CN103059784A - Water-based plastic-plastic compound adhesive for food and drug flexible package and preparation method thereof - Google Patents
Water-based plastic-plastic compound adhesive for food and drug flexible package and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based plastic-plastic compound adhesive for food and drug flexible packages and a preparation method thereof. The preparation method comprises the following steps of: carrying out pre-emulsification by using 20-30 parts by weight of deionized water, 0.4-1.0 part by weight of emulsifying agents and 75-90 parts by weight of monomer mixtures to obtain a pre-emulsion A; then carrying out the pre-emulsification by using 5-8 parts by weight of the deionized water, 0.2-0.3 part of the emulsifying agents and 3-20 parts by weight of the monomer mixtures to obtain a pre-emulsion B; preparing an initiator water solution C by using 1-3 parts by weight of the deionized water and 0.2-0.8 part by weight of initiators; and dropping the monomer mixture I with lower polarity and the monomer mixture II with higher polarity step by step by adopting a pre-emulsification seed emulsion polymerization process to obtain the water-based plastic-plastic compound adhesive for the food and drug flexible packages. The water-based plastic-plastic compound adhesive disclosed by the invention has the advantages of no organic solvent, no formaldehyde release, good adhesivity and high stripping strength and permanent adhesion and can be applied to a flexible package industry and substitute for a solvent type two-component polyurethane adhesive maturely applied to the present market.
Description
Technical field
This patent relates to a kind of composite adhesive, a kind of especially Shui Su that is applicable to food and medicine soft packaging ?mould composite adhesive and preparation method thereof.
Background technology
Food and medicine soft packaging Su ?mould compound package material and mainly adopt the dry type composite film method, namely use coating machine at plastics film coating one deck tackiness agent, remove solvent or moisture in the tackiness agent through dry baking tunnel again, carry out again heat pressure adhesive.Commercially available tackiness agent mainly contains solvent-borne type (such as dual-component polyurethane) and aqueous emulsion type two large classes.Solvent-type film-covered adhesive is brought HUMAN HEALTH and environment and is had a strong impact on, and is not easy to accumulating, is faced with superseded.And aqueous adhesive is with low cost take water as dispersion medium, and the noresidue solvent, meets environmental protection and wrapping material safety and sanitation standard.Acrylic acid emulsion adhesive is a large class of environmental type tackiness agent, U.S.'s ROHM AND HAAS has been introduced the aqueous adhesive of American market maturation, performance also can reach the compound requirement of normal food packing dry type, meets the defective that water whitens, price is high, the recombining process cycle is long but exist.US Patent No. 6,190,767B1 discloses a kind of preparation method of tackiness agent emulsion, monomer more than 50% is selected long-chain aliphatic acrylate, adopts polymerisable emulsifier, take the monomer microparticle as polymerization domain, make the good stable emulsion of water-fast wet fastness, non-polar substrate is had good adhesion.US Patent No. 6,013,772 disclose water-fast pressure-sensitive adhesive emulsion, and main monomer is 50～90% butyl acrylates (BA) and 10～the 50% the third alkene acid ?β ?hydroxyl ethyl ester (HEA) (Propylene glycol monoacrylate (HPA)).The multiple film latex solution of domestic esters of acrylic acid also has commodity to emerge.Chinese invention patent CN1740257A adopts low soap letex polymerization, and the pre-emulsification half-continuous process makes good emulsion stability, is applied to the compound of food product packing film, and cohesive strength can reach 1.0N/15mm.Chinese invention patent CN1730592A discloses the design of stone soft shell three-layer nuclear shell, polymkeric substance is had mobile preferably, introducing HEA between outer nuclear layer and shell carries out crosslinked, improved the force of cohesion of polymkeric substance, initial bonding strength and the stripping strength of multiple film glue reach preferably balance, be applied to the bonding of plastics film, can tolerate 130 ℃ of high temperature.Chinese invention patent CN101168650A discloses a kind of dry type composite film with the preparation method of single-component self-crosslink emulsion adhesive, adopts NMA, GMA, and one or more in the vinylsiloxane are as linking agent.Chinese invention patent CN1872934A is with Phthalic acid, diallyl