CN102134465A - Self-crosslinking aqueous complex film adhesive and preparation method thereof - Google Patents
Self-crosslinking aqueous complex film adhesive and preparation method thereof Download PDFInfo
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- CN102134465A CN102134465A CN2011100563760A CN201110056376A CN102134465A CN 102134465 A CN102134465 A CN 102134465A CN 2011100563760 A CN2011100563760 A CN 2011100563760A CN 201110056376 A CN201110056376 A CN 201110056376A CN 102134465 A CN102134465 A CN 102134465A
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- 238000004132 cross linking Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000853 adhesive Substances 0.000 title abstract description 12
- 230000001070 adhesive effect Effects 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 50
- 239000003999 initiator Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000004945 emulsification Methods 0.000 claims abstract description 35
- -1 alkyl ether ammonium sulfate Chemical class 0.000 claims abstract description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 24
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 24
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 24
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims abstract description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003292 glue Substances 0.000 claims description 66
- 239000000839 emulsion Substances 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000000872 buffer Substances 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 238000002242 deionisation method Methods 0.000 claims description 14
- 238000009413 insulation Methods 0.000 claims description 14
- 238000005070 sampling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 12
- 230000002335 preservative effect Effects 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229940117958 vinyl acetate Drugs 0.000 abstract 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 abstract 1
- 239000006172 buffering agent Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000003636 chemical group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000002110 toxicologic effect Effects 0.000 description 3
- 231100000027 toxicology Toxicity 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a self-crosslinking aqueous complex film adhesive and a preparation method thereof and belongs to the field of manufacturing of adhesives. The complex film adhesive with a solid content of 40 to 50 percent is prepared by using monomers, an emulsifier, an initiator, a buffering agent, deionized water, a pH regulator and an aqueous assistant as raw materials and by steps of pre-emulsification, seed reaction, polymerization and mixing, wherein the monomers include a hard monomer, a soft monomer and a functional monomer, wherein the hard monomer is vinylacetate; the soft monomer consists of butyl acrylate and ethyl acrylate; the functional monomer consists of acrylic acid or methacrylic acid, hydroxyethyl acrylate or hydroxypropyl acrylate, and N-hydroxymethyl acrylamide; and the emulsifier consists of alkyl ether ammonium sulfate and alkylphenol polyoxyethylene, which are in a weight ratio of 2:1. The complex film adhesive is prepared by using low-cost monomer vinylacetate as a raw material, so the cost is reduced; and the complex film adhesive has the advantages of high adhesive force, high peel-off strength and high environmental friendliness.
Description
Technical field
The present invention relates to adhesive field, especially relate to a kind of self-crosslinking aqueous multiple film glue and preparation method thereof.
Background technology
In recent years, art print, wrapping paper, advertisement calligraphy and painting, books strip of paper used for sealing and packaging paper bag carton mostly stick one deck polypropylene (BOPP) film with the outward appearance of improving paper or printed matter with improve its work-ing life.Color printing paper behind pad pasting is called laminating paper, claims multiple film paper again, its color glow, and have protection against the tide, antifouling property, liked by the human consumer.This BOPP film applying is called paper-plastic composite adhesive to the tackiness agent on the paper product, is called for short multiple film glue, the quality of its performance plays a decisive role to the quality of printed matter overlay film.Common laminated adhesive has solvent-borne type and emulsion-type two big classes, and the main sizing of solvent-borne type laminated adhesive is SBS and terpine resin, and solvent is toluene, No. 120 industrial napthas, vinyl acetic monomer etc.The solid content of this class glue is generally 40～50%, is diluted to 20～25% with the toluene equal solvent again during use.These solvents finally all are discharged in the air, cause severe contamination, and disaster hidden-trouble is serious.Owing to use noxious solvent and thinners such as toluene, not only diminish the healthy of operator, and the product stock poor stability, be prone to bad phenomenon such as wrinkling, foaming after the placement, be eliminated gradually at present.Emulsion type compound film glue is with water as solvent, and not only production cost is low, and have that preparation technology is simple, good stability, safety non-toxic, characteristics such as easy to use.More existing emulsion type compound film glue products on the market, but majority is that raw material makes with butyl acrylate, methyl methacrylate and vinylbenzene, and higher cost has limited its large-scale use, presses for and improves.
