CN108192019A - A kind of novel acrylic pressure sensitive adhesive - Google Patents

A kind of novel acrylic pressure sensitive adhesive Download PDF

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Publication number
CN108192019A
CN108192019A CN201810002452.1A CN201810002452A CN108192019A CN 108192019 A CN108192019 A CN 108192019A CN 201810002452 A CN201810002452 A CN 201810002452A CN 108192019 A CN108192019 A CN 108192019A
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acrylate
sensitive adhesive
pressure sensitive
methyl
parts
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CN108192019B (en
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袁宜恩
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Shanghai Baolijia New Material Co Ltd
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Shanghai Baolijia New Material Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/20Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/04Azo-compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/28Oxygen or compounds releasing free oxygen
    • C08F4/32Organic compounds
    • C08F4/34Per-compounds with one peroxy-radical
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24Homopolymers or copolymers of amides or imides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention provides a kind of novel acrylic pressure sensitive adhesive, and the raw material for preparing of the novel acrylic pressure sensitive adhesive includes at least:Acrylic acid, acrylate, solvent, initiator and plasticizer;Inventive formulation is simple, does not add the auxiliary agents such as anti-aging agent, tackifying resin, softening agent;All there are good adhesive property, such as metal, cement, paper, timber, ceramics to most of polar material surface or porous material surface.Also there is good adhesive property to the plastics such as polyvinyl chloride, polyester, polystyrene and polyolefin through sided corona treatment and fiber simultaneously;The pressure sensitive adhesive provided by the invention is reusable, remains to keep good adhesion properties after repeatedly pasting and removing and peel strength will not be decreased obviously;After fitting after going through long-time or bearing larger pressure, peel strength will not significantly improve, and can detach and not occur the pressure sensitive adhesive of glue-line transfer with adherend easily.

Description

A kind of novel acrylic pressure sensitive adhesive
Technical field
The present invention relates to a kind of protective film fields, are more related to a kind of novel acrylic pressure sensitive adhesive.
Background technology
With the continuous development of industry, more and more products need to carry out interim surface during production and transportation Protection, to prevent surface dirt and transport from scratching, therefore produces surface protection film.Resin pressure sensitive adhesive is broadly divided into poly- ammonia Esters, polyacrylate and organic silicon.Acrylate pressure sensitive adhesive because have simultaneously to various base materials excellent adhesive property and Good interfacial stress dispersibility and be widely used, by its polymerization methods, acrylate pressure sensitive adhesive is divided into solvent type pressure Quick glue, emulsion-type pressure-sensitive, thermotropic pressure sensitive glue, water soluble pressure-sensitive adnesive and UV type pressure sensitive adhesives.
Currently, acrylic acid ester emulsion type pressure sensitive adhesive achieves faster development, but with acrylate solvent pressure-sensitive adhesive and Speech, the adhesive property of emulsion-type pressure-sensitive, cohesive strength are all not so good as the identical solvent pressure-sensitive adhesive of monomer composition.In addition, lotion Water resistance, lower temperature resistance and polymerization stability, the film quality of type pressure sensitive adhesive are poor.Solvent-type acrylic ester pressure-sensitive, which has, to be divided Many advantages, such as son amount is low, just viscous big, wettability is good, rate of drying is fast, weatherability water-tolerant, so solvent-type acrylic ester Pressure sensitive adhesive still occupies considerable status in protective film application field, and performance is also required to constantly improve and improve.
The present invention provides a kind of reuse type acrylate pressure sensitive adhesive, is still protected after making the repeated stickup of pressure sensitive adhesive and stripping Good adhesive property is held, and peel strength will not be decreased obviously;Through going through for a long time or bearing larger pressure after fitting After power, acrylate pressure sensitive adhesive peel strength can detach easily with adherend without significantly improving and glue-line transfer does not occur.
Invention content
The present invention provides a kind of novel acrylic pressure sensitive adhesive, and the raw material for preparing of the novel acrylic pressure sensitive adhesive at least wraps Contain:Acrylic acid, acrylate, solvent, initiator and plasticizer.
As one embodiment of the present invention, the acrylate is selected from methyl acrylate, ethyl acrylate, acrylic acid N-propyl, 2- cyclohexyl methacrylates, butyl acrylate, isobutyl acrylate, hydroxy-ethyl acrylate, 2,3- dihydroxypropyls Acrylate, cyclohexyl 2- cyanoacrylates, 1,3- bis- (4- benzoyl -3- hydroxyphenoxies) propyl- 2- ylmethyl propylene Acid esters, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] first Base] -1,3- propane diyl] ester, isopropyl cyanoacrylate, 2- cyanoethyl acrylates, 2,3- glycidyl acrylic acid Ester, glycidyl methacrylate, 6- hydroxyls ethylhexyl acrylate, neopentylglycol dimethacrylate, 3- [(4'- cyano Biphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, 1,4 butanediol diacrylate, diethyl aminoethyl methacrylate and one kind in 1,9- nonanediol diacrylates or It is a variety of.
