein described specific amount ranges, (chlorination gathers simultaneously
Propylene-ethylene random copolymer, vinyl chloride-vinyl acetate-acrylate terpolymer, organosilicon-modified acrylate rubber
Glue, polystyrene-poly urethane-unsaturated polyester resin) peelable glue simultaneously take into account adhesive force, peel strength, elasticity, high temperature resistant
Etc. performance, there is unexpected technique effect, its performance be much better than using vinyl chloride-vinyl acetate resin, (methyl) methacrylate resin,
Peelable glue of the epoxy resin as film forming matter.And by experimental data it can clearly be seen that simultaneously using chlorinated polypropylene-ethene without
Rule copolymer, vinyl chloride-vinyl acetate-acrylate terpolymer, organosilicon-modified acrylate rubber, polystyrene-
The peelable glue of polyurethane-unsaturated polyester resin, its effect, which is much better than, is used alone one or more peelable glue therein, this
There is good synergy between three kinds of polymer；Using epoxy resin, acetylbutyrylcellulose, blocked polyurethane conduct
Film forming subsidiary material, it adheres to strippable property, heat-resisting quantity is largely increased；Relative to individually epoxy resin is used, it does not reach
Synergy between epoxy resin and acetylbutyrylcellulose, blocked polyurethane；Add polystyrene-poly urethane-insatiable hunger
The heat-resisting quantity of peelable glue can be improved with polyester resin.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than the present invention is protected
The limitation of scope is protected, although being explained with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Work as understanding, technical scheme can be modified or equivalent substitution, without departing from the reality of technical solution of the present invention
Matter and scope.
Claims (10)
1. a kind of peelable glue, it is characterised in that the component and dosage of its film forming matter be：Polystyrene-poly urethane-unsaturation is poly-
Ester resin 25-30 parts；Chlorinated polypropylene-ethylene atactic copolymer 20-40 parts；Vinyl chloride-vinyl acetate-acrylic ester ternary is common
Polymers 20-30 parts；Organosilicon-modified acrylate rubber 30-40 parts；Wherein, the polystyrene-poly urethane-unsaturated polyester (UP)
Resin contains the residue of (methyl) acryloxy；Chlorinity is 15wt%- in the chlorinated polypropylene-ethylene atactic copolymer
25wt%, its number-average molecular weight are 400,000-800,000.
2. peelable glue as claimed in claim 1, it is characterised in that in addition to film forming matter described in claim 1, the film forming matter
Also contain following component and the secondary film forming matter of content is：Acetylbutyrylcellulose 10-15 parts；Epoxy resin 10-15 parts；Closing
Type polyurethane 10-15 parts.
3. peelable glue as claimed in claim 2, it is characterised in that preferably：Chlorinated polypropylene-ethylene atactic copolymer 25-30
Part；Vinyl chloride-vinyl acetate-acrylate terpolymer 25-30 parts；Organosilicon-modified acrylate rubber 35-40 parts；It is poly-
Styrene-polyurethane-unsaturated polyester resin 25-30 parts.
4. peelable glue as claimed in claim 2 or claim 3, it is characterised in that secondary film forming matter, which forms, is：Acetylbutyrylcellulose 10-
15 parts；Epoxy resin 10-15 parts；Blocked polyurethane 10-15 parts；Organic tin catalyst 1-2 parts.
5. the peelable glue as described in claim any one of 1-3, it is characterised in that the chlorinated polypropylene-ethylene random copolymerization
Chlorinity is 15wt%-25wt% in thing；Vinyl chloride-vinyl acetate-acrylate terpolymer content of vinylchloride is 61.0
± 1.0wt%；39.0 ± 1.0wt% of vinyl acetate content.