ester (DAP), diallyl maleate, and HEA, NMA is function monomer, has introduced a kind of preparation method of aqueous laminating adhesive.Compare with the product of the companies such as ROHM AND HAAS, domestic esters of acrylic acid aqueous laminating adhesive also lacks technical competitive power, has many technological deficiencies: the wettability to the plastics film of low surface energy is not good; Because the interfacial migration effect of remaining small-molecule substance, its stripping strength with hold viscous force far away from the solvent-borne type product, and water tolerance is relatively poor; Easy to foaming in the upper machine coating process, rate of drying is slow, can not high-speed coating; The poor-performing of high-temp resisting high-humidity resisting environment can not reach the application requiring that anti-cooking food is packed.In order to improve the application quality of aqueous adhesive, some modified crosslinking agents have been developed in recent years, such as the inferior ethamine of polyfunctional group ring, the polyfunctional group carbodiimide, polyfunctional group aziridine, polyfunctional group be the azoles quinoline oh, vinylsiloxane, the performance of aqueous laminating adhesive is improved, and crosslinking temperature is higher, speed waits problem more slowly but exist, and the packaged form of two components is not easy to accumulating.The introducing of the normal temperature crosslinked system of DAAM/ADH can improve the package stability of emulsion, but can cause to the cohesive strength of glued membrane certain negative impact.
Summary of the invention
The object of the invention is to improve the technological deficiency of acrylic acid emulsion adhesive, provide that a kind of pre-emulsification seeded emulsion polymerization prepares that adhesivity is good, stripping strength and hold viscous force high, be applicable to Shui Su that the food and medicine soft packaging uses ?mould composite adhesive and preparation method thereof.
Purpose of the present invention is achieved through the following technical solutions:
Food and medicine soft packaging use Su ?mould the preparation method of composite adhesive, comprise the steps:
(1) in parts by weight, gets 20～30 parts of deionized waters, 0.4～1.0 part of emulsifying agent, 75～90 parts of monomer mixture I and carry out pre-emulsification and obtain pre-emulsion A; Getting 5～8 parts of deionized waters, 0.2～0.3 part of emulsifying agent, 3～20 parts of monomer mixture II carries out pre-emulsification and obtains pre-emulsion B again; Get 1～3 part of deionized water and 0.2～0.8 part of initiator preparation initiator solution C;
(2) in parts by weight, 60～90 parts of deionized waters, 0.1～0.2 part of emulsifying agent and 0.02～0.05 part of initiator preparation obtain bed material, are warming up to 65～75 ℃, begin to drip pre-emulsion A, control pre-emulsion A in 160 ?dropwised in 180 minutes;
(3) when pre-emulsion A drip 15 ?after 30 minutes, be warming up to 78～82 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C in 150 ?dropwised in 180 minutes;
(4) when pre-emulsion B drip 60 ?90 minutes the time, add in 0.5～1.5 part of internal plasticization monomer and 1～3 part cross-linking monomer in the residue pre-emulsion B and stir, then continue to drip;
(5) when pre-emulsion A drip 90 ?120 minutes the time, add 0.01～0.1 part of chain-transfer agent in the residue pre-emulsion A and stir, then continue to drip;
(6) dropwise, be warming up to 86 ?90 ℃ of insulation reaction 55 ?65 minutes;
(7) be cooled to 40～50 ℃, add 0.05～0.5 part of functional agent, after stirring, filter, packing, obtain food and medicine soft packaging use Su ?mould composite adhesive;
Described monomer mixture I be ethyl propenoate (EA), methyl acrylate (MA), methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate (EMA), N ?vinyl pyrrolidone (NVP), butyl acrylate (BA), 2 ?in ETHYL HEXYL ACRYLATE (2 ?EHA), lauryl methacrylate(LMA) (LMA) and the vinylbenzene (St) a kind of, two or three;
Described monomer mixture II is the unsaturated monomer that contains carboxyl, hydroxyl or amide group; The described carboxyl unsaturated monomer that contains is a kind of in vinylformic acid, methacrylic acid, methylene-succinic acid and the fumaric acid; The hydroxyl unsaturated monomer be Bing Xi Suan ?β ?hydroxyl ethyl ester (HEA), Jia base Bing Xi Suan ?β ?hydroxyl ethyl ester (HEMA) or Bing Xi Suan ?β ?hydroxypropyl acrylate (HPA); The amide-containing unsaturated monomer is diacetone-acryloamide(DAA) (DAAM) or acetoacetyl β-dimethyl-aminoethylmethacrylate (AAEM);
Described internal plasticization monomer is n-butyl maleate (DBM), diisooctyl maleate (DOM), dibutyl fumarate (DBF), a kind of in the dibutyl itaconate (DBI).
