CN108192019A - A kind of novel acrylic pressure sensitive adhesive - Google Patents
A kind of novel acrylic pressure sensitive adhesive Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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
- C09J133/24—Homopolymers or copolymers of amides or imides
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
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.
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| CN201810002452.1A CN108192019B (en) | 2018-01-02 | 2018-01-02 | Acrylic pressure-sensitive adhesive |
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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 |
| 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 |
| CN106520005A (en) * | 2016-11-11 | 2017-03-22 | 宁波朝辉新材料有限公司 | Protective film for prism film and preparation method of protective film |
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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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| CN110759887A (en) * | 2019-10-14 | 2020-02-07 | 湖南大学 | Crown ether compound and application thereof |
| 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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| CN108192019B (en) | 2020-03-20 |
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