CN113861897A - Modified emulsion type acrylate adhesive and preparation method thereof - Google Patents
Modified emulsion type acrylate adhesive and preparation method thereof Download PDFInfo
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- CN113861897A CN113861897A CN202111107099.1A CN202111107099A CN113861897A CN 113861897 A CN113861897 A CN 113861897A CN 202111107099 A CN202111107099 A CN 202111107099A CN 113861897 A CN113861897 A CN 113861897A
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- emulsion
- acrylate
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- acrylate adhesive
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- 239000000839 emulsion Substances 0.000 title claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 66
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000000080 wetting agent Substances 0.000 claims abstract description 16
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 14
- 239000008103 glucose Substances 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 11
- 239000002562 thickening agent Substances 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 34
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 22
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 21
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- 239000000872 buffer Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- -1 allyloxy nonylphenol Chemical compound 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 4
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- ZBTGXRBMYGTQHK-UHFFFAOYSA-N azanium;2-nonylphenolate Chemical compound N.CCCCCCCCCC1=CC=CC=C1O ZBTGXRBMYGTQHK-UHFFFAOYSA-N 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 18
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 18
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09J133/04—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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F220/12—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
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- 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
-
- 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a modified emulsion type acrylate adhesive which comprises, by weight, 0.1-10 parts of glucose, 0.3-0.6 part of an emulsifier, 35-45 parts of a soft monomer acrylate, 0.4-0.8 part of a functional monomer acrylate, 5-15 parts of a hard monomer acrylate, 0.4-1 part of an initiator, 45-60 parts of deionized water, 1-2 parts of ammonia water, 0.5-1.5 parts of a thickener and a proper amount of additives, wherein the proper amount of additives are a defoaming agent, a wetting agent and a buffering agent. The modified emulsion type acrylate adhesive prepared by the invention reduces the use of volatile organic solvents such as ethyl acetate, toluene and the like in the adhesive, is more environment-friendly, has longer storage time and better application effect.
Description
Technical Field
The invention relates to a modified emulsion type acrylate adhesive and a preparation method thereof, belonging to the technical field of adhesives.
Background
With the implementation of GB33372-2020 Limited volatile organic Compounds of adhesives, the national control of the content of volatile organic compounds in adhesives is more and more strict, the traditional coating industry is basically switched to water-based coatings, and the adhesive industry is also developing towards the solvent-free directions of water-based adhesives, hot-melt adhesives, ultraviolet curing adhesives and the like.
For example, patent (CN102964512A qingdao heil software limited) discloses an emulsion type acrylate pressure-sensitive adhesive and a preparation method thereof, and hydroxyethyl methacrylate is added for modification to finally prepare the emulsion type acrylate pressure-sensitive adhesive, which has good environmental protection property, but may leave watermarks or "ghosts" on the surface of the product when in use, generally because the protective film is removed to be a light fog-like substance remaining on the surface of the product, generally considered to be a result of migration of low molecular weight substances in the protective film adhesive from the surface of an object to be pasted on the protective film adhesive.
For example, a patent (CN 109321153A Guangdong Xinyu new material company limited) discloses an aqueous pressure-sensitive adhesive for an ultra-low viscosity protective film, an ultra-low viscosity protective film and a preparation method thereof, wherein an emulsion type pressure-sensitive adhesive prepared by selecting polydimethylsiloxane, butyl acrylate, isooctyl acrylate and the like with end-capped single-end double bonds utilizes ultra-low viscosity and high flexibility, and solves the technical problems that the aqueous pressure-sensitive adhesive in the prior art is difficult to be low in viscosity, poor in flexibility and easy to fall off powder, but the material is treated after being used; there still remains a significant problem.