Summary of the invention
The purpose of the embodiment of the invention provides a kind of self-crosslinking aqueous multiple film glue and preparation method thereof, solving on the current market solvent-type film-covered adhesive will dilute with noxious solvent, not environmental protection, and the high problem of emulsion type compound film glue product cost provides a kind of safety non-toxic, bonding strength height, aqueous laminating adhesive with low cost.
The objective of the invention is to be achieved through the following technical solutions:
Embodiment of the present invention provides a kind of self-crosslinking aqueous multiple film glue, should multiple film glue be to be raw material with monomer, emulsifying agent, initiator, buffer reagent, deionized water, pH regulator agent and aqueous promoter, the solid content that is prepared from through pre-emulsification, seed reaction, polyreaction and composite each step be 40～50% multiple film glue;
Wherein, described monomer comprises hard monomer, soft monomer and function monomer, and wherein hard monomer adopts vinyl acetate; Soft monomer is made up of butyl acrylate and ethyl propenoate; Function monomer is by any and Hydroxyethyl acrylate in the acrylic or methacrylic acid or in the Propylene glycol monoacrylate any, and N hydroxymethyl acrylamide is formed;
Described emulsifying agent is made up of by 2: 1 weight ratio alkyl oxide ammonium sulfate and alkylphenol polyoxyethylene;
Described aqueous promoter comprises: aqueous wetting agent, water-based defoamer and water-borne preservative.
Embodiment of the present invention also provides a kind of preparation method of self-crosslinking aqueous multiple film glue, comprising:
Composition of raw materials by above-mentioned self-crosslinking aqueous multiple film glue is got each raw material;
Pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 50～60% in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 50～60%, whole monomers, stirring and emulsifying is no less than 30 minutes, makes pre-emulsion;
Seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, and adding accounts for the initiator of initiator gross weight 30～40%, initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reacted 30～40 minutes;
Polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, be mixed together 5～10 minutes with pre-emulsion; After the reaction of the seed in the polymerization reaction kettle finished, temperature-stable dripped remaining pre-emulsion in the emulsification still in polymerization reaction kettle in the time of 80 ℃, dripped off in 3～4 hours, is warmed up to 82～85 ℃ then and continues insulation reaction 1～2h;
Composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion in the polymerization reaction kettle is adjusted between 7.0～8.5; After sampling and testing emulsion viscosity and solid content are qualified, in the emulsion of polymerization reaction kettle, add various aqueous promoters, continue to cool to below 40 ℃, filter discharging, promptly obtain self-crosslinking aqueous multiple film glue finished product.
The technical scheme that provides by the embodiment of the invention as can be seen, the monomer vinyl acetate reduces cost by adopting cheaply in the embodiment of the invention, contain carboxyl by adding, hydroxyl and amino function monomer participate in copolymerization, formation contains the polymer molecular chain of multiple functional group, can form certain crosslinked action between these molecular chains, and with the chemical group on plastic film surface various reactions take place, thereby improve bonding force and the stripping strength of the glued membrane of this multiple film glue to bonding base material, also improved the force of cohesion of glued membrane self, make its multiple film manufacturing procedure that can satisfy high requirement, its performance can compare favourably with the multiple film glue of oiliness.This self-crosslinking aqueous multiple film glue has that cost is low, complete processing is simple, toxicological harmless, the advantage of environmental protection.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Present embodiment provides a kind of self-crosslinking aqueous multiple film glue, should multiple film glue be to be raw material with monomer, emulsifying agent, initiator, buffer reagent, deionized water, pH regulator agent and aqueous promoter, the solid content that is prepared from through pre-emulsification, seed reaction, polyreaction and composite each step be 40～50% multiple film glue;
Wherein, described monomer comprises hard monomer, soft monomer and function monomer, and wherein hard monomer adopts vinyl acetate (VAc); Soft monomer is made up of butyl acrylate (BA) and ethyl propenoate (EA); Function monomer is by in any and Hydroxyethyl acrylate (HEA) or the Propylene glycol monoacrylate (HPA) in vinylformic acid (AA) or the methacrylic acid (MAA) any, and N hydroxymethyl acrylamide (NMA) is formed; By each raw material gross weight of monomer is 100%, and the weight percent of each raw material of monomer is: the part by weight that each monomer is formed is vinyl acetate 30～50%, butyl acrylate 20～40%, ethyl propenoate 10～20%, acrylic or methacrylic acid 1～5%, Hydroxyethyl acrylate or Propylene glycol monoacrylate 1～5%, N hydroxymethyl acrylamide 1～5%;
Emulsifying agent in the above-mentioned multiple film glue is made up of by 2: 1 weight ratio alkyl oxide ammonium sulfate and alkylphenol polyoxyethylene; The consumption of emulsifying agent is 2～4% of a total monomer weight.