Described interior cross-linking monomer such as relates generally at the multi-functional acrylate's monomer that contains the two keys of two or more C=C;
Described emulsifying agent be 2 ?Bing Xi Xian An ?2 ?in the methyl propane sulfonic acid sodium salt, sodium vinyl sulfonate, allyloxy Nonyl pheno (10) ether ammonium sulfate one or both; Described initiator be ammonium persulphate, Potassium Persulphate or 2,2' ?azo diisobutyl amidine dihydrochloride; Described chain-transfer agent is n-dodecyl mercaptan or uncle's lauryl mercaptan; Described functional agent is Surfynol420, Surfynol440 or Surfynol465.
For further realizing the object of the invention, described interior cross-linking monomer is Phthalic acid, diallyl ester (DAP), diallyl maleate, glycidyl allyl ether (GMA), 1,6 ?hexanediyl ester (HDDA), Vinylstyrene (DVB), 1,4 ?propylene glycol diacrylate, 1,2 ?in the Ethylene glycol dimethacrylate, TEGDMA, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate one or both.
In parts by weight, described monomer mixture I is preferably 70～85 parts.Described monomer mixture II is preferably 5～15 parts.Described internal plasticization monomer is preferably 1～1.5 part.
A kind of food and medicine soft packaging use Su ?mould composite adhesive, prepared by aforesaid method.
Compared with prior art, the present invention has following advantage and effect:
1) the present invention adopts pre-emulsification seeded emulsion polymerization technique, the monomer mixture II that the monomer mixture I that polarity is weak and polarity are stronger drips step by step, strengthen the stability of polymerization, and make the polymer billet top layer more polar group that distributes, thereby improve the base material cohesive strength.
2) the present invention adopts the internal plasticization monomer, improves snappiness and the base material adhesivity of glued membrane.Introducing contains the monomer of two or more pairs key as interior cross-linking monomer, increases polymericular weight, improves the glued membrane cohesive strength.
3) the present invention adopts low soap letex polymerization, make few stable emulsion of slagging tap, do not contain organic solvent, release formaldehyde not, be applied to the compound sticking between the plastics film, adhesivity is good, stripping strength and to hold viscous force high, can be applicable to Flexible-Packaging Industry, substitutes the in the market ripe solvent-based two-component polyurethane adhesive of using.
Embodiment
For better understanding the present invention, the present invention is described further below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1
Synthetic method: form and consumption according to the prescription of the listed embodiment 1 of table 1, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) get 20Kg deionized water, 0.6Kg2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 45Kg butyl acrylate, 10Kg methyl methacrylate and 25Kg2 ?ETHYL HEXYL ACRYLATE carry out pre-emulsification and obtain pre-emulsion A; Get again 6Kg deionized water, 0.2Kg2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 2Kg methacrylic acid, 3Kg Bing Xi Suan ?β ?hydroxyl ethyl ester and 1Kg diacetone-acryloamide(DAA) carry out pre-emulsification and obtain pre-emulsion B.Get 1Kg deionized water and 0.3Kg ammonium persulphate preparation initiator solution C;
(2) add in the four-hole boiling flask 70Kg deionized water, 0.1Kg2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, the preparation of 0.02Kg ammonium persulphate obtain bed material, be warming up to 65 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 160 minutes;
(3) after pre-emulsion A drips 20 minutes, be warming up to 80 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 150 minutes.