For example, a patent (CN 106010386a jiangtai polymer new material limited in jiangyin city) discloses an emulsion type pressure-sensitive adhesive and a PE protective film prepared from the same, and the emulsion type pressure-sensitive adhesive prepared from an epoxy group-containing organosilicon, an acrylic monomer, a functional monomer and the like solves the adverse phenomena of watermarks, "ghosts" or mottles and the like left after the protective film is covered, but also has the problem of waste treatment after the material is used.
Disclosure of Invention
The invention aims to provide a modified emulsion type acrylate adhesive and a preparation method thereof, which improve the protective film prepared by the adhesive on the basis of ensuring the environmental protection of a water-soluble adhesive.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
the modified emulsion type acrylate adhesive comprises, by weight, 0.1-10 parts of glucose, 0.3-0.6 part of an emulsifier, 35-45 parts of soft monomer acrylate, 0.4-0.8 part of functional monomer acrylate, 5-15 parts of hard monomer acrylate, 0.4-1 part of an initiator, 45-60 parts of deionized water, 1-2 parts of ammonia water, 0.5-1.5 parts of a thickener and a proper amount of additives, wherein the proper amount of additives comprise a defoaming agent, a wetting agent and a buffering agent.
Further, the emulsifier is at least one of nonylphenol polyoxyethylene ether ammonium sulfate salt, polyether sulfate, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, allyl polyether sulfate and allyloxy nonylphenol polyoxyethylene ether sulfate.
Further, the initiator is ammonium persulfate.
Further, the defoaming agent is any one of polyether defoaming agents, higher alcohols and derivatives thereof, and aliphatic hydrocarbons containing nonionic parts.
Further, the wetting agent is polyacrylic acid or hydroxymethyl cellulose.
The second purpose of the invention is to provide a preparation method of the modified emulsion type acrylate adhesive, which comprises the following steps:
uniformly stirring a mixed solution of an emulsifier and deionized water, and filtering to obtain a pre-emulsion A;
taking a mixed solution of an emulsifier and deionized water, adding soft monomer acrylate, hard monomer acrylate and functional single-extraction acrylate while stirring, dispersing at a high speed for 30min, adding pre-emulsion A and glucose, and continuing dispersing at a high speed for 30min to obtain pre-emulsion B;
uniformly stirring and mixing deionized water, a part of emulsifier and a buffer, heating, adding a part of pre-emulsion B and a part of initiator for reaction after the temperature is stable, dropwise adding the rest of initiator and the rest of pre-emulsion B after the reaction is finished, and continuing the reaction;
after the reaction is finished, firstly preserving heat, then cooling to below 60 ℃, neutralizing the pH value to 7-8 by using ammonia water, and adding a thickening agent, a proper amount of defoaming agent and a proper amount of wetting agent to prepare the modified emulsion type acrylate adhesive;
in the step of dropwise adding the rest of the initiator and the rest of the pre-emulsion B, the initiator is kept to be 5min later than the pre-emulsion B, and the dropwise adding is finished.
Further, the temperature is stabilized at 80 ℃ when the deionized water, partial emulsifier and buffer are heated after being uniformly stirred and mixed; the heat preservation temperature is 83-85 ℃, and the heat preservation time is 120 min.
Furthermore, the filtration adopts a high-efficiency filtration group, which comprises a five-core filter element filter with a 0.5 mu mPP filter element and a three-core filter with a 0.1 mu mPP filter element, and the pressure of the filtration pump is less than 0.1 MPa.
The third purpose of the invention is to provide the application of the modified emulsion acrylate adhesive prepared by the method in the protection film.
