CN109161363A

CN109161363A - High-barrier aqueous adhesive

Info

Publication number: CN109161363A
Application number: CN201811040276.7A
Authority: CN
Inventors: 刘燕; 王灿军; 刘建林
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-09-07
Filing date: 2018-09-07
Publication date: 2019-01-08
Anticipated expiration: 2038-09-07
Also published as: CN109161363B

Abstract

The present invention relates to packaging material fields, and in particular to a kind of high-barrier aqueous adhesive prepares the method for the aqueous adhesive and the purposes of the aqueous adhesive.The invention further relates to a kind of composite membranes, and it includes the bonding barrier layers formed by aqueous adhesive of the invention.The invention further relates to prepare the method for the composite membrane, the purposes of the composite membrane and packaging comprising the composite membrane.

Description

High-barrier aqueous adhesive

Technical field

The present invention relates to packaging material fields, and in particular to a kind of high-barrier aqueous adhesive prepares the aqueous gluing The purposes of the method for agent and the aqueous adhesive.The invention further relates to a kind of composite membrane, it includes by of the invention aqueous The bonding barrier layer that adhesive is formed.The invention further relates to prepare the method for the composite membrane, the purposes of the composite membrane and Packaging comprising the composite membrane.

Background technique

Although plastics package has been widely used to food and non-food stuff packaging material, common plastics are packed to gas (such as oxygen, carbon dioxide gas, fragrance) or the barrier property of steam are bad.Packaging material for food requires to have oxygen good Barrier property, reason are that the oxygen in environment can cause Food Oxidation, cause brown stain, rancid, spoiled and peculiar smell, generate mould Deng easy to cause damages to health.In addition, packaging material for food also needs to have carbon dioxide gas, fragrance, steam etc. centainly Barrier property.

To meet the needs of packaging material is to barrier property, usual way be coated on substrate high barrier material (PVA, PVDC), alternatively, barrier material (EVOH) is added while processing base material film using multi-layer co-extruded equipment, high resistant is directly extruded Diaphragm.However, these methods be easy to cause the increased costs of packaging, so that valence of the food manufacturer due to high-barrier packaging material Lattice factor and use non-barrier package, cause food spoilage in the shelf-life, fragrance is lost, external peculiar smell intrusion, makes the mouth of food Sense is deteriorated, and brings huge hidden danger to food safety.

In addition, in recent years, as food industry is not after development, to the printing of packaging material, intensity, heat sealability and appearance etc. It is required that also improving.To meet these requirements, it is sometimes desirable to together by the membrane material compound sticking of two kinds of unlike materials.It is existing Adhesive employed in technology is organic solvent-borne, will cause volatile organic compound in the process of packaging material The discharge of object (VOC), therefore pose a big pressure to environmental protection, it is damaged to environment.In addition, employed in the prior art Adhesive do not have the other function other than binding function usually.

Therefore, this field needs a kind of new adhesive, can satisfy packaging material barrier property, cementability, environmental protection plus The requirement of work cost etc..

Summary of the invention

The present inventor has creatively obtained a kind of aqueous adhesive by a large amount of research work, can assign packet Package material has excellent glue-joint strength, and processability and operability are good, not will cause with excellent barrier property VOC emission thus provides following inventions:

Aqueous adhesive

In one aspect, this application provides a kind of aqueous adhesive, it includes:

(1) barrier resin of 1%-30%；

(2) the pre-polymerization agent of 0.1%-20%；

(3) crosslinking and curing agent of 0.01%-20%；

(4) nano-inorganic substance of 0%-5%；

(5) heat stabilizer and/or light stabilizer of 0%-2%；

(6) the levelling tackifier of 0%-10%；

(7) surfactant of 0%-2%；With

(8) water of 11%-98.89%；

Wherein, each weight percent is the total weight based on the aqueous adhesive.

In certain embodiments, the barrier resin can be selected from: polyvinyl alcohol, polyvinylpyrrolidone and its mixed Close object.

In certain embodiments, the barrier resin can have about 3,000- about 300,000 molecular weight, such as It can have about 3,000- about 10,000, about 10,000- about 25,000, about 25,000- about 35,000, about 35,000- about 50, 000, about 50,000- about 100,000, about 100,000- about 120,000, about 120,000- about 150,000, about 150,000- be about 170,000, the molecular weight of about 170,000- about 220,000, about 220,000- about 250,000 or about 250,000- about 300,000.