(4) when pre-emulsion B drips 75 minutes, in residue pre-emulsion B, add the 0.7Kg n-butyl maleate, 0.9Kg Phthalic acid, diallyl ester and 0.5Kg1,6 ?hexanediyl ester and stirring, then continue to drip;
(5) when pre-emulsion A drips 100 minutes, in residue pre-emulsion A, add the 0.02Kg n-dodecyl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 88 ℃ of insulation reaction 60 minutes;
(7) be cooled to 45 ℃, add 0.1Kg Surfynol420, after stirring, filter, packing, obtain embodiment 1 food and medicine soft packaging use Su ?mould composite adhesive.
The food and medicine soft packaging use Su of table 1. embodiment 1 ?mould the composite adhesive synthesizing formula
Embodiment 2:
Synthesizing formula sees Table 2:
The food and medicine soft packaging use Su of table 2. embodiment 2 ?mould the composite adhesive synthesizing formula
Synthetic method: form and consumption according to the prescription of the listed embodiment 2 of table 2, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) getting 25Kg deionized water, 0.8Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 65Kg butyl acrylate, 10Kg methyl methacrylate carries out pre-emulsification and obtains pre-emulsion A; Get again 5Kg deionized water, 0.25Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 2Kg methacrylic acid, 8Kg Bing Xi Suan ?β ?hydroxyl ethyl ester and 1.5Kg diacetone-acryloamide(DAA) carry out pre-emulsification and obtain pre-emulsion B.Get 2Kg deionized water and 0.5Kg ammonium persulphate preparation initiator solution C;
(2) add 65Kg deionized water, 0.15Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, the preparation of 0.03Kg ammonium persulphate in the four-hole boiling flask and obtain bed material, be warming up to 68 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 180 minutes;
(3) after pre-emulsion A drips 30 minutes, be warming up to 78 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 160 minutes.
(4) when pre-emulsion B drips 70 minutes, in residue pre-emulsion B, add the 0.8Kg diisooctyl maleate, 0.6Kg Phthalic acid, diallyl ester and 0.9Kg divinyl benzo stir, and then continue to drip;
(5) when pre-emulsion A drips 100 minutes, in residue pre-emulsion A, add the 0.01Kg n-dodecyl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 88 ℃ of insulation reaction 55 minutes;
(7) be cooled to 50 ℃, add 0.2Kg Surfynol440, after stirring, filter, packing, obtain embodiment 2 food and medicine soft packaging use Su ?mould composite adhesive.
Embodiment 3:
Synthesizing formula sees Table 3:
The food and medicine soft packaging use Su of table 3. embodiment 3 ?mould the composite adhesive synthesizing formula
Synthetic method: form and consumption according to the prescription of the listed embodiment 3 of table 3, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) get 30Kg deionized water, 1.0Kg sodium vinyl sulfonate, 55Kg ethyl propenoate, 20Kg vinylbenzene and 10Kg2 ?ETHYL HEXYL ACRYLATE carry out pre-emulsification and obtain pre-emulsion A; Get again 6Kg deionized water, 0.2Kg sodium vinyl sulfonate, 1Kg vinylformic acid, 5Kg Bing Xi Suan ?β ?hydroxypropyl acrylate and 2Kg acetoacetyl β-dimethyl-aminoethylmethacrylate carry out pre-emulsification and obtain pre-emulsion B.Get 1.5Kg deionized water and 0.2Kg2,2' ?azo diisobutyl amidine dihydrochloride preparation initiator solution C;
(2) add 90Kg deionized water, 0.1Kg sodium vinyl sulfonate, 0.05Kg2 in the four-hole boiling flask, 2' ?the preparation of azo diisobutyl amidine dihydrochloride obtain bed material, be warming up to 75 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 170 minutes;
(3) after pre-emulsion A drips 20 minutes, be warming up to 82 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 150 minutes.
(4) when pre-emulsion B drips 60 minutes, in residue pre-emulsion B, add the 1.5Kg n-butyl maleate, 2.0Kg1,6 ?hexanediyl ester and stirring, then continue to drip;
(5) when pre-emulsion A drips 95 minutes, in residue pre-emulsion A, add uncle's 0.02Kg lauryl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 90 ℃ of insulation reaction 55 minutes;
(7) be cooled to 40 ℃, add 0.3Kg Surfynol465, after stirring, filter, packing, obtain embodiment 3 food and medicine soft packaging use Su ?mould composite adhesive.