Compared with the prior art, the invention has the following beneficial effects:
(1) the modified emulsion type acrylate adhesive prepared by modifying the acrylate derivative by adopting glucose and using deionized water as a diluent and a solvent reduces the use of volatile organic solvents such as ethyl acetate, toluene and the like in the adhesive, and is more environment-friendly;
(2) in the preparation process of the modified emulsion type acrylate adhesive, in the step of dropwise adding the rest initiator and the rest pre-emulsion B, the initiator is kept to be dropwise added later than the pre-emulsion B for 5min, and the raw materials in the pre-emulsion B can be ensured to react completely;
(3) according to the invention, a unique high-efficiency filtering group is adopted for filtering, so that other impurities in the raw materials can be fully filtered, the purity of the prepared modified emulsion type acrylate adhesive is ensured, the prepared product can be prevented from deteriorating due to long-time placement, and the storage time of the product is prolonged;
(4) the protective film prepared by the modified emulsion type acrylate adhesive solves the adverse phenomena of watermarks, ghosts or mottles and the like left after the protective film is covered, and can be conveniently treated after being used.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The acrylate adopted by the invention is divided into soft monomer acrylate, hard monomer acrylate and functional monomer acrylate. Wherein the soft monomer acrylate comprises at least one of butyl acrylate, ethyl acrylate and/or isooctyl acrylate; the hard monomer acrylate is methyl methacrylate; the functional monomer acrylate is hydroxyethyl acrylate and/or carboxyethyl acrylate.
Example 1
Taking 0.3 part by weight of nonylphenol polyoxyethylene ether ammonium sulfate salt as an emulsifier, 0.4 part by weight of ammonium persulfate as an initiator, 0.1 part by weight of glucose, 35 parts by weight of soft monomer acrylate, 0.4 part by weight of functional monomer acrylate, 5 parts by weight of hard monomer acrylate, 45 parts by weight of deionized water, 1 part by weight of ammonia water, 0.5 part by weight of a thickening agent, and a proper amount of a defoaming agent, a wetting agent and a buffering agent. Wherein the defoaming agent is polyether defoaming agent, and the wetting agent is polyacrylic acid.
0.1 weight portion of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate is dissolved in 16 weight portions of deionized water, after uniformly stirring, the suspended matters contained in the dissolved matters are removed by utilizing a high-efficiency filter group, wherein the high-efficiency filter group comprises a five-core filter element filter (using a 0.5 mu mPP filter element) and a three-core filter (using a 0.1 mu mPP filter element), and the filter pump pressure is less than 0.1MPa, so that the pre-emulsion A is prepared.
And additionally taking 0.1 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt, fully dissolving in 16 parts by weight of deionized water, taking 0.2 part by weight of hydroxyethyl acrylate, 0.2 part by weight of carboxyethyl acrylate, 20 parts by weight of butyl acrylate, 15 parts by weight of isooctyl acrylate and 5 parts by weight of methyl methacrylate, sequentially adding the monomers into the emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt water solution under the stirring condition, fully stirring and dispersing for 30min, adding 0.1 part by weight of glucose and the pre-emulsion A, and continuously stirring and dispersing for 30min to obtain the pre-emulsion B.
Adding 13 parts by weight of deionized water, 0.1 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate and a proper amount of buffer into the reaction kettle, stirring uniformly, and then heating. After the temperature is raised to 80 ℃, 0.2 part by weight of ammonium persulfate is added into the reaction kettle, part of the pre-emulsion B is dripped to be used as seed emulsion, and the temperature is kept for 5min after the seed emulsion is dripped to fully react. And (3) after the heat preservation is finished, synchronously dropwise adding the rest of the pre-emulsion B and 0.2 part by weight of aqueous solution of ammonium persulfate, and finishing dropping in 240 min. Keeping the ammonium persulfate to be dripped about 5min later than the pre-emulsion B, and keeping the temperature of the pre-emulsion B and the ammonium persulfate at 83-85 ℃ for 120min after the dripping is finished. After the heat preservation is finished, the temperature is reduced to below 50 ℃, a proper amount of antifoaming agent and wetting agent are added to improve the coating performance, and the pH value of the emulsion is adjusted to 7-8 by ammonia water. The prepared acrylic ester emulsion is filtered by a 200-mesh filter screen and then packaged for use.