As one embodiment of the present invention, the acrylate is selected from methyl acrylate, ethyl acrylate, 2- methyl Cyclohexyl acrylate, butyl acrylate, acrylamide, hydroxy-ethyl acrylate, 2,3- dihydroxypropyls acrylate, 2- methyl- 2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- propane Diyl] ester, 2- cyanoethyl acrylates, glycidyl methacrylate, 6- hydroxyls ethylhexyl acrylate, 3- [(4'- cyanogen Base biphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, 1,4 butanediol diacrylate and It is one or more in 1,9- nonanediol diacrylates.
As one embodiment of the present invention, the solvent is selected from the one or more such as toluene, methanol, ethyl acetate.
As one embodiment of the present invention, the initiator is selected from peroxide initiator and/or azo-initiator.
As one embodiment of the present invention, the peroxide initiator is potassium peroxydisulfate, ammonium persulfate, isopropylbenzene mistake Hydrogen oxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, peroxidating 12 Acyl, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, di-isopropyl peroxydicarbonate, dicetyl peroxydicarbonate two One kind in cyclohexyl.
As one embodiment of the present invention, the raw material for preparing of the acrylate pressure sensitive adhesive also includes benzo-crown ether.
As one embodiment of the present invention, the structural formula of the benzo-crown ether is as follows:
The R group is
As one embodiment of the present invention, the raw material for preparing of the acrylate pressure sensitive adhesive also includes organic titanium.
As one embodiment of the present invention, the raw material for preparing of the organic titanium includes:Butyl titanate and four (three ethyl alcohol Amine) zirconium.
Advantageous effect:
1. inventive formulation is simple, the auxiliary agents such as anti-aging agent, tackifying resin, softening agent are not added;
2. Performance of Pressure Sensitive Adhesive range provided by the invention is wider, to most of polar material surface or porous material surface all With good adhesive property, such as metal, cement, paper, timber, ceramics.Simultaneously to polyvinyl chloride, polyester, polystyrene Also there is good adhesive property with the plastics such as the polyolefin through sided corona treatment and fiber;
3. the pressure sensitive adhesive provided by the invention is reusable, remain to keep good viscous after repeatedly pasting and removing It connects characteristic and peel strength will not be decreased obviously;After fitting after going through long-time or bearing larger pressure, peel strength will not It significantly improves, can detach and not occur the pressure sensitive adhesive of glue-line transfer with adherend easily.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Object, step, method, product or device are not necessarily limited to those elements, but can include not expressly listed other elements or Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element do not pointed out, step or component.If in claim, this Phrase will make claim be closed, it be made not include the material in addition to the material of those descriptions, but relative normal Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body, It is only limited to the element described in the clause;Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range All ranges that any pairing of lower limit or preferred value is formed, regardless of whether the range separately discloses.For example, when open During range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end Value and all integers and score in the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " arbitrary It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents specific the present invention is not limited to this Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, it is approximate Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with It combines and/or exchanges, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before element of the present invention or component and "one" quantitative requirement to element or component (i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
The present invention provides a kind of novel acrylic pressure sensitive adhesive, and the raw material for preparing of the novel acrylic pressure sensitive adhesive at least wraps Contain:Acrylic acid, acrylate, solvent, initiator and plasticizer.
Acrylate
Heretofore described acrylate is selected from methyl acrylate, ethyl acrylate, n-propyl, 2- metering systems Sour cyclohexyl, butyl acrylate, isobutyl acrylate, hydroxy-ethyl acrylate, 2,3- dihydroxypropyls acrylate, cyclohexyl 2- Cyanoacrylate, 1,3- bis- (4- benzoyl -3- hydroxyphenoxies) propyl- 2- methyl acrylates, 2- methyl -2- propylene Sour 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- propane diyl] Ester, isopropyl cyanoacrylate, 2- cyanoethyl acrylates, 2,3- glycidyl acrylate, Glycidyl methacrylate Glyceride, 6- hydroxyls ethylhexyl acrylate, neopentylglycol dimethacrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] third Base 2- acrylate, 2- butyl octyls methacrylate, 2-ethyl hexyl acrylate, Isooctyl acrylate monomer, two propylene of 1,4- butanediols It is one or more in acid esters, diethyl aminoethyl methacrylate and 1,9- nonanediol diacrylates.
As one embodiment of the present invention, the acrylate is selected from methyl acrylate, ethyl acrylate, 2- methyl Cyclohexyl acrylate, butyl acrylate, acrylamide, hydroxy-ethyl acrylate, 2,3- dihydroxypropyls acrylate, 2- methyl- 2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- propane Diyl] ester, 2- cyanoethyl acrylates, glycidyl methacrylate, 6- hydroxyls ethylhexyl acrylate, 3- [(4'- cyanogen Base biphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, 1,4 butanediol diacrylate and It is one or more in 1,9- nonanediol diacrylates.