In certain embodiments, the barrier resin may include polyvinyl alcohol.In certain embodiments, described Polyvinyl alcohol can have about 500- about 3,000 degree of polymerization, and for example, about 500, about 1,000, about 1,500, about 1,650, about 1, 700, about 1,850, about 2,000, about 2,400 or about 2,600 degree of polymerization.In certain embodiments, the polyvinyl alcohol can To have at least about 78% degree of hydrolysis, such as it can have about 88%, about 95% or about 99% degree of hydrolysis.In certain implementations In scheme, the polyvinyl alcohol can have about 1700 degree of polymerization, and the degree of hydrolysis of about 88%- about 99%.

In certain embodiments, the barrier resin may include polyvinylpyrrolidone.In certain embodiments In, the polyvinylpyrrolidone can have about 3,000- about 40,000 molecular weight, such as can have about 3, and 500, about 5,500, about 10,100, about 32,000 or about 37,900 molecular weight.

In certain embodiments, the pre-polymerization agent can be selected from: epoxy resin, polyurethane, saturated polyester, ethylene amino Change acrylate copolymer, polyester resin, polyethyleneimine, urea, melamine, melamine resin (melamine resin), Polyamine epichlorohydrin resin, water soluble alkyd resin, opens Pu Shi resin and any combination thereof at ammonia-epichlorohydrin resin.

In the present invention, pre-polymerization agent refers to the substance that adhesive effect is played in adhesive, can be containing it is multiple (such as 2,3,4 or 5) reactive functionality (such as containing epoxy group, carbamate groups, hydroxyl, amino and/or alkenyl etc.) Oligomer, the reactive functionality (such as can be end group or the side of oligomer in any position of oligomer chain Base).In certain embodiments, the molecular weight that can have about 300- about 5000 of pre-polymerization agent, for example, about 300- about 1000, about The molecular weight of 1000- about 2000, about 2000- about 3000, about 3000- about 4000 or about 4000- about 5000.

Pre-polymerization agent of the invention be also possible to containing multiple (such as 2,3,4 or 5) can reactive functionality (such as Hydroxyl, amino and/or alkenyl etc.), small molecule, such as urea, melamine that polymer can be formed etc..

In certain embodiments, the crosslinking and curing agent can be selected from: aliphatic carboxylic acid and its derivative (such as lemon Acid, formic acid, acetic acid, acrylic acid, maleic acid, sorbic acid, itaconic acid, acetic anhydride, maleic anhydride), aliphatic aldehyde (such as first Aldehyde, acetaldehyde, glyoxal, dimethoxym ethane, paraformaldehyde, methacrylaldehyde, citral, valeral), oxazoline quasi polymer, isocyanates, three Allyl chlorinated isocyanurates and any combination thereof.

In certain embodiments, the nano-inorganic substance can be selected from: nano silicon oxide, nano aluminium oxide, nano oxygen Change titanium, nano zine oxide, nano phase ag_2 o, graphene, nano montmorillonite, nano talc, nanometer calcium carbonate, nano clay and Any combination thereof.In certain embodiments, the average grain diameter of the nano-inorganic substance is about 10nm- about 200nm, for example, about 10nm- about 20nm, about 20nm- about 50nm, about 50nm- about 100nm or about 100nm- about 20nm.

In certain embodiments, the heat stabilizer and light stabilizer can be independently selected from: inorganic lead salt and organic Lead salt thermal stabilizer, metallic soap and metal salt stabilizers, organic tin stabilizer, organic antimony stabilizer, rare-earth stabilizer, tristearin Acid, salicylate light stabilizer, benzoate light stabilizer, cyanoacrylate light stabilizer, benzophenone light Stabilizer, hindered amine light stabilizer, zinc class photomask agent class and its mixture and any combination thereof.

In certain embodiments, the levelling tackifier can be selected from: ethyl alcohol, methanol, isopropanol, butanol, ethylene glycol Ether, propylene glycol, vinyl pyrrolidone, polyalcohol, cellulose, chitosan, chitin, acrylamide, caprolactam and its Any combination.

In certain embodiments, the surfactant can be selected from alkyl phenol polyoxyethylene ether, dimethyl Base amine-oxides, fluorocarbon surfactant, hc-surfactant, alkylbenzene sulfonate and any combination thereof.

