CN105189580A - Acrylic emulsion resin having excellent adhesive property and preparation method therefor - Google Patents
Acrylic emulsion resin having excellent adhesive property and preparation method therefor Download PDFInfo
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- CN105189580A CN105189580A CN201480013397.6A CN201480013397A CN105189580A CN 105189580 A CN105189580 A CN 105189580A CN 201480013397 A CN201480013397 A CN 201480013397A CN 105189580 A CN105189580 A CN 105189580A
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- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- 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
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
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- 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
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- 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
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- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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Abstract
The present invention relates to an acrylic emulsion resin having an excellent adhesive property and a preparation method therefor and, specifically, to: an acrylic emulsion resin, characterized in that a mixed monomer and a crosslinking agent are co-polymerized, the mixed monomer comprising i) an acrylic monomer having an alkyl group of carbon number 1 to 18, and ii) at least one modified acrylic monomer selected from the group consisting of a modified acrylic monomer represented by formula 1 (the same as formula 1 indicated in claim 1) and a modified acrylic monomer represented by formula 2 (the same as formula 2 indicated in claim 1), and optionally comprising iii) at least one monomer selected from the group consisting of an allyl ester, a vinyl ester, an unsaturated acetate and an unsaturated nitrile and iv) at least one monomer selected from the group consisting of an unsaturated carboxylic acid and hydroxyl group-containing unsaturated monomer; and a preparation method therefor.
Description
Technical field
The present invention relates to a kind of have excellent adhesiveness can acrylic emulsion resin and preparation method thereof; More specifically, relate to a kind of acrylic emulsion resin and preparation method thereof, wherein, monomer mixture and linking agent copolymerization, described monomer mixture comprises: i) have C
1-C
18the Acrylic Acid Monomer of alkyl; And ii) be selected from the modified propylene acid mono represented by specified chemical formula; And not necessarily comprise iii) be selected from least one monomer of allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile; And iv) be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl.
Background technology
Pressure sensitive adhesive (PSAs) is the semisolid being bonded in material at low pressures, there is the viscoelastic property being different from tackiness agent, there is the basic property of initial tack, bonding and cohesive force, and in nearly all industry of such as Product labelling, advertisement, printing, chemistry, medical treatment product, home appliances, automobile, office appliance etc.
According to the monomer of the preparation for PSAs, PSAs can be divided into acrylic acid, based on rubber, based on silicon and based on the PSAs of EVA, and solvent-borne type, emulsion-type and hot-melting type can be divided into according to its shape.
Most conventional PSAs for adhesive tape, adhesive label etc. can be the PSAs based on solvent.But, should based on PSAs of solvent cause make after residual solvent entered air for a long time, thus the resident in house suffers from and such as has a headache; The stimulation of eyes, nose and throat; Cough; Scratch where it itches; Dizzy; Fatigue, the symptom of decreased attention etc., and, when long-term exposure is in this residual solvent, suffer from the sick house syndrome causing respiratory disease, heart trouble, cancer etc.
Reason for this reason, uses water as the emulsion PSAs based on water of dispersion medium, is conducive to environment protection and non-discharge harmful as the PSAs based on non-solvent.Many concerns are obtained.Because tackiness agent viscosity has nothing to do with the molecular weight as the polymkeric substance of dispersion, molecular weight can should be used higher than the polymkeric substance of the molecular weight of the polymkeric substance based on solvent based on the emulsion PSAs of water, the concentration range of wide in range solids content can be had, there is in low solid content district low ageing resistance, low viscosity and good bond properties, and with other polymkeric substance, there is good consistency.
But, owing to using water as solvent, drying rate slowly should be had based on the emulsion PSAs of water, for hydrophobic adhesive surface (such as, there is low surface tension and the material formed by polyolefine (such as polyethylene, polypropylene etc.)) there is low bond strength, the scope that narrow solidifying agent is selected, and the initial adhesion strength of deterioration.In addition, the emulsion PSAs based on water comprises emulsifying agent and dispersion agent, thus, compared with the physicals of the PSAs based on solvent, not there is excellent physicals, e.g., low water resisting property etc., and therefore can not replace the PSAs based on solvent immediately.
As this representative instance based on the emulsion PSAs of water, there is acrylic emulsion resin.The deterioration of above-mentioned physicals is considered to the various additives owing to adding in the process during emulsion polymerization and after adding.Especially, the tensio-active agent giving acrylic emulsion stability after coating is present in binder resin surface, thus the minimizing of the bond strength of the material of bonding is worked, and during being coated with, hinder the fusion in PSA between acrylic emulsion particle, cause cohesive force to reduce.