Initiator in the above-mentioned multiple film glue adopts ammonium persulphate or Potassium Persulphate, and the consumption of initiator is 0.2～0.6% of a total monomer weight.
Buffer reagent in the above-mentioned multiple film glue adopts sodium bicarbonate or bicarbonate of ammonia, and the consumption of buffer reagent is 0.1～0.3% of a monomer weight.
Ammoniacal liquor is adopted in pH regulator agent in the above-mentioned multiple film glue, and the consumption of pH regulator agent is 0.5～2% of a total monomer weight.
Aqueous promoter in the above-mentioned multiple film glue comprises: aqueous wetting agent, water-based defoamer and water-borne preservative, and aqueous wetting agent wherein adopts negatively charged ion or nonionogenic tenside, and the consumption of aqueous wetting agent is 0.1～0.5% of a total monomer weight; Water-based defoamer in the described aqueous promoter adopts the water-based defoamer that contains mineral oils, and the consumption of water-based defoamer is 0.1～0.5% of a total monomer weight; Water-borne preservative in the described aqueous promoter adopts isothiazolone-containing class water-borne preservative, and the consumption of water-borne preservative is 0.1～0.5% of a total monomer weight.
The preparation method of above-mentioned multiple film glue, undertaken by following step:
Pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 50～60% in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 50～60%, whole monomers, stirring and emulsifying is no less than 30 minutes, makes pre-emulsion;
Seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, and adding accounts for the initiator of initiator gross weight 30～40%, initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reacted 30～40 minutes;
Polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, be mixed together 5～10 minutes with pre-emulsion; After the reaction of the seed in the polymerization reaction kettle finished, temperature-stable dripped remaining pre-emulsion in the emulsification still in polymerization reaction kettle in the time of 80 ℃, dripped off in 3～4 hours, is warmed up to 82～85 ℃ then and continues insulation reaction 1～2h;
Composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion in the polymerization reaction kettle is adjusted between 7.0～8.5; (viscosity of test emulsion sampling is that 50～300mPas, solid content are 40～50% in the qualified back of sampling and testing emulsion viscosity and solid content, then be qualified), in the emulsion of polymerization reaction kettle, add various aqueous promoters, continue to cool to below 40 ℃, filter discharging, promptly obtain self-crosslinking aqueous multiple film glue finished product.
The monomer vinyl acetate reduces cost the multiple film glue of the embodiment of the invention by adopting cheaply, contain carboxyl by adding, hydroxyl and amino function monomer participate in copolymerization, formation contains the polymer molecular chain of multiple functional group, can form certain crosslinked action between these molecular chains, and with the chemical group on plastic film surface various reactions take place, thereby improve bonding force and the stripping strength of the glued membrane of this multiple film glue to bonding base material, also improved the force of cohesion of glued membrane self, make its multiple film manufacturing procedure that can satisfy high requirement, its performance can compare favourably with the multiple film glue of oiliness.This self-crosslinking aqueous multiple film glue has that cost is low, complete processing is simple, toxicological harmless, the advantage of environmental protection.