In certain embodiments, the aqueous adhesive may include about 1%- about 5%, about 5%- about 10%, about The barrier resin of 10%- about 15%, about 15%- about 20%, about 20%- about 25% or about 25%- about 30%.In certain implementations In scheme, the aqueous adhesive may include about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29% or 30% barrier resin.

In certain embodiments, the aqueous adhesive may include about 0.1%- about 1%, about 1%- about 5%, about The pre-polymerization agent of 5%- about 10%, about 10%- about 15% or about 15%- about 20%.In certain embodiments, the aqueous gluing Agent may include about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% Or 20% pre-polymerization agent.

In certain embodiments, the aqueous adhesive may include about 0.01%- about 0.1%, about 0.1%- about 1%, the crosslinking and curing agent of about 1%- about 5%, about 5%- about 10%, about 10%- about 15% or about 15%- about 20%.Certain In embodiment, the aqueous adhesive may include about 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% crosslinking and curing agent.

In certain embodiments, the aqueous adhesive may include 0%- about 1%, about 1%- about 2%, about 2%- about 3%, the nano-inorganic substance of about 3%- about 4% or about 4%- about 5%.In certain embodiments, the aqueous adhesive can be with Comprising about 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4% or 5% Nano-inorganic substance.

In certain embodiments, the aqueous adhesive may include 0%- about 0.5%, about 0.5%- about 1%, about The heat stabilizer and/or light stabilizer of 1%- about 1.5% or about 1.5%- about 2%.In certain embodiments, the water-base cement Stick may include about 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% or 2% thermostabilization Agent and/or light stabilizer.

In certain embodiments, the aqueous adhesive may include 0%- about 0.1%, about 0.1%- about 1%, about The levelling tackifier of 1%- about 5% or about 5%- about 10%.In certain embodiments, the aqueous adhesive include about 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% levelling tackifier.

In certain embodiments, the aqueous adhesive may include 0%- about 0.5%, about 0.5%- about 1%, about The surfactant of 1%- about 1.5% or about 1.5%- about 2%.In certain embodiments, the aqueous adhesive can wrap Containing about 0%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% or 2% surfactant.

In certain embodiments, the aqueous adhesive may include about 11%- about 15%, about 15%- about 20%, about 20%- about 30%, about 30%- about 40%, about 40%- about 50%, about 50%- about 60%, about 60%- about 70%, about 70%- are about 80%, the water of about 80%- about 90% or about 90%- about 98.89%.In certain embodiments, the aqueous adhesive can be with Comprising about 11%, 15%, 20%, 30%, 40%, 50%, 58%, 59%, 59.69%, 60%, 63%, 64%, 64.98%, 65%, 66%, 66.8%, 67%, 70%, 71%, 71.5%, 72%, 75%, 78%, 79%, 79.4%, 80%, 81%, 82%, 82.5%, 83%, 84%, 85%, 86%, 87%, 87.5%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5% or 98.89% water.

In certain embodiments, the aqueous adhesive may include: the barrier resin of about 1%- about 30%, about Pre-polymerization agent, the crosslinking and curing agent of about 0.01%- about 20% and the water of 11%-98.89% of 0.1%- about 20%.

In certain embodiments, the aqueous adhesive may include: the barrier resin of about 1%- about 30%, about The pre-polymerization agent of 0.1%- about 20%, the crosslinking and curing agent of about 0.01%- about 20%, the nano-inorganic substance of 0%- about 5%, 0%- are about 10% levelling tackifier and the water of about 11%- about 98.89%.

In certain embodiments, the aqueous adhesive may include: the barrier resin of about 1%- about 30%, about The pre-polymerization agent of 0.1%- about 20%, the crosslinking and curing agent of about 0.01%- about 20%, the heat stabilizer of 0%- about 2% and/or light are steady Determine the surfactant of agent, 0%- about 2% and the water of about 11%- about 98.89%.

In certain embodiments, the barrier resin can be selected from: polyvinyl alcohol, polyvinyl alcohol and polyvinyl pyrrole The mixture of alkanone.Preferably, in the mixture of the polyvinyl alcohol and polyvinylpyrrolidone, polyvinyl alcohol and polyethylene pyrrole The weight ratio of pyrrolidone is about 1-5:0.5-1, for example, about 1:0.5.