In addition, reduce the surface tension of PSA thus wild phase is a kind of form of tensio-active agent for the wetting agent of the wettability on the surface of silicon separate-type paper, thus cause and those problem Similar Problems caused by tensio-active agent.Antifoams and various inorganic additives also make the physicals deterioration based on the emulsion PSAs of water.
In order to propose the problems referred to above and increase the bonding to the material with low surface tension, attempt various method.Especially, the resin based on rubber with acrylic emulsion mixed with resin or can add tackifier further.
But when this resin based on rubber and acrylic emulsion mixed with resin, the described resin based on rubber and described acrylic emulsion resin have low consistency, thus reduce transparency and deteriorated thermostability, oxidative stability, weather resistance etc.In addition, based on the acrylic emulsion of 100 weight parts, tackifier can be added with the amount of 50 weight parts and carry out enhancing adhesive strength.But when the amount of tackifier is more than 50 weight part, bond strength reduces to a certain extent and stability in storage is deteriorated.
Therefore, being badly in need of exploitation and Acrylic Acid Monomer can copolymerization and the material with low surface tension is had to the technology of the high acrylic emulsion PSA bonded.
Summary of the invention
Technical problem
The technical object that the problems referred to above and being intended to that the present invention is intended to propose this area are sought for a long time.
As the result of various further investigation and various different experiments, the present inventor has prepared the acrylic emulsion resin comprising the modified propylene acid mono represented by specified chemical formula, and confirm when using described acrylic emulsion resin-made for acrylic emulsion PSA, described acrylic emulsion PSA even demonstrates high bonding to the material with low surface tension, thus completes the present invention.
Technical scheme
According to an aspect of the present invention, provide acrylic emulsion resin, wherein, monomer mixture and linking agent copolymerization, described monomer mixture comprises: i) have C
1-C
18the Acrylic Acid Monomer of alkyl; And ii) be selected from least one modified propylene acid mono of the modified propylene acid mono represented by following formula 1 and the modified propylene acid mono represented by following formula 2.
Wherein, in above formula 1, n is 0 to 20; And
In above formula 2, n ' is 0 to 18.
Term " monomer mixture " refers to comprise any monomer mixture preparing the above-mentioned monomer of acrylic emulsion resin that can be not particularly limited by its polymerization as used herein.Such as, above-mentioned monomer can add with admixture and be polymerized or can sequentially add and be polymerized, and other amendments various are possible.
In specific embodiment, described acrylic emulsion resin can use the linking agent of monomer mixture and 0.1wt% to 5wt% to prepare by being polymerized, and this monomer mixture comprises: the i of 75wt% to 95wt%) there is C
1-C
18the Acrylic Acid Monomer of alkyl and the ii of 0.5wt% to 20wt%) be selected from least one modified propylene acid mono of the modified propylene acid mono of formula 1 and the modified propylene acid mono of formula 2, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin.
Meanwhile, can by being used alone described Acrylic Acid Monomer and prepared by described modified acroleic acid monomer copolymerization according to acrylic emulsion resin of the present invention.But especially, described acrylic emulsion resin can be prepared other monomer copolymerizations of copolymerization by further using with described Acrylic Acid Monomer.
Especially, described acrylic emulsion resin can use monomer mixture and linking agent to be prepared by copolymerization, and this monomer mixture comprises: i) have C
1-C
18the Acrylic Acid Monomer of alkyl; Ii) at least one modified propylene acid mono of the modified propylene acid mono of formula 1 and the modified propylene acid mono of formula 2 is selected from; Iii) at least one monomer of allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile is selected from; And iv) be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl.
So, when using other monomers except described Acrylic Acid Monomer and described modified propylene acid mono to prepare described acrylic emulsion resin by polymerization, based on the gross weight of acrylic emulsion resin, the amount of above composition can be: the i of 60wt% to 80wt%) there is C
1-C
18the Acrylic Acid Monomer of alkyl, the ii of 0.5wt% to 20wt%) be selected from least one modified propylene acid mono of the modified propylene acid mono of formula 1 and the modified propylene acid mono of formula 2, the iii of 0.5wt% to 20wt%) be selected from least one monomer of allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile, the iv of 0.5wt% to 10wt%) be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl, and the linking agent of 0.1wt% to 3wt%.
The present inventor confirms, as mentioned above, when using modified propylene acid mono to prepare acrylic emulsion resin, and described modified propylene acid mono and Acrylic Acid Monomer copolymerization, thus strengthen the bonding to the material with low surface tension.
Below, each monomer will be described in detail.