Embodiment 2
Present embodiment provides a kind of self-crosslinking aqueous multiple film glue, can be used on the BOPP film applying to paper product, and this multiple film glue comprises following raw material:
The preparation method of above-mentioned multiple film glue, undertaken by following step:
(1) pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for gross weight 50% in the deionized water that accounts for gross weight 50%, the emulsifying agent, account for the alkylphenol polyoxyethylene of gross weight 70%, whole monomers, start more than the stirring and emulsifying 30min, make pre-emulsion;
(2) seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water that accounts for gross weight 45%, the emulsifying agent, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, add the initiator that accounts for gross weight 30～40%, add fashionable initiator and be made into the initiator solution of 5～10% mass concentrations, reaction 30～40min with deionization;
(3) polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, be mixed together 5～10min; After the seed reaction finished in the polymerization reaction kettle, temperature-stable began to drip remaining pre-emulsion in the emulsification still in the time of 80 ℃, drip off in 3～4h, made polymerization reaction kettle be warmed up to 82～85 ℃ then and continued insulation reaction 1～2h;
(4) composite: the insulation reaction of polymerization reaction kettle drops to 50 ℃ with the polymerization reaction kettle temperature after finishing, and adds the pH regulator agent, and the pH value of emulsion is adjusted between 7.0～8.5; (viscosity of test emulsion sampling is that 50～300mPas, solid content are 40～50% to the qualified back of sampling and testing viscosity and solid content, then be qualified), add various aqueous promoters (aqueous wetting agent, water-based defoamer and water-borne preservative), continue to cool to below 40 ℃, filter discharging, promptly obtain this multiple film glue finished product.The solid content that detects this multiple film glue at last is 49.5%, and viscosity is 120mPas, and the pH value is 7.5.
Embodiment 3
Present embodiment provides a kind of self-crosslinking aqueous multiple film glue, can be used on the BOPP film applying to paper product, and this multiple film glue comprises following raw material:
The preparation method of above-mentioned multiple film glue, undertaken by following step:
(1) pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 60% in the deionized water, emulsifying agent of the ionized water gross weight 45% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 65%, whole monomers, start more than the stirring and emulsifying 30min, make pre-emulsion;
(2) seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 50% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, the initiator that adds 30～40wt%, add and fashionablely initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reaction 30～40min;
(3) polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, together emulsification 5～10min; After the reaction of the seed in the polymerization reaction kettle finished, temperature-stable began to drip remaining pre-emulsion in the emulsification still in the time of 80 ℃, drip off in 3～4h, made polymerization reaction kettle be warmed up to 82～85 ℃ then and continued insulation reaction 1～2h;
(4) composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion is adjusted between 7.0～8.5; (viscosity of test emulsion sampling is that 50～300mPas, solid content are 40～50% to the qualified back of sampling and testing viscosity and solid content, then be qualified), add various aqueous promoters (aqueous wetting agent, water-based defoamer and water-borne preservative), continue to cool to below 40 ℃, filter discharging, promptly obtain multiple film glue finished product.The solid content that detects this multiple film glue at last is 40.6%, and viscosity is 60mPas, and the pH value is 8.0.
Embodiment 4
Present embodiment provides a kind of self-crosslinking aqueous multiple film glue, can be used on the BOPP film applying to paper product, and this multiple film glue comprises following raw material:
The preparation method of above-mentioned multiple film glue, undertaken by following step:
(1) pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 55% in the deionized water, emulsifying agent of the ionized water gross weight 40% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 60%, whole monomers, start more than the stirring and emulsifying 30min, make pre-emulsion;
(2) seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 45% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, the initiator that adds 30～40wt%, add and fashionablely initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reaction 30～40min;
(3) polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, together emulsification 5～10min; After the reaction of the seed in the polymerization reaction kettle finished, temperature-stable began to drip remaining pre-emulsion in the emulsification still in the time of 80 ℃, drip off in 3～4h, made polymerization reaction kettle be warmed up to 82～85 ℃ then and continued insulation reaction 1～2h;
(4) composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion is adjusted between 7.0～8.5; (viscosity of test emulsion sampling is that 50～300mPas, solid content are 40～50% to the qualified back of sampling and testing viscosity and solid content, then be qualified), add various aqueous promoters (aqueous wetting agent, water-based defoamer and water-borne preservative), continue to cool to below 40 ℃, filter discharging, promptly obtain multiple film glue finished product.Detecting the solid content that makes multiple film glue at last is 44.8%, and viscosity is 90mPas, and the pH value is 7.0.