Embodiment 4:
Synthesizing formula sees Table 4:
The food and medicine soft packaging use Su of table 4. embodiment 4 ?mould the composite adhesive synthesizing formula
Synthetic method: form and consumption according to the prescription of the listed embodiment 4 of table 4, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) get 24Kg deionized water, 0.3Kg 2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.3Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 55Kg methyl acrylate, 25Kg lauryl methacrylate(LMA) carry out pre-emulsification and obtain pre-emulsion A; Get again 8Kg deionized water, 0.1Kg2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.15Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 4Kg methylene-succinic acid, 8Kg Jia base Bing Xi Suan ?β ?hydroxyl ethyl ester and 2Kg diacetone-acryloamide(DAA) carry out pre-emulsification and obtain pre-emulsion B.Get 2Kg deionized water and 0.6Kg Potassium Persulphate preparation initiator solution C;
(2) add in the four-hole boiling flask 85Kg deionized water, 0.05Kg 2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.1Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, the preparation of 0.04Kg Potassium Persulphate obtain bed material, be warming up to 70 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 170 minutes;
(3) after pre-emulsion A drips 25 minutes, be warming up to 80 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 160 minutes.
(4) when pre-emulsion B drips 65 minutes, in residue pre-emulsion B, add the 0.7Kg dibutyl fumarate, the 2Kg glycidyl allyl ether also stirs, and then continues to drip;
(5) when pre-emulsion A drips 120 minutes, in residue pre-emulsion A, add the 0.06Kg n-dodecyl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 88 ℃ of insulation reaction 55 ?65 minutes;
(7) be cooled to 45 ℃, add 0.3Kg Surfynol440, after stirring, filter, packing, obtain embodiment 4 food and medicine soft packaging use Su ?mould composite adhesive.
Embodiment 5:
Synthesizing formula sees Table 5:
The food and medicine soft packaging use Su of table 5 embodiment 5 ?mould the composite adhesive synthesizing formula
Synthetic method: form and consumption according to the prescription of the listed embodiment 5 of table 5, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) get 20Kg deionized water, 0.6Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 55Kg 2 ?ETHYL HEXYL ACRYLATE, 20Kg methyl methacrylate carry out pre-emulsification and obtain pre-emulsion A; Get again 6Kg deionized water, 0.25Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, 4Kg fumaric acid, 8Kg Bing Xi Suan ?β ?hydroxypropyl acrylate and 3Kg acetoacetyl β-dimethyl-aminoethylmethacrylate carry out pre-emulsification and obtain pre-emulsion B.Get 3Kg deionized water and 0.3Kg ammonium persulphate preparation initiator solution C;
(2) add 85Kg deionized water, 0.15Kg allyloxy polyoxyethylene nonylphenol ether ammonium sulfate, the preparation of 0.03Kg ammonium persulphate in the four-hole boiling flask and obtain bed material, be warming up to 70 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 180 minutes;
(3) after pre-emulsion A drips 30 minutes, be warming up to 82 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 170 minutes.
(4) when pre-emulsion B drips 85 minutes, in residue pre-emulsion B, add the 1.2Kg dibutyl itaconate, the 1.5Kg trimethylolpropane trimethacrylate also stirs, and then continues to drip;
(5) when pre-emulsion A drips 110 minutes, in residue pre-emulsion A, add uncle's 0.02Kg lauryl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 88 ℃ of insulation reaction 65 minutes;
(7) be cooled to 40 ℃, add 0.5Kg Surfynol420, after stirring, filter, packing, obtain embodiment 5 food and medicine soft packaging use Su ?mould composite adhesive.