Based on the gross weight of acrylic emulsion resin, the i in above-mentioned scope can be comprised) Acrylic Acid Monomer.When the amount of Acrylic Acid Monomer is less than above scope, the initial tack of acrylic emulsion resin can not be obtained.On the other hand, when the amount of Acrylic Acid Monomer exceedes above-mentioned scope, when peeling off from here after using, described acrylic emulsion resin is exceedingly transferred in the material of bonding.
In addition, the alkyl of Acrylic Acid Monomer i) can have 1 to 18 carbon atom.When the quantity of the carbon atom of alkyl is more than 18, described acrylic emulsion resin is too soft, thus makes bond properties deterioration.
I) Acrylic Acid Monomer can be, such as, be selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, heptylacrylate, Isooctyl acrylate monomer, Octyl methacrylate, (methyl) 2-EHA, isodecyl acrylate, decyl-octyl methacrylate, lauryl methacrylate, isobornyl methacrylate, the at least one of (methyl) octadecyl acrylate and (methyl) lauryl acrylate.Especially, based on the gross weight of Acrylic Acid Monomer, Acrylic Acid Monomer i) can be the methyl methacrylate of the ethyl acrylate of 20wt% to 70wt%, the butyl acrylate of 20wt% to 70wt% and 2wt% to 10wt%.
Based on the gross weight of acrylic emulsion resin, ii can be comprised with the scope of above-mentioned amount) the modified propylene acid mono of above formula 1 or 2.When the acrylic resin modified amount of formula 1 or 2 is less than above-mentioned amount, enhancing to the bonding of the material with low surface tension can not be expected.On the other hand, when the amount of the modified propylene acid mono of formula 1 or 2 exceedes above-mentioned amount, the amount of Acrylic Acid Monomer reduces relatively, thus can not obtain the initial tack of acrylic emulsion resin.
Meanwhile, when described acrylic emulsion resin comprises other monomers with described Acrylic Acid Monomer and described modified acroleic acid monomers copolymerizable further, as mentioned above, based on the gross weight of acrylic emulsion resin, can with 0.5wt% to 20wt%, especially comprise iii with the amount of 2wt% to 15wt%) monomer.As iii) the amount of monomer when being less than 0.5wt%, the bond properties of acrylic emulsion resin does not almost change, thus is difficult to obtain enough bond propertiess.On the other hand, as iii) the amount of monomer more than 20wt% time, described acrylic emulsion resin starts overvulcanization, thus makes it bond remarkable deterioration.
Iii) monomer can be, such as, at least one of vinyl acetate, vinyl butyrate, propionate, vinyl laurate, V-Pyrol RC, vinylbenzene, the monomer based on modified vinyl represented by following formula 3, vinyl cyanide and methacrylonitrile is selected from.Especially, iii) monomer can be the monomer based on modified vinyl of following formula 3:
Wherein, n " be 0 to 18.
As by the present inventor confirm, the monomer based on modified vinyl of above formula 3 and described Acrylic Acid Monomer and described modified acroleic acid monomer copolymerization, thus promote that acrylic emulsion resin is to the further enhancing of bonding of material with low surface tension.
As mentioned above, based on the gross weight of acrylic emulsion resin, iv can be comprised with the amount of 0.5wt% to 10wt%) monomer.As iv) the amount of monomer when being less than 0.5wt%, described acrylic emulsion resin becomes too soft, thus can not obtain enough bond propertiess.On the other hand, as iv) the amount of monomer more than 10wt% time, described acrylic emulsion resin becomes excessively hard, thus significantly deterioration bonding.
Iv) monomer can be, such as, at least one of vinylformic acid, methylene-succinic acid, maleic anhydride, fumaric acid, β-crotonic acid, methacrylic acid, β-dimethyl-aminoethylmethacrylate, (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl lauryl and (methyl) dihydroxypropyl propylene glycol ester is selected from.
In specific embodiment, based on the gross weight of acrylic emulsion resin, the monomer mixture for the preparation of acrylic emulsion resin can comprise the unsaturated monomer containing epoxy group(ing) of 0.1wt% to 3wt% further.When the amount of the unsaturated monomer containing epoxy group(ing) is in above-mentioned scope, described acrylic emulsion resin has enough bondings.
The described unsaturated monomer containing epoxy group(ing) can be, such as, be selected from least one of (methyl) glycidyl acrylate, (methyl) vinylformic acid-Alpha-Methyl glycidyl ester, glycidyl allyl ether, (methyl) vinylformic acid oxocyclohex ester and (methyl) vinylformic acid-3,4-epoxycyclohexanecarboxylate.More specifically, the described unsaturated monomer containing epoxy group(ing) can be (methyl) glycidyl acrylate and glycidyl allyl ether.