6. the peelable glue as described in claim any one of 1-3, it is characterised in that the polystyrene-poly urethane-unsaturation is poly-
The polymerization of ester resin is：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 20-50 parts behenic acid, 10-50 parts fumaric acid, 20-50 parts maleic anhydride, 5-20 parts phthalic anhydride, 60-100 parts
Ethylene glycol, 100-120 parts pentaerythrite, 20-40 parts glycerine, 80-200 parts cyclohexanone, 1-50 part concentrated sulfuric acids are sequentially added and are equipped with
In the reaction vessel that electric stirring, water knockout drum, thermometer, electric jacket heat, heat, stirring, be warming up to 140 DEG C, reaction 2.5 is small
When；It is warming up to 155 DEG C to react 0.5 hour, is cooled to 100 DEG C and adds 10-100 part propane diols, react 1h, vacuumize, contained
There is the unsaturated polyester (UP) of terminal hydroxy group, cool down, it is standby；
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
Take unsaturated polyester (UP) 50-80 parts containing terminal hydroxy group, the IPDI IPDI 100- of first step synthesis
160 parts, Mn=6000 PPG 20-50 parts, dibutyl tin laurate 0.2-5 parts, 50-100 parts cyclohexanone add
In reaction vessel, 100 DEG C of reaction 2h are warming up to, when-NCO% is stable, obtain the polyurethane unsaturated polyester (UP) that end group is-NCO
Copolymer；Hydroxy propyl methacrylate 60-100 parts are added, while add dibutyl tin laurate 0.1-3 parts and phenols inhibition
Agent 0.1-5 parts continue to react, and into system, NCO exhausts, and stop reaction, vacuumize, and obtain the poly- ammonia that end group is acryloxy
Ester unsaturated polyester (UP) copolymer；
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
The end group for taking second step to synthesize is polyurethane unsaturated polyester (UP) copolymer 1 00-250 parts of acryloxy, styrene 80-
140 parts, AIBN 1-5 parts, 80-180 part cyclohexanone, be heated to 80 DEG C under inert gas shielding, react 2 hours, continue to heat up
To 115 DEG C, react 1 hour, be evaporated under reduced pressure desolvation, that is, obtain described polystyrene-poly urethane-unsaturated polyester (UP) tree
Fat.
7. the peelable glue as described in claim any one of 1-3, it is characterised in that it also contains：Pigment 1-3 parts；Thixotropic agent
0.1-0.5 parts；Defoamer 0.1-0.5 parts；Antioxidant 0.1-0.5 parts；Solvent 20-60 parts.
A kind of 8. peelable glue as claimed in claim 7, it is characterised in that the polystyrene-poly urethane-unsaturated polyester (UP) tree
The polymerization of fat is：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 20-50 parts behenic acid, 10-50 parts fumaric acid, 20-50 parts maleic anhydride, 5-20 parts phthalic anhydride, 60-100 parts
Ethylene glycol, 100-120 parts pentaerythrite, 20-40 parts glycerine, 80-200 parts cyclohexanone, 1-50 part concentrated sulfuric acids are sequentially added and are equipped with
In the reaction vessel that electric stirring, water knockout drum, thermometer, electric jacket heat, heat, stirring, be warming up to 140 DEG C, reaction 2.5 is small
When；It is warming up to 155 DEG C to react 0.5 hour, is cooled to 100 DEG C and adds 10-100 part propane diols, react 1h, vacuumize, contained
There is the unsaturated polyester (UP) of terminal hydroxy group, cool down, it is standby；
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
Take unsaturated polyester (UP) 50-80 parts containing terminal hydroxy group, the IPDI IPDI 100- of first step synthesis
160 parts, Mn=6000 PPG 20-50 parts, dibutyl tin laurate 0.2-5 parts, 50-100 parts cyclohexanone add
In reaction vessel, 100 DEG C of reaction 2h are warming up to, when-NCO% is stable, obtain the polyurethane unsaturated polyester (UP) that end group is-NCO
Copolymer；Hydroxy propyl methacrylate 60-100 parts are added, while add dibutyl tin laurate 0.1-3 parts and phenols inhibition
Agent 0.1-5 parts continue to react, and into system, NCO exhausts, and stop reaction, vacuumize, and obtain the poly- ammonia that end group is acryloxy
Ester unsaturated polyester (UP) copolymer；
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
The end group for taking second step to synthesize is polyurethane unsaturated polyester (UP) copolymer 1 00-250 parts of acryloxy, styrene 80-
140 parts, AIBN 1-5 parts, 80-180 part cyclohexanone, be heated to 80 DEG C under inert gas shielding, react 2 hours, continue to heat up
To 115 DEG C, react 1 hour, be evaporated under reduced pressure desolvation, that is, obtain described polystyrene-poly urethane-unsaturated polyester (UP) tree
Fat.