In sum, the monomer vinyl acetate reduces cost the multiple film glue of the self-crosslinking formula of the embodiment of the invention by adopting cheaply, contain carboxyl by adding, hydroxyl and amino function monomer participate in copolymerization, formation contains the polymer molecular chain of multiple functional group, can form certain crosslinked action between these molecular chains, and with the chemical group on plastic film surface various reactions take place, thereby improve bonding force and the stripping strength of the glued membrane of this multiple film glue to bonding base material, also improved the force of cohesion of glued membrane self, make its multiple film manufacturing procedure that can satisfy high requirement, its performance can compare favourably with the multiple film glue of oiliness.This self-crosslinking aqueous multiple film glue has that cost is low, complete processing is simple, toxicological harmless, the advantage of environmental protection.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. self-crosslinking aqueous multiple film glue, it is characterized in that, should multiple film glue be to be raw material with monomer, emulsifying agent, initiator, buffer reagent, deionized water, pH regulator agent and aqueous promoter, the solid content that is prepared from through pre-emulsification, seed reaction, polyreaction and composite each step be 40～50% multiple film glue;
Wherein, described monomer comprises hard monomer, soft monomer and function monomer, and wherein hard monomer adopts vinyl acetate; Soft monomer is made up of butyl acrylate and ethyl propenoate; Function monomer is by any and Hydroxyethyl acrylate in the acrylic or methacrylic acid or in the Propylene glycol monoacrylate any, and N hydroxymethyl acrylamide is formed;
Described emulsifying agent is made up of by 2: 1 weight ratio alkyl oxide ammonium sulfate and alkylphenol polyoxyethylene;
Described aqueous promoter comprises: aqueous wetting agent, water-based defoamer and water-borne preservative.
2. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that described monomer is 100% by each raw material gross weight, and the consumption of each raw material is in the monomer:
Vinyl acetate 30～50%, butyl acrylate 20～40%, ethyl propenoate 10～20%, acrylic or methacrylic acid 1～5%, Hydroxyethyl acrylate or Propylene glycol monoacrylate 1～5%, N hydroxymethyl acrylamide 1～5%.
3. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that the consumption of described emulsifying agent is 2～4% of a total monomer weight.
4. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that described initiator adopts ammonium persulphate or Potassium Persulphate, and the consumption of initiator is 0.2～0.6% of a total monomer weight.
5. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that described buffer reagent adopts sodium bicarbonate or bicarbonate of ammonia, and the consumption of buffer reagent is 0.1～0.3% of a monomer weight.
6. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that ammoniacal liquor is adopted in described pH regulator agent, and the consumption of pH regulator agent is 0.5～2% of a total monomer weight.
7. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that the aqueous wetting agent in the described aqueous promoter adopts negatively charged ion or nonionogenic tenside, and the consumption of aqueous wetting agent is 0.1～0.5% of a total monomer weight; Water-based defoamer in the described aqueous promoter adopts the water-based defoamer that contains mineral oils, and the consumption of water-based defoamer is 0.1～0.5% of a total monomer weight; Water-borne preservative in the described aqueous promoter adopts isothiazolone-containing class water-borne preservative, and the consumption of water-borne preservative is 0.1～0.5% of a total monomer weight.