It is described as a kind of preferred embodiment of the present invention from order to increase for the angle of the repeat performance of product Acrylate is selected from methyl acrylate, 2- cyclohexyl methacrylates, 2,3- dihydroxypropyls acrylate, 2- methyl -2- third Olefin(e) acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- propane two Base] ester, glycidyl methacrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate, 6- hydroxyls oneself It is one or more in base acrylate and 2- butyl octyl methacrylates.
Solvent
Heretofore described solvent, which is selected from, can promote between acrylic acid and acrylate monomer under the action of initiator Reactive polymeric reacts.
As one embodiment of the present invention, the solvent is selected from toluene, ethyl acetate, methyl ethyl ketone, denaturation wine It is one or more in essence and hexane.
From the actual effect of the present invention, in order to prepare the more excellent acrylate pressure sensitive adhesive of repeat performance, sheet Solvent described in invention is one or more in benzene, methanol, ethyl acetate.
Initiator
The type of initiator has very much, and common initiator is free radical type initiator in pressure sensitive adhesive.Free radical type draws It sends out agent and often includes per-compound initiator and azo-initiator and redox initiator etc..Wherein, per-compound Initiator is divided into as organic peroxide evocating agent and inorganic peroxide initiator.Radical initiator can cause alkenes, The free radical polymerization and copolyreaction of double vinyl monomers, crosslinking curing and the high molecular crosslink that can be used for unsaturated polyester (UP) are anti- It should.
As one embodiment of the present invention, heretofore described initiator be selected from using peroxide initiator and/or Azo-initiator.
As the example of peroxide initiator, potassium peroxydisulfate, ammonium persulfate, isopropyl benzene hydroperoxide, uncle can be included Butylhydroperoxide, cumyl peroxide, di-t-butyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, peroxidating T-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate.
As the example of azo-initiator, azodiisobutyronitrile (AIBN), azobisisoheptonitrile can be enumerated (ABVN), 2,2 '-azo-two-(2- methylbutyronitriles) (AMBN) etc..
In the present invention, for the acrylate pressure sensitive adhesive that processability is excellent, the preferred azo-initiator of inventor can promote Has long-acting excellent performance into the peel strength in the repeat performance for the acrylate pressure sensitive adhesive being prepared.
Benzo-crown ether
Benzo-crown ether all has alkali metal, alkaline-earth metal, rare earth ion special selectivity and coordinating so that Benzo-crown ether is widely used in the identification of metal ion.Aobvious someone is used for pressure sensitive adhesive field.
In the present invention, the structural formula of the benzo-crown ether is as follows:
The R group is
In the present invention, any one side well known by persons skilled in the art may be used in the preparation method of the benzo-crown ether Method is prepared.For example, using dibenzo-18 crown-6 as raw material, under the conditions of paraformaldehyde and hydrobromic acid acetum, first Tetrabromo methyl benzo -18- crown-s 6 are made, then in Na2S2It is reacted in the solution of 2- acrylates, is as a result Heretofore described benzo-crown ether can be prepared.
Organic titanium
Titanium ion outermost layer has unoccupied orbital, can form coordinate bond with providing the atom of lone pair electrons.In the present invention, with Butyl titanate is titanium source, the source using four (triethanolamine) zirconiums to provide lone pair electrons.
Specific preparation method is as follows:In anhydrous conditions, it is 2.5 by the mass ratio of glycerine and isopropanol:Three are added to when 1 In mouth flask, after being heated to 85 DEG C, 30min is stirred;Then under agitation, the mass fraction for adding in gross mass is 32% Butyl titanate and four (triethanolamine) zirconiums that the mass fraction of gross mass is 20%, keep temperature, continue stirring 2 hours, you can Heretofore described organic titanium is prepared.
Plasticizer
Invention introduces plasticizer as special auxiliary agent, plasticizer includes the one of O-phthalic acids and fatty acid ester Kind or several blendings.
In the present invention, the O-phthalic acids plasticizer is commercially available, is bought from Shanghai Kun Rui Chemical Co., Ltd.s, brand It is the new physics and chemistry of Japan, model DOTH, No. CAS is 2915-49-3.
In the present invention, the fatty acid ester plasticiser is commercially available, is bought from upper ocean fish child Industrial Co., Ltd., brand is BASF, model are dinch, and No. CAS is 166412-78-8.