In certain embodiments, the pre-polymerization agent can be selected from: epoxy resin, melamine resin, saturated polyester, poly- ammonia Ester, melamine, polyethyleneimine, polyamine epichlorohydrin resin, polyester resin and any combination thereof.In certain embodiment party In case, the pre-polymerization agent can be selected from: the mixture of epoxy resin and melamine resin, saturated polyester, polyurethane, melamine, Polyethyleneimine, polyamine epichlorohydrin resin, polyester resin.Preferably, the mixing of the epoxy resin and melamine resin In object, the weight ratio of epoxy resin and melamine resin can be about 0.1-1:1-5, for example, about 0.3:1.

In certain embodiments, the crosslinking and curing agent can be selected from: citric acid, glyoxal, oxazoline quasi polymer, Formaldehyde, formic acid, isocyanates, maleic anhydride and any combination thereof.

In certain embodiments, the nano-inorganic substance can be nano aluminium oxide.

In certain embodiments, the heat stabilizer or light stabilizer can be rare-earth stabilizer.

In certain embodiments, the levelling tackifier can be ethyl alcohol.

In certain embodiments, the surfactant can be hc-surfactant.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, epoxy resin, melamine tree Rouge, citric acid and water.In certain embodiments, the aqueous adhesive may include: the polyvinyl alcohol of about 9%- about 11%, The citric acid of the mixture of the epoxy resin of about 1%- about 2% and melamine resin, 0.1%-1%, Yi Jishui.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, saturated polyester, glyoxal And water.In certain embodiments, the aqueous adhesive includes: polyvinyl alcohol, the about 8%- about 11% of about 20%- about 30% Saturated polyester, about 3%- about 5% glyoxal, Yi Jishui.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, polyvinylpyrrolidone, Polyurethane, oxazoline quasi polymer and water.In certain embodiments, the aqueous adhesive may include: about 20%- is about Polyurethane, the about 0.01%- about 0.1% of 30% polyvinyl alcohol and the mixture of polyvinylpyrrolidone, about 8%- about 11% Oxazoline quasi polymer, Yi Jishui.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, melamine, formaldehyde and Water.In certain embodiments, the aqueous adhesive may include: the polyvinyl alcohol of about 20%- about 30%, about 5%- are about The formaldehyde of 10% melamine, about 0.1%- about 1%, Yi Jishui.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, polyethyleneimine, nanometer Aluminium oxide, ethyl alcohol, formic acid and water.In certain embodiments, the aqueous adhesive may include: about 12%-'s about 15% The second of the polyethyleneimine of polyvinyl alcohol, about 0.1%- about 0.5%, the nano aluminium oxide of about 1%- about 5%, about 8%- about 10% The formic acid of alcohol, about 4%- about 6%, Yi Jishui.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, polyamideepichlorohydrin Resin, rare-earth stabilizer, hc-surfactant, isocyanates and water.In certain embodiments, the aqueous adhesive can With comprising: the polyvinyl alcohol of about 18%- about 20%, the polyamine epichlorohydrin resin of about 5%- about 10%, about 0.1%- are about The isocyanates of the hc-surfactant of 0.5% rare-earth stabilizer, about 0.01%- about 0.05%, about 10%- about 16%, And water.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, polyurethane, oxazoline class Polymer, rare-earth stabilizer, hc-surfactant and water.In certain embodiments, the aqueous adhesive may include: The polyvinyl alcohol of about 10%- about 15%, the polyurethane of about 3%- about 5%, the oxazoline quasi polymer of about 1%- about 3%, about The rare-earth stabilizer of 0.1%- about 0.5% and the mixture of hc-surfactant, Yi Jishui.Wherein, rare-earth stabilizer and carbon The ratio of hydrogen surfactant can be adjusted according to actual needs, such as the two ratio can be about 1:0.5- about 1:1.

In certain embodiments, aqueous adhesive of the invention may include: polyvinyl alcohol, polyester resin, rare earth are steady Determine agent, hc-surfactant, maleic anhydride and water.In certain embodiments, the aqueous adhesive may include: about The polyvinyl alcohol of 10%- about 15%, the polyester resin of about 3%- about 5%, the rare-earth stabilizer of about 0.1%- about 0.5%, about The maleic anhydride of the hc-surfactant of 0.1%- about 0.5%, about 0.1%- about 0.5%, Yi Jishui.