In specific embodiment, described linking agent can be selected from: organic crosslinking agent, as polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, allyl methacrylate(AMA), 1, 6-hexanediyl ester, ethylene glycol dimethyl diacrylate, glycol diacrylate, ethylene glycol ethoxylate diacrylate, ethylene glycol propoxylate diacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol propoxylate diacrylate, trimethyl propane ethyoxylate triacrylate, trimethyl propane propoaylate triacrylate, tetramethylolmethane ethyoxylate triacrylate, tetramethylolmethane propoaylate triacrylate, the at least one of vinyl trimethoxy silane and Vinylstyrene.Especially, described linking agent can be at least one being selected from polyethyleneglycol diacrylate and polypropyleneglycol diacrylate.
Present invention also offers a kind of method preparing described acrylic emulsion resin.
In a particular embodiment, the method preparing described acrylic emulsion resin by being used alone Acrylic Acid Monomer and modified propylene acid mono comprises the linking agent of polymeric monomer intermixture and 0.1wt% to 5wt%, and this monomer mixture comprises: the i of 75wt% to 95wt%) there is C
1-C
18the Acrylic Acid Monomer of alkyl and the ii of 0.5wt% to 20wt%) be selected from least one modified propylene acid mono of the modified propylene acid mono of above formula 1 and the modified propylene acid mono of above formula 2, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin.
In another particular embodiment of the invention, except described Acrylic Acid Monomer and described modified propylene acid mono, other monomers of copolymerization method of preparing described acrylic emulsion resin can comprise the linking agent of polymeric monomer intermixture and 0.1wt% to 3wt% by further using with Acrylic Acid Monomer, this monomer mixture comprises: the i of 60wt% to 80wt%) there is C
1-C
18the Acrylic Acid Monomer of alkyl; The ii of 0.5wt% to 20wt%) be selected from least one modified propylene acid mono of the modified propylene acid mono of above formula 1 and the modified propylene acid mono of above formula 2; The iii of 0.5wt% to 20wt%) be selected from least one monomer of allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile; With the iv of 0.5wt% to 10wt%) be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin.
In a particular embodiment, the polymerization of monomer mixture and linking agent is not particularly limited, but can be undertaken by the letex polymerization easily controlling reaction heat.Especially, described polyreaction can comprise: the first step, prepares solution by adding water, ionogen and tensio-active agent to reactor, and the temperature to 80 DEG C raising reactor removes oxygen, and dissolves initiator in gained solution; Second step, by preparing emulsion to adding water, ionogen and tensio-active agent for the preparation of the monomer mixture of acrylic emulsion resin and the mixture of linking agent; 3rd step, preparing acrylic emulsion resin by adding the solution prepared by the first step, the emulsion prepared by second step and initiator successively, being warming up to 80 DEG C, and cooling gained solution to room temperature; With the 4th step, regulate the pH of acrylic emulsion resin to 6 to 9.
Described initiator can be water-soluble polymerization initiator (persulphate or basic metal, hydrogen peroxide, superoxide, hydroperoxide etc. as ammonium), and can be combined with at least one reductive agent and realize letex polymerization at low temperatures.Described reductive agent can be sodium bisulfite, Sodium Pyrosulfite, V-Brite B, Sulfothiorine, sodium formaldehyde sulfoxylate, xitix etc.
Consider the physicals of pressure sensitive adhesive, described polymerization can be carried out to 100 DEG C, more preferably 40 DEG C at 0 DEG C to the temperature of 90 DEG C, and described temperature can use as the method being used alone initiator, initiator is combined with at least one reductive agent regulates.
Ionogen for polyreaction is used for regulating pH and making the acrylic emulsion resin of preparation have stability.Especially, described ionogen can be at least one being selected from sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate and sodium-chlor.Especially, described ionogen can be sodium carbonate.
Described tensio-active agent is used for during polyreaction, produce initial micella, regulates the size of the micella produced, and makes the micella of generation have stability.Described tensio-active agent is made up of hydrophilic radical and lipophilic group and is classified as anion surfactant, cats product and nonionogenic tenside.Main use anion surfactant and nonionogenic tenside and can be combined to realize mechanical stability and chemical stability.
The example of anion surfactant includes, but are not limited to, alkyl diphenyl ether disulphonic acid sodium, Voranol EP 2001 sodium sulfate, polyoxyethylene laurel ether sodium sulfate and dialkyl sodium sulfosuccinate.The example of nonionogenic tenside includes, but are not limited to, polyoxyethylene alkane aryl oxide, polyoxyethylene and polyoxyethylene alkyl ester.These anion surfactants can be used alone or their at least two kinds can be combined, and these nonionogenic tensides can be used alone or their at least two kinds can be combined.The situation that the comparable anion surfactant of its situation and nonionogenic tenside are combined is more effective.