Embodiment 6:
Synthesizing formula sees Table 6:
The food and medicine soft packaging use Su of table 6. embodiment 6 ?mould the composite adhesive synthesizing formula
Synthetic method: form and consumption according to the prescription of the listed embodiment 6 of table 6, as follows synthesised food medicine soft packaging use Su ?mould composite adhesive:
(1) get 30Kg deionized water, 0.6Kg 2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.4Kg sodium vinyl sulfonate, 35Kg methyl acrylate, 15Kg β-dimethyl-aminoethylmethacrylate and 25Kg 2 ?ETHYL HEXYL ACRYLATE carry out pre-emulsification and obtain pre-emulsion A; Get again 8Kg deionized water, 0.15Kg 2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.05Kg sodium vinyl sulfonate, 5Kg methylene-succinic acid, 5Kg Bing Xi Suan ?β ?hydroxyl ethyl ester and 2Kg diacetone-acryloamide(DAA) carry out pre-emulsification and obtain pre-emulsion B.Get 2Kg deionized water and 0.4Kg ammonium persulphate preparation initiator solution C;
(2) add in the four-hole boiling flask 75Kg deionized water, 0.02Kg 2 ?Bing Xi Xian An ?2 ?methyl propane sulfonic acid sodium salt, 0.13Kg sodium vinyl sulfonate, the preparation of 0.05Kg ammonium persulphate obtain bed material, be warming up to 75 ℃, begin to drip pre-emulsion A, control pre-emulsion A dropwised in 180 minutes;
(3) when pre-emulsion A drip 15 ?after 30 minutes, be warming up to 78 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C dropwised in 150 minutes.
(4) when pre-emulsion B drip 60 ?90 minutes the time, in residue pre-emulsion B, add the 1.5Kg n-butyl maleate, 0.3Kg diallyl maleate and 2Kg 1,6 ?hexanediyl ester and stirring, then continue to drip;
(5) when pre-emulsion A drips 100 minutes, in residue pre-emulsion A, add the 0.05Kg n-dodecyl mercaptan and stir then continuation dropping;
(6) dropwise, be warming up to 86 ℃ of insulation reaction 50 minutes;
(7) be cooled to 50 ℃, add 0.15Kg Surfynol440, after stirring, filter, packing, obtain embodiment 6 food and medicine soft packaging use Su ?mould composite adhesive.
The embodiment product performance detect:
The food and medicine soft packaging use Su that respectively embodiment 1～6 is obtained ?mould composite adhesive and carry out the tests such as solid divides, viscosity, time of drying, environmental-protecting performance; Tackiness agent is coated on the plastic film in 120 m/mins speed by moulding plastic compounding machine, be respectively after 3 meters, temperature are respectively three joint drying tunnel heat dryings of 70 ℃, 80 ℃ and 90 ℃ through length, then the composite pressure that adopts 4～5 kgfs obtains composite film material to be measured with itself and composite plastic film or aluminium plating film pressing, with reference to GB/T8808 to the composite film material peel strength test.Above test data is as shown in table 7:
Table 7. embodiment 1 ?6 food and medicine soft packaging use Su ?mould composite adhesive performance
By as seen from Table 7, the prepared food and medicine soft packaging of the present invention use Su ?mould composite adhesive and be used for plastic film and plastic film, in plastic film and aluminium plating film compound, stripping strength all reaches more than the 1.2N/15mm, this be much higher than " GB/T10004 ?2008 packaging composite plastic films, the bag dry laminating, extrude compound " in for the stripping strength requirement more than the common package compound film 0.6N/15mm.In addition, adopt food and medicine soft packaging use Su of the present invention ?mould the compound caudacoria of composite adhesive after placing 30 days, stripping strength still remains on very high level, thus this tackiness agent to hold viscous force also very outstanding.And the environmental-protecting performance of product is very good, and formaldehyde, benzene series solvent, phthalate etc. all do not detect, the food and medicine soft packaging use Su that the present invention makes ?mould composite adhesive can satisfy soft packaging Su ?mould the Application of composite requirement.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