Commercially available raw material be can use to obtain aqueous adhesive of the invention, selectable marketable material includes but unlimited In: polyvinyl alcohol -1799, polyvinyl alcohol -1788, epoxy resin CYD803, melamine resin DY104, saturated polyester BPE-9985, Polyvinylpyrrolidone K17, polyurethane 58887, polyurethane X-PU632, oxazoline quasi polymer 500, polyethyleneimine SP- 003, nano aluminium oxide C1-L20M, polyamine epichlorohydrin resin 1200S3, rare-earth stabilizer XT-1, rare-earth stabilizer XT- 2, rare-earth stabilizer XT-3, hc-surfactant 2223, hc-surfactant 343, hc-surfactant 434, isocyanide Acid esters 44V20, polyester resin 51530.

As needed, antioxidant, defoaming agent, colorant etc. can also be included in aqueous adhesive of the invention.

Composite membrane

Aqueous adhesive of the invention can be used for the compound of various packaging base materials, such as polymer film and polymer film Compound or polymer film and paper it is compound, can be realized simultaneously the dual function of bonding and barrier.

Therefore, this application provides a kind of composite membranes, and it includes the bonding formed by aqueous adhesive of the invention barriers Layer.

In certain embodiments, the composite membrane successively may include first base material layer, the bonding barrier layer and Two substrate layers, the first base material layer can be mainly made of polymer or paper, and second substrate layer can be mainly by polymerizeing Object or paper composition.

In composite membrane of the invention, the material of substrate layer does not have special limitation, it is preferable that first base material layer and the second base At least one of material layer can be mainly made of polymer.

In certain embodiments, the polymer in the polymer and second substrate layer in the first base material layer is only It on the spot can be selected from polyethylene (PE), polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) and polyphenyl Ethylene (PS).

In certain embodiments, the polyethylene can be selected from: linear low density polyethylene (LLDPE), low-density are poly- Ethylene (LDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) (HDPE).

In certain embodiments, the main component of the first base material layer and the second substrate layer can be selected from following group It closes:

(1) polyethylene and polyethylene；

(2) polypropylene and polypropylene；

(3) nylon and polypropylene；

(4) polyethylene terephthalate and polyethylene；

(5) polyethylene terephthalate and polypropylene；

(6) polypropylene and polyethylene；

(7) nylon and polyethylene；

(8) paper and polyethylene；

(9) paper and polypropylene；

(10) polystyrene and polypropylene.

When the above a certain combination is used as the main component of first base material layer and the second substrate layer, first base material layer can be with It is any member of the combination, and the second substrate layer is another member of the combination.

For example, the main component of first base material layer is polyethylene, at this time the master of the second substrate layer when using combination (1) Wanting ingredient is polyethylene identical or different with the polyethylene property of first base material layer.

For example, the main component of first base material layer is polypropylene, at this time the master of the second substrate layer when using combination (2) Wanting ingredient is polypropylene identical or different with the polypropylene property of first base material layer,

For example, the main component of first base material layer can be nylon (the second substrate layer at this time when being combined using (3) Main component be polypropylene), or can be polypropylene (at this time the main component of the second substrate layer be nylon).

For example, the main component of first base material layer can be polyethylene terephthalate when being combined using (4) (main component of the second substrate layer is polyethylene at this time), or can be the polyethylene (main component of the second substrate layer at this time For polyethylene terephthalate).

For example, the main component of first base material layer can be polyethylene terephthalate when being combined using (5) (main component of the second substrate layer is polypropylene at this time), or can be the polypropylene (main component of the second substrate layer at this time For polyethylene terephthalate).

For example, the main component of first base material layer can be polypropylene (the second substrate at this time when being combined using (6) The main component of layer is polyethylene), or can be polyethylene (main component of the second substrate layer is polypropylene at this time).

For example, the main component of first base material layer can be nylon (the second substrate layer at this time when being combined using (7) Main component be polyethylene), or can be polyethylene (at this time the main component of the second substrate layer be nylon).

For example, the main component of first base material layer can be paper (second substrate layer at this time when being combined using (8) Main component is polyethylene), or can be polyethylene (main component of the second substrate layer is paper at this time).

For example, the main component of first base material layer can be paper (second substrate layer at this time when being combined using (9) Main component is polypropylene), or can be polypropylene (main component of the second substrate layer is paper at this time).

For example, the main component of first base material layer can be polystyrene (the second base at this time when being combined using (10) The main component of material layer is polypropylene), or can be polypropylene (main component of the second substrate layer is polystyrene at this time).