Example 2
Taking 0.45 part by weight of nonylphenol polyoxyethylene ether ammonium sulfate salt as an emulsifier, 0.7 part by weight of ammonium persulfate as an initiator, 5 parts by weight of glucose, 40 parts by weight of soft monomer acrylate, 0.6 part by weight of functional monomer acrylate, 10 parts by weight of hard monomer acrylate, 50 parts by weight of deionized water, 1.5 parts by weight of ammonia water, 1 part by weight of thickener, and a proper amount of defoamer, wetting agent and buffer. Wherein the defoaming agent is higher alcohol and its derivatives, and the wetting agent is hydroxymethyl cellulose.
0.15 weight portion of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate is dissolved in 16 weight portions of deionized water, after uniformly stirring, the suspended matters contained in the dissolved matters are removed by utilizing a high-efficiency filter group, wherein the high-efficiency filter group comprises a five-core filter element filter (using a 0.5 mu mPP filter element) and a three-core filter (using a 0.1 mu mPP filter element), and the filter pump pressure is less than 0.1MPa, so that the pre-emulsion A is prepared.
And additionally taking 0.15 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt, fully dissolving in 16 parts by weight of deionized water, taking 0.3 part by weight of hydroxyethyl acrylate, 0.3 part by weight of carboxyethyl acrylate, 20 parts by weight of ethyl acrylate, 20 parts by weight of isooctyl acrylate and 10 parts by weight of methyl methacrylate, sequentially adding the monomers into the emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt water solution under the stirring condition, fully stirring and dispersing for 30min, adding 5 parts by weight of glucose and the pre-emulsion A, and continuously stirring and dispersing for 30min to obtain the pre-emulsion B.
Adding 18 parts by weight of deionized water, 0.15 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate and a proper amount of buffer into a reaction kettle, stirring uniformly, and then heating. After the temperature is raised to 80 ℃, 0.3 part by weight of ammonium persulfate is added into the reaction kettle, part of the pre-emulsion B is dripped to be used as seed emulsion, and the temperature is kept for 5min after the seed emulsion is dripped to fully react. And (3) after the heat preservation is finished, synchronously dropwise adding the rest of the pre-emulsion B and 0.4 part by weight of aqueous solution of ammonium persulfate, and finishing dropping in 240 min. Keeping the ammonium persulfate to be dripped about 5min later than the pre-emulsion B, and keeping the temperature of the pre-emulsion B and the ammonium persulfate at 83-85 ℃ for 120min after the dripping is finished. After the heat preservation is finished, the temperature is reduced to below 50 ℃, a proper amount of antifoaming agent and wetting agent are added to improve the coating performance, and the pH value of the emulsion is adjusted to 7-8 by 1.5 parts by weight of ammonia water. The prepared acrylic ester emulsion is filtered by a 200-mesh filter screen and then packaged for use.
Example 3
Taking 0.6 part by weight of nonylphenol polyoxyethylene ether ammonium sulfate salt as an emulsifier, 1 part by weight of ammonium persulfate as an initiator, 10 parts by weight of glucose, 45 parts by weight of soft monomer acrylate, 0.8 part by weight of functional monomer acrylate, 15 parts by weight of hard monomer acrylate, 60 parts by weight of deionized water, 2 parts by weight of ammonia water, 1.5 parts by weight of a thickening agent, and a proper amount of a defoaming agent, a wetting agent and a buffering agent. Wherein the defoamer is aliphatic hydrocarbon containing nonionic part, and the wetting agent is hydroxymethyl cellulose.
0.2 weight portion of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate is dissolved in 20 weight portions of deionized water, after uniformly stirring, the suspended matters contained in the dissolved matters are removed by utilizing a high-efficiency filter group, wherein the high-efficiency filter group comprises a five-core filter element filter (using a 0.5 mu mPP filter element) and a three-core filter (using a 0.1 mu mPP filter element), and the filter pump pressure is less than 0.1MPa, so that the pre-emulsion A is prepared.