Meanwhile, the pH of acrylic emulsion resin can use alkaline matter to regulate.In this, described acrylic emulsion resin has the pH of 6 to 9, more preferably has the pH of 7 to 8.Described alkaline matter can be inorganic substance, as the oxyhydroxide, muriate, carbonate etc. of unit price or polyvalent metal; Ammonia; Organic amine etc.
Present invention also offers the acrylic emulsion pressure sensitive adhesive (PSA) based on water comprising the acrylic emulsion resin using aforesaid method to prepare, that is, the acrylic emulsion PSA based on water by disperseing described acrylic emulsion resin-made standby in water.Present invention also offers adhesive sheet, it comprises by being coated with the described binder layer formed to binder film or sheet based on the acrylic emulsion PSA of water.
Described binder film or sheet can be have low surface tension based on polyolefinic substrate, and in the case, also can have enough bondings according to adhesive sheet of the present invention.The adhesive sheet comprising binder layer can be applied to inner/outer material, house decorative material, the film of advertisement or the binder film of label for building or sheet.Described binder layer can have 10 μm of thickness to 100 μm, preferably 20 μm to 30 μm.
Embodiment
Now, the present invention is described in detail with reference to following examples.These embodiments are provided only to should not be construed as restriction to scope and spirit of the present invention for purpose of explanation.
< embodiment 1>
the preparation of acrylic emulsion resin
To the Sodium Lauryl Sulphate BP/USP of the 3L glass reactor ion exchanged water and 20g (30wt%) that add 280g of equipment thermostat container, agitator, dropping funnel, nitrogen injection lines and reflux exchanger as tensio-active agent.While stirring gained solution, with the air of nitrogen surrogate response device inside, and temperature is wherein risen to 70 DEG C in nitrogen atmosphere and keeps 60 minutes.
The polypropyleneglycol diacrylate of the methyl methacrylate of the butyl acrylate of 308g, the ethyl acrylate of 570g, 50g, the phenoxyethyl acrylate of 50g, the vinylformic acid of 20g and 3g is added in 3L beaker respectively and monomer mixture is prepared in mixing, and adds the solution that be made up of as the sodium carbonate of anion surfactant, 5g and the water of 650g the alkyl diphenyl ether disulphonic acid sodium solution of 50g (30wt%) wherein and use agitator stirring to prepare creamy emulsion.
The ammonium persulfate solution of described emulsion and 150g (10wt%) continues to be added to glass reactor more than 4 hours with equal proportion.When completing, adding of ammonium persulfate solution and emulsion, is fashionable, and the temperature of reactor is increased to 80 DEG C in 30 minutes, and gained solution keeps one hour at 80 DEG C, is then cooled to room temperature to prepare acrylic emulsion PSA.
After this, the ammoniacal liquor of 30wt% is added to described acrylic emulsion PSA to regulate pH to 7.5.
the manufacture of adhesive sheet
The acrylic emulsion PSA prepared in embodiment 1 is coated on silicon be coated with on the release scraps of paper, and the described release scraps of paper through coating are dry in the baking oven of 100 DEG C, and within 2 hours, to form thickness be 20 μm of acrylic emulsion binder layers.Release for gained scraps of paper lamination together with art paper is formed adhesive sheet, and described adhesive sheet is cut into the size of 1 inch of x200mm, thus complete the manufacture of adhesive tape sample.
< embodiment 2>
Except using the monomer mixture of the 2-methoxyl group-4-chavicol of the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 300g, 570g, 50g, 50g, the vinylformic acid of 20g and the polypropyleneglycol diacrylate of 10g, prepare acrylic emulsion resin in the same manner as example 1.
< embodiment 3>
Except the monomer mixture of polypropyleneglycol diacrylate using the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 338g, 570g, 50g, the phenoxyethyl acrylate of 20g, the vinylformic acid of 20g and 2g, prepare acrylic emulsion resin in the same manner as example 1.
< embodiment 4>
Except using the monomer mixture of the 2-methoxyl group-4-chavicol of the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 330g, 570g, 50g, 20g, the vinylformic acid of 20g and the polypropyleneglycol diacrylate of 10g, prepare acrylic emulsion resin in the same manner as example 1.
< comparative example 1>
Except the monomer mixture of polypropyleneglycol diacrylate using the ethyl acrylate of the butyl acrylate of 358g, 570g, the methyl methacrylate of 50g, the vinylformic acid of 20g and 2g, prepare acrylic emulsion resin in the same manner as example 1.