- Food and medicine soft packaging use Su ?mould the preparation method of composite adhesive, it is characterized in that comprising the steps:(1) in parts by weight, gets 20～30 parts of deionized waters, 0.4～1.0 part of emulsifying agent, 75～90 parts of monomer mixture I and carry out pre-emulsification and obtain pre-emulsion A; Getting 5～8 parts of deionized waters, 0.2～0.3 part of emulsifying agent, 3～20 parts of monomer mixture II carries out pre-emulsification and obtains pre-emulsion B again; Get 1～3 part of deionized water and 0.2～0.8 part of initiator preparation initiator solution C;(2) in parts by weight, 60～90 parts of deionized waters, 0.1～0.2 part of emulsifying agent and 0.02～0.05 part of initiator preparation obtain bed material, are warming up to 65～75 ℃, begin to drip pre-emulsion A, control pre-emulsion A in 160 ?dropwised in 180 minutes;(3) when pre-emulsion A drip 15 ?after 30 minutes, be warming up to 78～82 ℃, and begin to drip pre-emulsion B and initiator solution C, control pre-emulsion B and initiator solution C in 150 ?dropwised in 180 minutes;(4) when pre-emulsion B drip 60 ?90 minutes the time, add in 0.5～1.5 part of internal plasticization monomer and 1～3 part cross-linking monomer in the residue pre-emulsion B and stir, then continue to drip;(5) when pre-emulsion A drip 90 ?120 minutes the time, add 0.01～0.1 part of chain-transfer agent in the residue pre-emulsion A and stir, then continue to drip;(6) dropwise, be warming up to 86 ?90 ℃ of insulation reaction 55 ?65 minutes;(7) be cooled to 40～50 ℃, add 0.05～0.5 part of functional agent, after stirring, filter, packing, obtain food and medicine soft packaging use Su ?mould composite adhesive;Described monomer mixture I be ethyl propenoate, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, N ?vinyl pyrrolidone, butyl acrylate, 2 ?in ETHYL HEXYL ACRYLATE, lauryl methacrylate(LMA) and the vinylbenzene a kind of, two or three;Described monomer mixture II is the unsaturated monomer that contains carboxyl, hydroxyl or amide group; The described carboxyl unsaturated monomer that contains is a kind of in vinylformic acid, methacrylic acid, methylene-succinic acid and the fumaric acid; The hydroxyl unsaturated monomer be Bing Xi Suan ?β ?hydroxyl ethyl ester, Jia base Bing Xi Suan ?β ?hydroxyl ethyl ester or Bing Xi Suan ?β ?hydroxypropyl acrylate; The amide-containing unsaturated monomer is diacetone-acryloamide(DAA) or acetoacetyl β-dimethyl-aminoethylmethacrylate;Described internal plasticization monomer is n-butyl maleate, diisooctyl maleate, dibutyl fumarate, a kind of in the dibutyl itaconate.Described interior cross-linking monomer such as relates generally at the multi-functional acrylate's monomer that contains the two keys of two or more C=C;Described emulsifying agent be 2 ?Bing Xi Xian An ?2 ?in the methyl propane sulfonic acid sodium salt, sodium vinyl sulfonate, allyloxy polyoxyethylene nonylphenol ether ammonium sulfate one or both; Described initiator be ammonium persulphate, Potassium Persulphate or 2,2' ?azo diisobutyl amidine dihydrochloride; Described chain-transfer agent is n-dodecyl mercaptan or uncle's lauryl mercaptan; Described functional agent is Surfynol420, Surfynol440 or Surfynol465.
- Food and medicine soft packaging use Su according to claim 1 ?mould the preparation method of composite adhesive, it is characterized in that: described interior cross-linking monomer is Phthalic acid, diallyl ester, diallyl maleate, glycidyl allyl ether, 1,6 ?hexanediyl ester, Vinylstyrene, 1,4 ?propylene glycol diacrylate, 1,2 ?in the Ethylene glycol dimethacrylate, TEGDMA, trimethylolpropane trimethacrylate, tetramethylol methane tetraacrylate one or both.
- Food and medicine soft packaging use Su according to claim 1 ?mould the preparation method of composite adhesive, it is characterized in that: in parts by weight, described monomer mixture I is 70～85 parts.
- Food and medicine soft packaging use Su according to claim 1 ?mould the preparation method of composite adhesive, it is characterized in that: in parts by weight, described monomer mixture II is 5～15 parts.
- Food and medicine soft packaging use Su according to claim 1 ?mould the preparation method of composite adhesive, it is characterized in that: in parts by weight, described internal plasticization monomer is 1～1.5 part.
- 6. a food and medicine soft packaging use is moulded ?and is moulded composite adhesive, it is characterized in that it is by claim 1 ?5 each described method preparations.
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