A kind of 9. peelable glue as claimed in claim 8, it is characterised in that described polystyrene-poly urethane-unsaturated polyester (UP)
Polyurethane copolymer number-average molecular weight is 5000~150000；Molecular weight distribution is in 1.5-3.
10. a kind of Self-leveling peelable glue, it is characterised in that it is made up of following component and content：
Main film forming matter：Chlorinated polypropylene-ethylene atactic copolymer 25-30 parts；Vinyl chloride-vinyl acetate-acrylic ester ternary is common
Polymers 25-30 parts；Organosilicon-modified acrylate rubber 35-40 parts；Polystyrene-poly urethane-unsaturated polyester resin 25-30
Part；
Subsidiary film forming matter forms：Acetylbutyrylcellulose 10-15 parts；Epoxy resin 10-15 parts；Blocked polyurethane 10-
15 parts；Organic tin catalyst 1-2 parts；
Pigment 1-3 parts；Thixotropic agent 0.1-0.5 parts；Defoamer 0.1-0.5 parts；Antioxidant 0.1-0.5 parts；Solvent 20-60 parts；
The preparation method of the polystyrene-poly urethane-unsaturated polyester resin is：
(1) synthesis of the unsaturated polyester (UP) containing terminal hydroxy group
By 40 parts of behenic acids, 30 parts of fumaric acid, 40 parts of maleic anhydrides, 20 parts of phthalic anhydrides, 80 parts of ethylene glycol, 100 parts of seasons
Penta tetrol, 20 parts of glycerine, 100 parts of cyclohexanone, 2.6 parts of concentrated sulfuric acids are sequentially added equipped with electric stirring, water knockout drum, thermometer, electricity
In the reaction vessel of hot jacket heating, heat, stirring, be warming up to 140 DEG C, react 2.5 hours；It is small to be warming up to 155 DEG C of reactions 0.5
When, it is cooled to 100 DEG C and adds 20 parts of propane diols, react 1h, vacuumize, obtain the unsaturated polyester (UP) containing terminal hydroxy group, cools down, it is standby
With；
(2) synthesis of polyurethane unsaturated polyester (UP) copolymer
150 parts of 60 parts of unsaturated polyester (UP), IPDI, the polyether polyols containing terminal hydroxy group for taking the first step to synthesize
0.5 part, 80 parts 20 parts of alcohol, dibutyl tin laurate cyclohexanone are added in reaction vessel, are warming up to 100 DEG C of reaction 2h, when-
When NCO% is stable, the polyurethane unsaturated polyester (UP) copolymer that end group is-NCO is obtained；90 parts of hydroxy propyl methacrylate is added,
0.3 part of dibutyl tin laurate is added simultaneously and 0.5 part of phenolic inhibitor continues to react, and into system, NCO exhausts, and stops anti-
Should, vacuumize, obtain the polyurethane unsaturated polyester (UP) copolymer that end group is acryloxy；
(3) synthesis of polystyrene-poly urethane-unsaturated polyester (UP) polyurethane copolymer
Take second step synthesize end group for acryloxy 120 parts of 200 parts of polyurethane unsaturated polyester (UP) copolymer, styrene,
1.5 parts, 150 parts cyclohexanone of AIBN, 80 DEG C are heated under inert gas shielding, react 2 hours, be continuously heating to 115 DEG C,
Reaction 1 hour, desolvation is evaporated under reduced pressure, that is, obtains described polystyrene-poly urethane-unsaturated polyester resin.
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| 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 |
| 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 |
| 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 |
| 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 |
| CN113788928B (en) * | 2021-09-07 | 2023-05-12 | 肇庆市宝骏化工有限公司 | High-temperature-resistant high-elongation polyurethane acrylic resin and application thereof in preparation of ultraviolet light curing peelable glue |
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| DE60213914T2 (en) * | 2001-06-26 | 2007-02-22 | Sumitomo Bakelite Co. Ltd. | Masking tape for packaging electronic components |
| KR101789369B1 (en) * | 2004-12-10 | 2017-10-23 | 미츠비시 가스 가가쿠 가부시키가이샤 | Laminate film |
| CN101255324B (en) * | 2007-02-26 | 2010-05-19 | 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 |
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