< comparative example 2>
Except the monomer mixture of polypropyleneglycol diacrylate using the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 108g, 570g, 50g, the phenoxyethyl acrylate of 250g, the vinylformic acid of 20g and 2g, prepare acrylic emulsion resin in the same manner as example 1.
< comparative example 3>
Except using the monomer mixture of the 2-methoxyl group-4-chavicol of the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 200g, 570g, 50g, 150g, the vinylformic acid of 20g and the polypropyleneglycol diacrylate of 10g, prepare acrylic emulsion resin in the same manner as example 1.
< comparative example 4>
Except the monomer mixture of polypropyleneglycol diacrylate using the methyl methacrylate of the ethyl acrylate of the butyl acrylate of 308g, 570g, 50g, the ethyl propenoate of 50g, the vinylformic acid of 20g and 2g, prepare acrylic emulsion resin in the same manner as example 1.
< EXPERIMENTAL EXAMPLE 1>
The bond properties of the acrylic emulsion resin using following methods assessment to prepare according to embodiment 1 to 4 and comparative example 1 to 4.Result shows in table 1 below.
* room temperature bonding (90 ° of strippings) test: under the prerequisite of not infiltrating bubble, the adhesive tape sample comprising the acrylic emulsion resin respectively prepared is attached on material (SUS or HDPE), by 2kg roller on the surface of adhesive tape sample with the speed to-and-fro movement 5 times of 300mm/min, and by gained sample at room temperature aging 30 minutes, then use TA texture analyser to carry out 90 ° of strippings to described aging adhesive tape with the speed of 5mm/ second.
* loop tack test: the loop tack measuring each adhesive tape according to FINAT method of testing.Testing standard is the method for the initial tack measuring each adhesive tape sample making annular according to the measurement of FTM9-loop tack.
* thermo-resistance measurement: each adhesive tape sample is attached in 500ml annular polyethylene (PE) bottle, and then gained sample storage is cooled to room temperature in 2 hours in the baking oven of 60 DEG C.In this, the time that adhesive tape sample is separated with described bottle is measured.
[table 1]
CF: bond damage
As shown in Table 1, can confirm, comprise the phenoxyethyl acrylate or 2-methoxyl group-4-chavicol that are represented by above formula 1 or 2 as the acrylic emulsion resin of embodiment 1 to 4 that can strengthen the monomer bonded with high density polyethylene(HDPE) (HDPE), thus demonstrate higher than the stripping strength of the acrylic emulsion resin of comparative example 1 to 4 and the initial tack to HDPE.
On the contrary, can confirm, the acrylic emulsion resin of comparative example 1 does not comprise according to modified propylene acid mono of the present invention, thus the low bonding demonstrated HDPE, amount due to the phenoxyethyl acrylate wherein comprised exceedes the amount of recommendation, the acrylic emulsion resin of comparative example 2 demonstrates the bonding reduced to a certain extent, and, amount due to the 2-methoxyl group-4-chavicol wherein comprised exceedes the amount of recommendation, and the acrylic emulsion resin of comparative example 3 stands bond damage.
Namely, when using the modified propylene acid mono (as phenoxyethyl acrylate, 2-methoxyl group-4-chavicol etc.) as above-mentioned predetermined amount to prepare acrylic emulsion resin, the height that the acrylic emulsion resin prepared can demonstrate for the material with low surface tension bonds.
Although the object that the preferred embodiment of the present invention is only explanation is open, when do not depart from the following claims disclosed scope of the present invention and essence, it is possible for skilled person will appreciate that various amendment, interpolation and substituting.
Industrial applicibility
As mentioned above, acrylic emulsion resin according to the present invention is prepared by using the modified acroleic acid monomer polymerization represented by specified chemical formula, thus demonstrates the bonding of the enhancing to the material with low surface tension.Therefore, regardless of the performance of bonded material, use the standby acrylic emulsion PSA of described acrylic emulsion resin-made to have excellent bond strength, thus do not need and mix with the resin etc. based on rubber that propenyl has a bad consistency, and therefore also can have transparency.
Claims (16)
1. an acrylic emulsion resin, wherein, monomer mixture and linking agent copolymerization, described monomer mixture comprises and i) has C
1-C
18the Acrylic Acid Monomer of alkyl; And ii) be selected from least one modified propylene acid mono of the modified propylene acid mono represented by following formula 1 and the modified propylene acid mono represented by following formula 2:
Wherein, in above formula 1, n is 0 to 20; And
In above formula 2, n ' is 0 to 18.