In composite membrane of the invention, first base material layer and the second substrate layer can be bonded together by being bonded barrier layer. In certain embodiments, the bonding barrier layer can be by the coated formation of aqueous adhesive any one of as described above 's.

In composite membrane of the invention, the thickness of each layer is not particularly limited.In certain embodiments, it is bonded barrier layer Thickness can be about 2 μm-about 6 μm, such thickness is conducive to the drying of aqueous adhesive.

The overall thickness of composite membrane of the invention is also not particularly limited.In certain embodiments, the composite membrane Overall thickness can be about 30 μm-about 150 μm, for example, about 30 μm-about 40 μm, about 40 μm-about 50 μm, about 50 μm-about 60 μm, about 60 μm-about 70 μm, about 70 μm-about 80 μm, about 80 μm-about 90 μm, about 90 μm-about 100 μm, about 100 μm-about 110 μm, about 110 μm- About 120 μm, about 120 μm-about 130 μm, about 130 μm-about 140 μm or about 140 μm-about 150 μm.

Composite membrane of the invention has good peel strength.In certain embodiments, GB8808 according to national standards Method measure, the peel strength of the composite membrane can be about 1.5N- about 3N, for example, about 1.5N- about 1.6N, about 1.6N- about 1.7N, about 1.7N- about 1.8N, about 1.8N- about 1.9N, about 1.9N- about 2.0N, about 2.0N- about 2.1N, about 2.1N- are about 2.2N, about 2.2N- about 2.3N, about 2.3N- about 2.4N, about 2.4N- about 2.5N, about 2.5N- about 2.6N, about 2.6N- about 2.7N, about 2.7N- about 2.8N, about 2.8N- about 2.9N or about 2.9N- about 3.0N.

Meanwhile composite membrane of the invention has good gas barrier property.In certain embodiments, such as according to state Family standard GB/T 1038-2000 is measured, and the oxygen transit dose of the composite membrane can be about 0.2- about 2.5cm³/m²· 1MPa for 24 hours, for example, about 0.2- about 0.5cm³/m²1MPa, about 0.5- about 1cm for 24 hours³/m²1MPa, about 1- be about for 24 hours 1.5cm³/m²1MPa, about 1.5- about 2cm for 24 hours³/m²1MPa or about 2- about 2.5cm for 24 hours³/m²1MPa for 24 hours, example Such as from about 0.2cm³/m²·24h·1MPa、0.3cm³/m²·24h·1MPa、0.4cm³/m²·24h·1MPa、0.5cm³/m²· 24h·1MPa、0.6cm³/m²·24h·1MPa、0.7cm³/m²·24h·1MPa、0.8cm³/m²·24h·1MPa、 0.9cm³/m²·24h·1MPa、1.0cm³/m²·24h·1MPa、1.1cm³/m²·24h·1MPa、1.2cm³/m²·24h· 1MPa、1.3cm³/m²·24h·1MPa、1.4cm³/m²·24h·1MPa、1.5cm³/m²·24h·1MPa、1.6cm³/m²· 24h·1MPa、1.7cm³/m²·24h·1MPa、1.8cm³/m²·24h·1MPa、1.9cm³/m²·24h·1MPa、 2.0cm³/m²·24h·1MPa、2.1cm³/m²·24h·1MPa、2.2cm³/m²·24h·1MPa、2.3cm³/m²·24h· 1MPa、2.4cm³/m²1MPa or 2.5cm for 24 hours³/m²(test pressure difference is 1MPa to 1MPa, and temperature is 23 DEG C, wet for 24 hours 65%) degree is.

In certain embodiments, the case where such as first base material layer and the second substrate layer are all mainly made of polymer Under, the composite membrane can have the good transparency, such as with good light transmittance and lower mist degree.

Composite membrane of the invention is particularly suited for use in packaging field.In certain embodiments, the composite membrane can be Packaging film, the first base material layer can be protective layer, and second substrate layer can be sealant.

In certain embodiments, the protective layer can be mainly by polyamide, polypropylene or poly terephthalic acid second two Alcohol ester composition.

In certain embodiments, the sealant can be mainly made of polyethylene or polypropylene.

In certain embodiments, the main component of the protective layer and sealant can be selected from following combination:

(1) main component of protective layer is PP, and the main component of sealant is PE；

(2) main component of protective layer is PA, and the main component of sealant is PE；

(3) main component of protective layer is PP, and the main component of sealant is PP；

(4) main component of protective layer is PET, and the main component of sealant is PE；

(5) main component of protective layer is PA, and the main component of sealant is PP.