In the present invention, the preparation method of the novel acrylic pressure sensitive adhesive is as follows:
(1) weigh 1 part of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 2 parts of propyl 2- acrylate, 6- hydroxyls oneself 1 part of base acrylate, 2 parts of 2- butyl octyls methacrylate, 1 part of glycidyl methacrylate, benzo-crown ether 0.5 Part, 10 parts of deionized water, 0.5 part of lauryl sodium sulfate are added in reaction kettle, under mechanical stirring, slowly promote reaction temperature Degree is added with stirring 0.01 part of 5 parts of deionized water and azodiisobutyronitrile, insulation reaction is after 0.5 hour at 70 DEG C;Gradually it is added dropwise 2 parts of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 6 parts of propyl 2- acrylate, 5 parts of 6- hydroxyls ethylhexyl acrylate, 6 parts of 2- butyl octyls methacrylate, 9 parts of glycidyl methacrylate, 1.5 parts of benzo-crown ether, 15 parts of deionized water, Rear insulation reaction is added dropwise 1 hour in 0.1 part of azodiisobutyronitrile, 0.5 part of lauryl sodium sulfate;
(2) 1 part of acrylic acid, 2 parts of methyl acrylate, 3 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyls third are weighed 5 parts of olefin(e) acid ester, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 3 parts of ester, 1 part of acrylamide, 0.5 part of lauryl sodium sulfate, 5 parts of ethyl acetate, azo 0.01 part of bis-isobutyronitrile, is added drop-wise to after mixing, under mechanical agitation in the mixed solution of step (1), then insulation reaction 0.5 hour Afterwards, 4 parts of acrylic acid, 5 parts of methyl acrylate, 12 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyl propylene is gradually added dropwise 15 parts of acid esters, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 12 parts of ester, 3 parts of organic titanium, 10 parts of ethyl acetate, 2 parts of acrylamide, azodiisobutyronitrile 1 Part, the mixed solution that 0.5 part of lauryl sodium sulfate after reacting 0.5 hour under stiring, stands, removes water layer, then stirring Mix down that the reaction was continued 2 hours;Then 40 DEG C are cooled to, ethyl acetate and O-phthalic acids plasticizer is added, adjusts product Solid content is 45%.
It is above-mentioned,
2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] and ester structural formula it is as follows:
The structural formula of 2- butyl octyl methacrylates is as follows:
Mechanism is explained:The present invention is prepared novel acrylic pressure sensitive adhesive and belongs to reuse type acrylate pressure sensitive adhesive, After being used for multiple times, since having good adhesive property, and peel strength will not be decreased obviously.It is prepared by the present invention Obtained novel acrylic pressure sensitive adhesive is the acrylate pressure sensitive adhesive of Reverse core-shell structure, is had in the outer layer growing of internal layer nuclear structure small The outer layer shell structure of particle shell composition, there are " gap " between little particle shell, the repetition for acrylate pressure sensitive adhesive in the present invention Using providing possibility.Meanwhile the present invention between the organic titanium with reference to the present invention, is formd netted using azo-type initiator Structure, the technical foundation that the maintenance for the peel strength after being used for multiple times of novel acrylic pressure sensitive adhesive of the present invention provides. Meanwhile in the present invention benzo-crown ether addition, resilience and cohesive strength for acrylate pressure sensitive adhesive of the invention provide point The support of sub- rank, while your " phase transition " process of acrylate pressure sensitive adhesive in use can be promoted.
1. present embodiment of embodiment provides a kind of novel acrylic pressure sensitive adhesive, the system of the novel acrylic pressure sensitive adhesive Standby raw material includes at least:
Acrylic acid, acrylate, solvent, initiator and plasticizer.
A kind of novel acrylic pressure sensitive adhesive described in 2. embodiment 1 of embodiment, the acrylate are selected from acrylic acid Methyl esters, ethyl acrylate, n-propyl, 2- cyclohexyl methacrylates, butyl acrylate, isobutyl acrylate, propylene Sour hydroxyl ethyl ester, 2,3- dihydroxypropyls acrylate, cyclohexyl 2- the cyanoacrylates, (4- benzoyl -3- hydroxyls of 1,3- bis- Phenoxy group) propyl- 2- methyl acrylates, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxygen Generation -2- propylene -1- bases) oxygroup] methyl] -1,3- propane diyl] ester, isopropyl cyanoacrylate, 2- cyano ethyl acrylic acid Ester, 2,3- glycidyl acrylate, glycidyl methacrylate, 6- hydroxyls ethylhexyl acrylate, neopentyl glycol diformazan Base acrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, third Olefin(e) acid monooctyl ester, Isooctyl acrylate monomer, 1,4 butanediol diacrylate, diethyl aminoethyl methacrylate and 1,9- nonyls two It is one or more in alcohol diacrylate.