And additionally taking 0.2 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt, fully dissolving in 20 parts by weight of deionized water, taking 0.4 part by weight of hydroxyethyl acrylate, 0.4 part by weight of carboxyethyl acrylate, 20 parts by weight of ethyl acrylate, 25 parts by weight of isooctyl acrylate and 15 parts by weight of methyl methacrylate, sequentially adding the monomers into the emulsifier nonylphenol polyoxyethylene ether ammonium sulfate salt water solution under the stirring condition, fully stirring and dispersing for 30min, adding 10 parts by weight of glucose and the pre-emulsion A, and continuously stirring and dispersing for 30min to obtain the pre-emulsion B.
20 parts by weight of deionized water, 0.2 part by weight of emulsifier nonylphenol polyoxyethylene ether ammonium sulfate and a proper amount of buffer are added into the reaction kettle, and the temperature is raised after the mixture is uniformly stirred. After the temperature is raised to 80 ℃, 0.4 part by weight of ammonium persulfate is added into the reaction kettle, part of the pre-emulsion B is dripped to be used as seed emulsion, and the temperature is kept for 5min after the seed emulsion is dripped to fully react. And (3) after the heat preservation is finished, synchronously dropwise adding the rest of the pre-emulsion B and 0.6 part by weight of aqueous solution of ammonium persulfate, and finishing dropping in 240 min. Keeping the ammonium persulfate to be dripped about 5min later than the pre-emulsion B, and keeping the temperature of the pre-emulsion B and the ammonium persulfate at 83-85 ℃ for 120min after the dripping is finished. After the heat preservation is finished, the temperature is reduced to below 50 ℃, a proper amount of antifoaming agent and wetting agent are added to improve the coating performance, and the pH value of the emulsion is adjusted to 7-8 by using 2 parts by weight of ammonia water. The prepared acrylic ester emulsion is filtered by a 200-mesh filter screen and then packaged for use.
In addition, the emulsifier not only can use nonylphenol polyoxyethylene ether ammonium sulfate salt, but also can use polyether sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, allyl polyether sulfate and allyloxy nonylphenol polyoxyethylene ether sulfate as the emulsifier, but the emulsifying effect of the nonylphenol polyoxyethylene ether ammonium sulfate salt is the most obvious through experiments.
Comparative example 1
The difference from the example 1 is that glucose is not added, and the mixed solution is filtered by using conventional filtration to prepare the emulsion type acrylate adhesive.
Test example 1
The invention also provides a protective film prepared from the modified emulsion type acrylate adhesive prepared in the embodiments 1-3, the protective film and the emulsion type acrylate adhesive prepared in the comparative example 1 are subjected to open-air standing treatment, the time of peculiar smell deterioration is tested, the adhesive force is tested by applying on a steel plate, glass, a PP plate and a PE plate, and the poor phenomena of remaining watermarks, bubbles, ghost shadows, flower spots and the like are observed. The test results are shown in Table 1.
The pasting method comprises the following steps:
1) uniformly coating the modified emulsion type acrylate adhesive on the corona surface of the base material, and putting the base material into an oven, wherein the temperature is low, and the condition that water in a solvent is completely baked is ensured; coiling after compounding, and standing for 24H at normal temperature;
2) and (5) testing after standing, and cutting and discharging for use.
TABLE 1 Performance testing of the products of examples 1-3 and comparative example 1
The modified emulsion type acrylate adhesive prepared by modifying the acrylate derivative with glucose and using deionized water as a diluent and a solvent reduces the use of volatile organic solvents such as ethyl acetate, toluene and the like in the adhesive, and is more environment-friendly.