8. self-crosslinking aqueous multiple film glue as claimed in claim 1 is characterized in that, the solid content that the pre-emulsification of described warp, seed reaction, polyreaction and composite each step are prepared from is that 40～50% multiple film glue specifically comprises:
Pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 50～60% in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 70～80%, whole monomers, stirring and emulsifying is no less than 30 minutes, makes pre-emulsion;
Seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, and adding accounts for the initiator of initiator gross weight 30～40%, initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reacted 30～40 minutes;
Polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, be mixed together 5～10 minutes with pre-emulsion; After the reaction of polymerization reaction kettle seed finished, temperature-stable dripped remaining pre-emulsion in the emulsification still in polymerization reaction kettle in the time of 80 ℃, dripped off in 3～4 hours, is warmed up to 82～85 ℃ then and continues insulation reaction 1～2h;
Composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion in the polymerization reaction kettle is adjusted between 7.0～8.5; After sampling and testing viscosity and solid content are qualified, add various aqueous promoters, continue to cool to below 40 ℃, filter discharging, promptly obtain self-crosslinking aqueous multiple film glue finished product.
9. the preparation method of a self-crosslinking aqueous multiple film glue is characterized in that, comprising:
Composition of raw materials by aforesaid right requirement 1～7 each described self-crosslinking aqueous multiple film glue is got each raw material;
Pre-emulsification: in the emulsification still, drop into the alkyl oxide ammonium sulfate that accounts for alkyl oxide ammonium sulfate gross weight 50～60% in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, account for the alkylphenol polyoxyethylene of alkylphenol polyoxyethylene gross weight 50～60%, whole monomers, stirring and emulsifying is no less than 30 minutes, makes pre-emulsion;
Seed reaction: in polymerization reaction kettle, drop into remaining alkyl oxide ammonium sulfate and remaining alkylphenol polyoxyethylene in the deionized water, emulsifying agent of the ionized water gross weight 40～50% that accounts for, buffer reagent, start and stir and intensification, when temperature arrives 75 ℃, the above-mentioned pre-emulsion that makes that drops into 5～10wt% is in polymerization reaction kettle, and adding accounts for the initiator of initiator gross weight 30～40%, initiator is made into the initiator solution of 5～10% mass concentrations with deionization, reacted 30～40 minutes;
Polyreaction: remaining initiator is joined in the emulsification still with the initiator solution that deionization is made into 5～10% mass concentrations, be mixed together 5～10 minutes with pre-emulsion; After the reaction of the seed in the polymerization reaction kettle finished, temperature-stable dripped remaining pre-emulsion in the emulsification still in polymerization reaction kettle in the time of 80 ℃, dripped off in 3～4 hours, is warmed up to 82～85 ℃ then and continues insulation reaction 1～2h;
Composite: as after the polymerization reaction kettle insulation reaction finishes, the polymerization reaction kettle temperature to be dropped to 50 ℃, add the pH regulator agent, the pH value of emulsion in the polymerization reaction kettle is adjusted between 7.0～8.5; After sampling and testing emulsion viscosity and solid content are qualified, in the emulsion of polymerization reaction kettle, add various aqueous promoters, continue to cool to below 40 ℃, filter discharging, promptly obtain self-crosslinking aqueous multiple film glue finished product.
10. the preparation method of self-crosslinking aqueous multiple film glue as claimed in claim 9 is characterized in that, described sampling and testing viscosity and solid content is qualified comprises:
The viscosity of test emulsion sampling is 50～300mPas, then is qualified;
The solid content of test emulsion sampling is 40～50%, then is qualified.
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| CN103131359A (en) * | 2013-03-21 | 2013-06-05 | 辽宁吕氏化工（集团）有限公司 | Environment-friendly quick-drying type adhesive |
| CN109401688A (en) * | 2018-10-31 | 2019-03-01 | 江苏国胶化学科技有限公司 | A kind of aqueous laminating adhesive producing process and its device |
| CN110655885A (en) * | 2019-11-11 | 2020-01-07 | 怀化学院 | Laminating adhesive and preparation method thereof |
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| CN102140320B (en) * | 2010-08-19 | 2012-12-12 | 北京高盟新材料股份有限公司 | Water-based polyacrylic emulsion laminating adhesive and preparation method thereof |
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| CN101955742A (en) | 2011-01-26 |
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