A kind of novel acrylic pressure sensitive adhesive described in 3. embodiment 1 of embodiment, the acrylate are selected from acrylic acid Methyl esters, ethyl acrylate, 2- cyclohexyl methacrylates, butyl acrylate, acrylamide, hydroxy-ethyl acrylate, 2,3- dihydroxies Base propyl acrylate, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- Base) oxygroup] methyl] -1,3- propane diyl] ester, 2- cyanoethyl acrylates, glycidyl methacrylate, 6- hydroxyls Ethylhexyl acrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, It is one or more in 1,4 butanediol diacrylate and 1,9- nonanediol diacrylates.
A kind of novel acrylic pressure sensitive adhesive described in 4. embodiment 1 of embodiment, the solvent be selected from toluene, methanol, The one or more such as ethyl acetate.
A kind of novel acrylic pressure sensitive adhesive described in 5. embodiment 1 of embodiment, the initiator draw selected from peroxide Send out agent and/or azo-initiator.
A kind of novel acrylic pressure sensitive adhesive described in 6. embodiment 5 of embodiment, the peroxide initiator are over cure Sour potassium, ammonium persulfate, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide, mistake Aoxidize dibenzoyl, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, dicetyl peroxydicarbonate One kind in diisopropyl ester, di-cyclohexylperoxy di-carbonate.
A kind of novel acrylic pressure sensitive adhesive described in 7. embodiment 1 of embodiment, the preparation of the acrylate pressure sensitive adhesive Raw material also includes benzo-crown ether.
A kind of novel acrylic pressure sensitive adhesive described in 8. embodiment 7 of embodiment, the structural formula of the benzo-crown ether is such as Under:
The R group is
A kind of novel acrylic pressure sensitive adhesive described in 9. embodiment 1 of embodiment, the preparation of the acrylate pressure sensitive adhesive Raw material also includes organic titanium.
A kind of novel acrylic pressure sensitive adhesive described in 10. embodiment 9 of embodiment, which is characterized in that the organic titanium The raw material for preparing include:Butyl titanate and four (triethanolamine) zirconiums.
With reference to specific embodiment, acrylate pressure sensitive adhesive of the present invention is described further.
Embodiment 1:The present embodiment provides a kind of novel acrylic pressure sensitive adhesive, the preparation of the novel acrylic pressure sensitive adhesive is former Material includes at least:Acrylic acid, acrylate, solvent, initiator and plasticizer.
In the present embodiment, the preparation method of the novel acrylic pressure sensitive adhesive is as follows:
(1) weigh 1 part of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 2 parts of propyl 2- acrylate, 6- hydroxyls oneself 1 part of base acrylate, 2 parts of 2- butyl octyls methacrylate, 1 part of glycidyl methacrylate, benzo-crown ether 0.5 Part, 10 parts of deionized water, 0.5 part of lauryl sodium sulfate are added in reaction kettle, under mechanical stirring, slowly promote reaction temperature Degree is added with stirring 0.01 part of 5 parts of deionized water and azodiisobutyronitrile, insulation reaction is after 0.5 hour at 70 DEG C;Gradually it is added dropwise 2 parts of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 6 parts of propyl 2- acrylate, 5 parts of 6- hydroxyls ethylhexyl acrylate, 6 parts of 2- butyl octyls methacrylate, 9 parts of glycidyl methacrylate, 1.5 parts of benzo-crown ether, 15 parts of deionized water, 0.1 part of azodiisobutyronitrile, 0.5 part of lauryl sodium sulfate, are added dropwise rear insulation reaction 1 hour;
(2) 1 part of acrylic acid, 2 parts of methyl acrylate, 3 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyls third are weighed 5 parts of olefin(e) acid ester, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 3 parts of ester, 1 part of acrylamide, 0.5 part of lauryl sodium sulfate, 5 parts of ethyl acetate, azo 0.01 part of bis-isobutyronitrile, is added drop-wise to after mixing, under mechanical agitation in the mixed solution of step (1), then insulation reaction 0.5 hour Afterwards, 4 parts of acrylic acid, 5 parts of methyl acrylate, 12 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyl propylene is gradually added dropwise 15 parts of acid esters, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 12 parts of ester, 3 parts of organic titanium, 10 parts of ethyl acetate, 2 parts of acrylamide, azodiisobutyronitrile 1 Part, the mixed solution of 0.5 part of lauryl sodium sulfate after reacting 0.5 hour under stiring, stand, remove water layer, then stirring Mix down that the reaction was continued 2 hours;Then 40 DEG C are cooled to, ethyl acetate and O-phthalic acids plasticizer is added, adjusts product Solid content is 45%.
In the present embodiment, the structural formula of the benzo-crown ether is as follows:
The R group is
In this implementation, the preparation method of the organic titanium is as follows:In anhydrous conditions, by glycerine and the mass ratio of isopropanol It is 2.5:It is added in three-necked flask when 1, after being heated to 85 DEG C, stirs 30min;Then under agitation, gross mass is added in Mass fraction be 32% butyl titanate and gross mass mass fraction be 20% four (triethanolamine) zirconiums, keep temperature, Continue stirring 2 hours, you can heretofore described organic titanium is prepared.