In addition, as can be seen from the above table, in the step of dropwise adding the remaining initiator and the remaining pre-emulsion B in the preparation process of the modified emulsion type acrylate adhesive, the initiator is kept to be dropwise added later than the pre-emulsion B for 5min, and the raw materials in the pre-emulsion B can be ensured to react completely; in the second aspect, the high-efficiency filtering group is adopted for filtering to filter out other impurities in the raw materials, so that the purity of the prepared modified emulsion type acrylate adhesive is ensured, the prepared product can be prevented from deteriorating due to long-time placement, and the storage time of the product is prolonged; in the third aspect, compared with the protective film prepared from the emulsion type acrylate adhesive, the protective film prepared from the modified emulsion type acrylate adhesive has stronger adhesive force and strong adaptability, can adapt to various base materials, and does not have the adverse phenomena of watermarks, bubbles, ghosts or spots and the like.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The modified emulsion type acrylate adhesive is characterized by comprising, by weight, 0.1-10 parts of glucose, 0.3-0.6 part of an emulsifier, 35-45 parts of a soft monomer acrylate, 0.4-0.8 part of a functional monomer acrylate, 5-15 parts of a hard monomer acrylate, 0.4-1 part of an initiator, 45-60 parts of deionized water, 1-2 parts of ammonia water, 0.5-1.5 parts of a thickener and a proper amount of additives, wherein the proper amount of additives are a defoaming agent, a wetting agent and a buffering agent.
2. The modified emulsion acrylate adhesive of claim 1, wherein the emulsifier is at least one of ammonium nonylphenol polyoxyethylene ether sulfate, polyether sulfate, sodium dodecylbenzene sulfonate, sodium dodecylsulfate, allyl polyether sulfate, and allyloxy nonylphenol polyoxyethylene ether sulfate.
3. The modified emulsion acrylate adhesive of claim 1 wherein the initiator is ammonium persulfate.
4. The modified emulsion acrylate adhesive of claim 1, wherein the defoamer is any one of polyether defoamer, higher alcohols and derivatives thereof, and aliphatic hydrocarbons containing nonionic part.
5. The modified emulsion acrylate adhesive of claim 1 wherein the wetting agent is polyacrylic acid or hydroxymethyl cellulose.
6. The preparation method of the modified emulsion acrylate adhesive according to claims 1-5, wherein the method comprises the following steps:
uniformly stirring a mixed solution of an emulsifier and deionized water, and filtering to obtain a pre-emulsion A;
taking a mixed solution of an emulsifier and deionized water, adding soft monomer acrylate, hard monomer acrylate and functional single-extraction acrylate while stirring, stirring and dispersing for 30min, adding the pre-emulsion A and glucose, and continuing stirring and dispersing for 30min to obtain a pre-emulsion B;
uniformly stirring and mixing deionized water, a part of emulsifier and a buffer, heating, adding a part of pre-emulsion B and a part of initiator for reaction after the temperature is stable, dropwise adding the rest of initiator and the rest of pre-emulsion B after the reaction is finished, and continuing the reaction;
after the reaction is finished, firstly preserving heat, then cooling to below 60 ℃, neutralizing the pH value to 7-8 by using ammonia water, and adding a thickening agent, a proper amount of defoaming agent and a proper amount of wetting agent to prepare the modified emulsion type acrylate adhesive;
in the step of dropwise adding the rest of the initiator and the rest of the pre-emulsion B, the initiator is kept to be 5min later than the pre-emulsion B, and the dropwise adding is finished.
7. The method for preparing the modified emulsion acrylate adhesive according to claim 6, wherein the temperature is stabilized at 80 ℃ when the deionized water, the partial emulsifier and the buffer are heated after being uniformly mixed; the heat preservation temperature is 83-85 ℃, and the heat preservation time is 120 min.
8. The preparation method of the modified emulsion acrylate adhesive according to claim 6, wherein the filtration is performed by using a high-efficiency filtration group comprising a five-core filter element filter with 0.5 μm PP filter element and a three-core filter with 0.1 μm PP filter element, and the pressure of the filtration pump is below 0.1 MPa.
9. Use of a modified emulsion acrylate adhesive prepared according to any one of claims 6-8 in a protective film.
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