In certain embodiments, composite membrane of the invention can also include other layers, such as printing layer, also can be set Additional adhesive layer or additional barrier layer, to further increase adhesive strength or barrier property.

In certain embodiments, composite membrane of the invention can be made by the method for preparing composite membrane described below.

The method for preparing composite membrane

Using aqueous adhesive of the invention, composite membrane can be prepared by the way that dry type is the methods of compound.In dry type is compound, First coating binder on a substrate, later dries the solvent in adhesive, then another substrate and aforementioned substrates are pasted It closes, then carries out maturation process, obtain composite membrane.

Therefore, in certain embodiments, the method may include following steps:

Step 1: first base material, the second substrate and aqueous adhesive of the invention are provided；

Step 2: aqueous adhesive of the invention is coated on the surface of the first base material；

Step 3: the first base material after coating is heated；

Step 4: under the conditions of being heated and pressurizeed, being bonded the second substrate with the first base material handled through step 3, obtain To semi-finished product film；

Step 5: the semi-finished product film that step 4 obtains is cured.

Preferably, the first base material and the second substrate can be selected from polymer film and paper each independently.

The present invention is prepared in the method for composite membrane, the not special limitation of the selection for substrate, it is preferable that first At least one of substrate and the second substrate are polymer films.

In certain embodiments, the polymer film can be selected from polyethylene film (PE film), polypropylene screen (PP film), gather Amide film (PA film), polyethylene terephthalate film (PET film) and polystyrene film (PS film).

In certain embodiments, the polypropylene screen can be selected from: oriented polypropylene (OPP) film (OPP film), biaxial tension are poly- Propylene film (BOPP film) and cast polypropylene film (CPP film).

In certain embodiments, the polyethylene film can be selected from: linear low density polyethylene film (LLDPE film), low Density polyethylene film (LDPE film), medium density polyethylene film (MDPE film), density polyethylene film with high (HDPE film).

In certain embodiments, the first base material and the second substrate can be selected from following combination:

(1) polyethylene film and polyethylene film (PE film/PE film)；

(2) polypropylene screen and polypropylene screen, such as oriented polypropylene (OPP) film and cast polypropylene film (OPP film/CPP film)；

(3) nylon membrane and polypropylene screen (PA film/PP film)；

(4) polyethylene terephthalate film and polyethylene film (PET film/PE film)；

(5) polyethylene terephthalate film and polypropylene screen, such as polyethylene terephthalate film and curtain coating Polypropylene screen (PET film/CPP film)；

(6) polypropylene screen and polyethylene film, such as oriented polypropylene (OPP) film and polyethylene film (OPP film/PE film)；

(7) nylon membrane and polyethylene film (PA film/PE film)；

(8) paper and polyethylene film；

(9) paper and polypropylene screen；

(10) polystyrene film and polypropylene screen.

When will the above a certain combination be used as first base material and the second substrate when, first base material can be the combination it is any at Member, and the second substrate is another member of the combination.

For example, when using combination (1) when, first base material is polyethylene film, at this time the second substrate be with as first base material Polyethylene film property is identical or different another polyethylene film.

For example, when using combination (2) when, first base material is polypropylene screen, at this time the second substrate be with as first base material Polypropylene screen property is identical or different another polypropylene screen.

For example, first base material can be nylon membrane (the second substrate is polypropylene screen at this time) when being combined using (3), Or it can be polypropylene screen (the second substrate is nylon membrane at this time).

For example, first base material can be polyethylene terephthalate film (at this time second when being combined using (4) Substrate is polyethylene film), or can be polyethylene film (the second substrate is polyethylene terephthalate film at this time).

For example, first base material can be polyethylene terephthalate film (at this time second when being combined using (5) Substrate is polypropylene screen), or can be polypropylene screen (the second substrate is polyethylene terephthalate film at this time).

For example, first base material can be polypropylene screen, and (the second substrate is polyethylene at this time when being combined using (6) Film), or can be polyethylene film (the second substrate is polypropylene screen at this time).

For example, first base material can be nylon membrane (the second substrate is polyethylene film at this time) when being combined using (7), Or it can be polyethylene film (the second substrate is nylon membrane at this time).

For example, first base material can be paper (the second substrate is polyethylene film at this time) when being combined using (8), or It can be polyethylene film (the second substrate is paper at this time).