The O-phthalic acids plasticizer is commercially available, is bought from Shanghai Kun Rui Chemical Co., Ltd.s, and brand is Japanese new Physics and chemistry, model DOTH, No. CAS is 2915-49-3.
Embodiment 2:Difference lies in the novel acrylic pressure sensitive adhesive prepares raw material not comprising benzo with embodiment 1 Crown ether.
Embodiment 3:Difference lies in the novel acrylic pressure sensitive adhesive prepares raw material not comprising organic with embodiment 1 Titanium.
Embodiment 4:Difference lies in the preparation method of the novel acrylic pressure sensitive adhesive is as follows with embodiment 1:
Weigh 8 parts of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 8 parts of propyl 2- acrylate, 6- hydroxyl hexyls 6 parts of acrylate, 8 parts of 2- butyl octyls methacrylate, 2 parts of benzo-crown ether, are gone at 10 parts of glycidyl methacrylate 25 parts of ionized water, 7 parts of methyl acrylate, 15 parts of 2- cyclohexyl methacrylates, 20 parts of 2,3- dihydroxypropyls acrylate, 2- Methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1, 3- propane diyl] 15 parts of ester, 1 part of acrylamide, 20 parts of ethyl acetate, 3 parts of organic titanium, 2 parts of lauryl sodium sulfate be added to In reaction kettle, under mechanical stirring, reaction temperature is slowly promoted at 70 DEG C, 5 parts of deionized water is added with stirring and azo two is different 1.12 parts of butyronitrile, insulation reaction is after 3 hours;Then 40 DEG C are cooled to, adds ethyl acetate and O-phthalic acids plasticizer, is adjusted The solid content for saving product is 45%.
Embodiment 5:Difference lies in the preparation method of the novel acrylic pressure sensitive adhesive is as follows with embodiment 1:
(1) 1 part of acrylic acid, 2 parts of methyl acrylate, 3 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyls third are weighed 5 parts of olefin(e) acid ester, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 3 parts of ester, 1 part of acrylamide, 0.5 part of lauryl sodium sulfate, 5 parts of ethyl acetate, azo 0.01 part of bis-isobutyronitrile, after mixing, then insulation reaction after 0.5 hour, be gradually added dropwise 4 parts of acrylic acid, 5 parts of methyl acrylate, 12 parts of 2- cyclohexyl methacrylates, 15 parts of 2,3- dihydroxypropyls acrylate, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxyls Ylmethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- propane diyl] 12 parts of ester, organic titanium 3 Part, the mixed solution of 10 parts of ethyl acetate, 2 parts of acrylamide, 1 part of azodiisobutyronitrile, 0.5 part of lauryl sodium sulfate, After the lower reaction of stirring 2.5 hours;
(2) weigh 1 part of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 2 parts of propyl 2- acrylate, 6- hydroxyls oneself 1 part of base acrylate, 2 parts of 2- butyl octyls methacrylate, 1 part of glycidyl methacrylate, benzo-crown ether 0.5 Part, 10 parts of deionized water, 0.5 part of lauryl sodium sulfate are added in reaction kettle, and the mixed of step (1) is added drop-wise under mechanical agitation It closes in solution, slowly promotes reaction temperature at 70 DEG C, be added with stirring 0.01 part of 5 parts of deionized water and azodiisobutyronitrile, protect After temperature reaction 0.5 hour;2 parts of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate 6 is gradually added dropwise Part, 5 parts of 6- hydroxyls ethylhexyl acrylate, 6 parts of 2- butyl octyls methacrylate, 9 parts of glycidyl methacrylate, benzene And 1.5 parts of crown ether, 15 parts of deionized water, 0.1 part of azodiisobutyronitrile, 0.5 part of lauryl sodium sulfate, it is kept the temperature after being added dropwise Reaction 0.5 hour is stood, and removes water layer, then the reaction was continued under stiring 2 hours;Then 40 DEG C are cooled to, adds acetic acid second Ester and O-phthalic acids plasticizer, the solid content for adjusting product are 45%.