2. acrylic emulsion resin according to claim 1, wherein, the linking agent copolymerization of monomer mixture and 0.1wt% to 5wt%, described monomer mixture comprises: 75wt% to 95wt% has C
1-C
18at least one modified propylene acid mono of the modified propylene acid mono of the Acrylic Acid Monomer of alkyl and the formula that is selected from 1 of 0.5wt% to 20wt% and the modified propylene acid mono of formula 2, wherein, the amount of described monomer and linking agent is the gross weight based on ACRYLIC EMULSION system resin.
3. an acrylic emulsion resin, wherein, monomer mixture and linking agent copolymerization, described monomer mixture comprises and i) has C
1-C
18the Acrylic Acid Monomer of alkyl; Ii) the modified propylene acid mono represented by following formula 1 and at least one modified propylene acid mono of modified propylene acid mono represented by following formula 2 is selected from; Iii) at least one monomer of allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile is selected from; And iv) be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl:
Wherein, in above formula 1, n is 0 to 20; And
In above formula 2, n ' is 0 to 18.
4. acrylic emulsion resin according to claim 3, wherein, the linking agent copolymerization of monomer mixture and 0.1wt% to 3wt%, described monomer mixture comprises: 60wt% to 80wt% has C
1-C
18the Acrylic Acid Monomer of alkyl; At least one modified propylene acid mono of the modified propylene acid mono of the formula that is selected from 1 of 0.5wt% to 20wt% and the modified propylene acid mono of formula 2; At least one monomer being selected from allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile of 0.5wt% to 20wt%; With at least one monomer being selected from unsaturated carboxylic acid and the unsaturated monomer containing hydroxyl of 0.5wt% to 10wt%, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin.
5. the acrylic emulsion resin according to claim 1 or 3, wherein, i) Acrylic Acid Monomer is selected from (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, heptylacrylate, Isooctyl acrylate monomer, (methyl) Octyl acrylate, (methyl) ethyl acrylate, isodecyl acrylate, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) isobornyl acrylate, the at least one of (methyl) octadecyl acrylate and (methyl) lauryl acrylate.
6. acrylic emulsion resin according to claim 3, wherein, iii) monomer be at least one being selected from vinyl acetate, vinyl butyrate, propionate, vinyl laurate, V-Pyrol RC, vinylbenzene, the monomer based on modified vinyl represented by following formula 3, vinyl cyanide and methacrylonitrile:
Wherein, n " be 0 to 18.
7. acrylic emulsion resin according to claim 6, wherein, iii) monomer be the monomer based on modified vinyl represented by above formula 3.
8. acrylic emulsion resin according to claim 3, wherein, iv) monomer be at least one being selected from vinylformic acid, methylene-succinic acid, maleic anhydride, fumaric acid, β-crotonic acid, methacrylic acid, β-dimethyl-aminoethylmethacrylate, (methyl) acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) hy-droxybutyl, the own ester of (methyl) vinylformic acid hydroxyl, (methyl) vinylformic acid hydroxyl monooctyl ester, (methyl) vinylformic acid hydroxyl lauryl and (methyl) dihydroxypropyl propylene glycol ester.
9. the acrylic emulsion resin according to claim 1 or 3, wherein, described linking agent is at least one being selected from polyethyleneglycol diacrylate and polypropyleneglycol diacrylate.
10. prepare a method for acrylic emulsion resin according to claim 1, described method comprises the linking agent of polymeric monomer intermixture and 0.1wt% to 5wt%, and this monomer mixture comprises: i) 75wt%'s to 95wt% has C
1-C
18the Acrylic Acid Monomer of alkyl; And ii) at least one modified propylene acid mono being selected from the modified propylene acid mono represented by following formula 1 and the modified propylene acid mono represented by following formula 2 of 0.5wt% to 20wt%, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin:
Wherein, in formula 1, n is 0 to 20; And
In formula 2, n ' is 0 to 18.
11. 1 kinds of methods preparing acrylic emulsion resin according to claim 3, described method comprises the linking agent of polymeric monomer intermixture and 0.1wt% to 3wt%, and this monomer mixture comprises: i) 60wt%'s to 80wt% has C
1-C
18the Acrylic Acid Monomer of alkyl; Ii) at least one modified propylene acid mono being selected from the modified propylene acid mono represented by following formula 1 and the modified propylene acid mono represented by following formula 2 of 0.5wt% to 20wt%; Iii) at least one monomer being selected from allyl ester, vinyl ester, unsaturated acetic ester and unsaturated nitrile of 0.5wt% to 20wt%; And iv) 0.5wt% to 10wt% be selected from unsaturated carboxylic acid and at least one monomer of unsaturated monomer containing hydroxyl, wherein, the amount of monomer and linking agent is the gross weight based on acrylic emulsion resin:
Wherein, in formula 1, n is 0 to 20; And
In formula 2, n ' is 0 to 18.