Embodiment 6:Difference lies in the preparation method of the novel acrylic pressure sensitive adhesive is as follows with embodiment 1:
(1) weigh 1 part of acrylic acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 2 parts of propyl 2- acrylate, 6- hydroxyls oneself 1 part of base acrylate, 2 parts of 2- butyl octyls methacrylate, 1 part of glycidyl methacrylate, 0.5 part of organic titanium, 10 parts of deionized water, 0.5 part of lauryl sodium sulfate are added in reaction kettle, under mechanical stirring, slowly promote reaction temperature At 70 DEG C, 0.01 part of 5 parts of deionized water and azodiisobutyronitrile are added with stirring, insulation reaction is after 0.5 hour;Gradually it is added dropwise third 2 parts of olefin(e) acid, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] 6 parts of propyl 2- acrylate, 5 parts of 6- hydroxyls ethylhexyl acrylate, 2- 6 parts of butyl octyl methacrylate, 9 parts of glycidyl methacrylate, 1.5 parts of organic titanium, 15 parts of deionized water, azo 0.1 part of bis-isobutyronitrile, 0.5 part of lauryl sodium sulfate, are added dropwise rear insulation reaction 1 hour;
(2) 1 part of acrylic acid, 2 parts of methyl acrylate, 3 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyls third are weighed 5 parts of olefin(e) acid ester, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 3 parts of ester, 1 part of acrylamide, 0.5 part of lauryl sodium sulfate, 5 parts of ethyl acetate, azo 0.01 part of bis-isobutyronitrile, is added drop-wise to after mixing, under mechanical agitation in the mixed solution of step (1), then insulation reaction 0.5 hour Afterwards, 4 parts of acrylic acid, 5 parts of methyl acrylate, 12 parts of 2- cyclohexyl methacrylates, 2,3- dihydroxypropyl propylene is gradually added dropwise 15 parts of acid esters, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygen Base] methyl] -1,3- propane diyl] 12 parts of ester, 3 parts of benzo-crown ether, 10 parts of ethyl acetate, 2 parts of acrylamide, two isobutyl of azo The mixed solution of 1 part of nitrile, 0.5 part of lauryl sodium sulfate after reacting 0.5 hour under stiring, stands, removes water layer, then The reaction was continued under stiring 2 hours;Then 40 DEG C are cooled to, adds ethyl acetate and O-phthalic acids plasticizer, adjusts production The solid content of product is 45%.
Embodiment 7:Difference lies in the benzo-crown ether is dibenzo-18 crown-6 with embodiment 1.
Embodiment 8:Difference lies in the initiator replaces with dibenzoyl peroxide with embodiment 1.
Embodiment 9:Difference lies in the novel acrylic pressure sensitive adhesive prepares raw material not comprising 3- with embodiment 1 [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate.
Embodiment 10:Difference lies in the novel acrylic pressure sensitive adhesive prepares raw material not comprising 2- first with embodiment 1 Base -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- bases) oxygroup] methyl] -1,3- Propane diyl] ester.
Test:
1st, it is just viscous:According to GB/T4852-2002《Pressure-sensitive tape tack test method (rolling ball method)》, it is oblique using spin Slope stops experiment and is tested the maximum ball size that the adhesive faces of (measurement angle be 20 °) length according to the rules can be clung, Evaluate pressure sensitive adhesive tack size.Steel ball grain size is big, and pressure sensitive adhesive initial cohesiveness is big.
2nd, 180 ° of peel strengths
According to GB/T2792-1995《180 ° of peeling strength test methods of pressure-sensitive tape》, using electronic universal tester Be measured (by viscous material be PET film, detachment rate 300mm/min).
3rd, fissility is repeated
Sample is repeated into paste 100 times in cleaned glass surface, is then pasted on PET film surface, and test it 180 ° of peel strengths.
Test result:
Embodiment Just viscous/# 180 ° of peel strength/N/25mm Repeat fissility/N/25mm Water resistance Residue glue
Embodiment 1 14 13 11 Without albefaction Without residue glue
Embodiment 2 7 6 3 Without albefaction Without residue glue
Embodiment 3 8 7 5 Without albefaction Without residue glue
Embodiment 4 8 8 6 Without albefaction Without residue glue
Embodiment 5 10 8 6 Without albefaction Without residue glue
Embodiment 6 11 8 6 Without albefaction Without residue glue
Embodiment 7 13 11 7 Without albefaction Without residue glue
Embodiment 8 12 11 7 Without albefaction Without residue glue
Embodiment 9 13 11 9 Without albefaction Without residue glue
Embodiment 10 13 11 9 Without albefaction Without residue glue
Aforementioned example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim The range as wide as possible that requirement is contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is that appended claim is not illustrated the present invention Feature exemplary selectional restriction.And the progress in science and technology will not formed due to the inaccuracy that language is expressed and not The possible equivalent or son being presently considered are replaced, and these variations also should in the conceived case be interpreted by appended Claim covers.

Claims (10)

1. a kind of novel acrylic pressure sensitive adhesive, which is characterized in that the raw material for preparing of the novel acrylic pressure sensitive adhesive includes at least:
Acrylic acid, acrylate, solvent, initiator and plasticizer.
2. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the acrylate is selected from acrylic acid first Ester, ethyl acrylate, n-propyl, 2- cyclohexyl methacrylates, butyl acrylate, isobutyl acrylate, acrylic acid Hydroxyl ethyl ester, 2,3- dihydroxypropyls acrylate, cyclohexyl 2- the cyanoacrylates, (4- benzoyl -3- hydroxy benzenes of 1,3- bis- Oxygroup) propyl- 2- methyl acrylates, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxygen Generation -2- propylene -1- bases) oxygroup] methyl] -1,3- propane diyl] ester, isopropyl cyanoacrylate, 2- cyano ethyl acrylic acid Ester, 2,3- glycidyl acrylate, glycidyl methacrylate, 6- hydroxyls ethylhexyl acrylate, neopentyl glycol diformazan Base acrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, third Olefin(e) acid monooctyl ester, Isooctyl acrylate monomer, 1,4 butanediol diacrylate, diethyl aminoethyl methacrylate and 1,9- nonyls two It is one or more in alcohol diacrylate.
3. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the acrylate is selected from acrylic acid first Ester, ethyl acrylate, 2- cyclohexyl methacrylates, butyl acrylate, acrylamide, hydroxy-ethyl acrylate, 2,3- dihydroxy Propyl acrylate, 2- methyl -2- acrylic acid 1,1'- [2- (hydroxymethyl) -2- [[(2- methyl-1s-oxo -2- propylene -1- Base) oxygroup] methyl] -1,3- propane diyl] ester, 2- cyanoethyl acrylates, glycidyl methacrylate, 6- hydroxyls Ethylhexyl acrylate, 3- [(4'- cyanobiphenyl -4- bases) oxygroup] propyl 2- acrylate, 2- butyl octyls methacrylate, It is one or more in 1,4 butanediol diacrylate and 1,9- nonanediol diacrylates.
4. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the solvent is selected from toluene, methanol, second The one or more such as acetoacetic ester.
5. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the initiator causes selected from peroxide Agent and/or azo-initiator.
6. a kind of novel acrylic pressure sensitive adhesive described in claim 5, which is characterized in that the peroxide initiator is persulfuric acid Potassium, ammonium persulfate, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide, peroxide Change dibenzoyl, dilauroyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, dicetyl peroxydicarbonate two One kind in isopropyl ester, di-cyclohexylperoxy di-carbonate.
7. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the preparation of the acrylate pressure sensitive adhesive is former Material also includes benzo-crown ether.
8. a kind of novel acrylic pressure sensitive adhesive described in claim 7, which is characterized in that the structural formula of the benzo-crown ether is such as Under:
The R group is
9. a kind of novel acrylic pressure sensitive adhesive described in claim 1, which is characterized in that the preparation of the acrylate pressure sensitive adhesive is former Material also includes organic titanium.
10. a kind of novel acrylic pressure sensitive adhesive described in claim 9, which is characterized in that the organic titanium prepares raw material packet Contain:Butyl titanate and four (triethanolamine) zirconiums.
CN201810002452.1A 2018-01-02 2018-01-02 Acrylic pressure-sensitive adhesive Active CN108192019B (en)

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CN109232814A (en) * 2018-09-17 2019-01-18 江苏创客新材料科技有限公司 A kind of high adsorption automatic vent type protective film
CN110759887A (en) * 2019-10-14 2020-02-07 湖南大学 Crown ether compound and application thereof
CN112226183A (en) * 2020-10-26 2021-01-15 浙江龙游道明光学有限公司 Removable pressure sensitive adhesive composition
CN114015386A (en) * 2021-11-05 2022-02-08 深圳日高胶带新材料有限公司 Emulsion type acrylate pressure-sensitive adhesive capable of being repeatedly torn off and stuck for use

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CN105542671A (en) * 2015-12-18 2016-05-04 广州市白云化工实业有限公司 Packaging adhesive film for photovoltaic modules
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JP2012046757A (en) * 2011-09-28 2012-03-08 Hitachi Chem Co Ltd Adhesive for connecting circuit, and circuit connection method and connection body using the same
CN105542671A (en) * 2015-12-18 2016-05-04 广州市白云化工实业有限公司 Packaging adhesive film for photovoltaic modules
CN105802547A (en) * 2016-04-14 2016-07-27 上海政太纳米科技股份有限公司 EVA hot melt adhesive for book binding
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CN109232814A (en) * 2018-09-17 2019-01-18 江苏创客新材料科技有限公司 A kind of high adsorption automatic vent type protective film
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CN110759887B (en) * 2019-10-14 2020-08-28 湖南大学 Crown ether compound and application thereof
CN112226183A (en) * 2020-10-26 2021-01-15 浙江龙游道明光学有限公司 Removable pressure sensitive adhesive composition
CN114015386A (en) * 2021-11-05 2022-02-08 深圳日高胶带新材料有限公司 Emulsion type acrylate pressure-sensitive adhesive capable of being repeatedly torn off and stuck for use

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