12. 1 kinds of acrylic emulsion pressure sensitive adhesives (PSA) based on water, it comprises acrylic emulsion resin according to claim 1.
13. 1 kinds of acrylic emulsion PSA based on water, it comprises acrylic emulsion resin according to claim 3.
14. 1 kinds of adhesive sheets, it comprises the binder layer by being formed to binder film or the adhesive sheet coating acrylic emulsion PSA based on water according to claim 12.
15. 1 kinds of adhesive sheets, it comprises the binder layer by being formed to binder film or the adhesive sheet coating acrylic emulsion PSA based on water according to claim 13.
16. adhesive sheets according to claims 14 or 15, wherein, described binder film or adhesive sheet be have low surface tension based on polyolefinic substrate.
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| PCT/KR2014/004512 WO2015008930A1 (en) | 2013-07-19 | 2014-05-21 | Acrylic emulsion resin having excellent adhesive property and preparation method therefor |
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| KR (1) | KR101614341B1 (en) |
| CN (1) | CN105189580B (en) |
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| CN110563881A (en) * | 2019-09-29 | 2019-12-13 | 陕西科技大学 | double-bonded vanillyl alcohol modified styrene-acrylic emulsion and preparation method thereof |
| CN110563880A (en) * | 2019-09-29 | 2019-12-13 | 陕西科技大学 | double-bond vanillin-modified styrene-acrylic emulsion and preparation method thereof |
| CN110627948A (en) * | 2019-09-29 | 2019-12-31 | 陕西科技大学 | A kind of double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof |
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| CN105199581A (en) * | 2015-10-26 | 2015-12-30 | 刘朝辉 | Low-cost sea water resistant paint and preparation method thereof |
| KR102516241B1 (en) * | 2016-12-27 | 2023-03-29 | 주식회사 엘지화학 | Acrylic emulsion adhesive and method for preparing the same |
| CN115477900B (en) * | 2022-10-18 | 2023-06-30 | 深圳市高仁电子新材料有限公司 | Acrylic optical adhesive with three-layer structure and preparation method thereof |
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| JP2001172595A (en) * | 1999-12-20 | 2001-06-26 | Toagosei Co Ltd | Removable type adhesive film or sheet |
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| KR101171977B1 (en) * | 2008-06-05 | 2012-08-08 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition, polarizing plate and liquid crystal display device comprising the same |
| JP5478900B2 (en) * | 2009-01-07 | 2014-04-23 | 日東電工株式会社 | Light diffusable pressure-sensitive adhesive composition, light diffusable pressure-sensitive adhesive layer, and light diffusable pressure-sensitive adhesive sheet |
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2014
- 2014-05-21 WO PCT/KR2014/004512 patent/WO2015008930A1/en active Application Filing
- 2014-05-21 CN CN201480013397.6A patent/CN105189580B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101910346A (en) * | 2008-01-14 | 2010-12-08 | Lg化学株式会社 | Pressure-sensitive adhesive composition, protective film, polarizer and liquid crystal display comprising the same |
| CN102083933A (en) * | 2008-07-01 | 2011-06-01 | Lg化学株式会社 | Adhesive composition, protective film for a polarizing plate, polarizing plate, and liquid crystal display |
| CN101654604A (en) * | 2008-08-20 | 2010-02-24 | Lg化学株式会社 | Composition of acrylic pressure-sensitive adhesive and surface finishing material comprising the same |
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| CN110563881A (en) * | 2019-09-29 | 2019-12-13 | 陕西科技大学 | double-bonded vanillyl alcohol modified styrene-acrylic emulsion and preparation method thereof |
| CN110563880A (en) * | 2019-09-29 | 2019-12-13 | 陕西科技大学 | double-bond vanillin-modified styrene-acrylic emulsion and preparation method thereof |
| CN110627948A (en) * | 2019-09-29 | 2019-12-31 | 陕西科技大学 | A kind of double-bonded eugenol modified styrene-acrylic emulsion and preparation method thereof |
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| WO2015008930A1 (en) | 2015-01-22 |
| TWI516508B (en) | 2016-01-11 |
| KR20150010573A (en) | 2015-01-28 |
| KR101614341B1 (en) | 2016-04-21 |
| CN105189580B (en) | 2017-04-19 |
| TW201509965A (en) | 2015-03-16 |
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