For example, first base material can be paper (the second substrate is polypropylene screen at this time) when being combined using (9), or It can be polypropylene screen (the second substrate is paper at this time).

For example, first base material can be polystyrene film, and (the second substrate is polypropylene at this time when being combined using (10) Film), or can be polypropylene screen (the second substrate is polystyrene film at this time).

Method of the invention is particularly suitable for prepare the packaging film with sealant and protective layer.In certain embodiments In, the first base material has good dimensional stability, can be used for being formed protective layer, and second substrate has good Chemical inertness, osmotic-pressure-tolerant and heat sealability, can be used for forming sealant.

In certain embodiments, the first base material can be selected from: PA membrane (such as BOPA film), polypropylene screen (such as BOPP film), polyethylene terephthalate film.

In certain embodiments, second substrate can be selected from: polyethylene film, polypropylene screen (such as CPP film).

(1) first base material is BOPP film, and the second substrate is PE film；

(2) first base material is BOPA film, and the second substrate is PE film；

(3) first base material is BOPP film, and the second substrate is CPP film；

(4) first base material is PET film, and the second substrate is PE film；

(5) first base material is BOPA film, and the second substrate is CPP film.

The thickness of substrate, which can according to need, to be selected, and is not particularly limited.

In certain embodiments, the thickness of the first base material can be about 10 μm-about 250 μm, for example, about 10 μm-about 50 μm, about 50 μm-about 100 μm, about 100 μm about -150 μm, about 150 μm-about 200 μm or about 200 μm-about 250 μm, for example, about 10 μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μm、110μm、120μm、130μm、140μm、150μ M, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm or 250 μm.

In certain embodiments, the thickness of second substrate can be about 10 μm-about 250 μm, for example, about 10 μm-about 50 μm, about 50 μm-about 100 μm, about 100 μm-about 150 μm, about 150 μm-about 200 μm or about 200 μm-about 250 μm, for example, about 10 μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm、100μm、110μm、120μm、130μm、140μm、150μ M, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm or 250 μm.

In order to enable substrate equably to infiltrate adhesive, the film as substrate preferably has suitable surface tension. Preferably, the surface tension coefficient of first base material and the second substrate can be about 38 dynes or more respectively.On the surface of substrate In the case that power is not high, preferably substrate is handled, so that its surface roughening, so that when adhesive is contacted with substrate surface When, it can produce good effect of impregnation, fastness is pasted in increase.

In certain embodiments, in step 2, aqueous adhesive can be about 0.3 Ke-about 8 grams with every square meter, such as often put down Rice about 0.3 Ke-about 1 grams, about 1 Ke-about 5 grams of every square meter, about 5 Ke-about 8 grams of every square meter, such as 2 grams of every square meter, 3 grams of every square meter, 4 grams of every square meter, 5 grams of every square meter, 6 grams of every square meter, 7 grams of every square meter or 8 grams of every square meter of amount (dry weight) are coated in first base material.

In certain embodiments, one or many coatings can be carried out.

In step 3, the first base material after gluing can be heated, to remove the solvent in adhesive.Certain In embodiment, the heating in step 3 can divide three sections of progress, temperature successively can be about 60 DEG C-about 75 DEG C, about 65 DEG C-about 75 DEG C, about 70 DEG C-about 85 DEG C.In certain embodiments, points of four sections progress of the heating in step 3, temperature be followed successively by about 60 DEG C- About 70 DEG C, about 70 DEG C-about 75 DEG C, about 75 DEG C-about 80 DEG C, about 75 DEG C-about 85 DEG C.

In certain embodiments, the temperature heated in step 4 can be about 50 DEG C-about 65 DEG C, for example, about 50 DEG C, 55 DEG C, 60 DEG C or 60 DEG C.

In steps of 5, semi-finished product film can be placed to a period of time in a heated condition, cured, to accelerate gluing Curing reaction in agent.In certain embodiments, the temperature of curing can be about about 80 DEG C of 40-, for example, about 40 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 65 DEG C, 70 DEG C or 80 DEG C.In certain embodiments, the time of curing can be about 12- about 72 hours, such as About 24 hours, 48 hours, 50 hours or 72 hours.

Aqueous adhesive of the invention can also be used only as barrier coating fluid, be coated on substrate, form barrier Layer, it is compound with other substrates later using solvent-free compound adhesive or solvent borne compound adhesive as adhesive.Therefore, in certain realities It applies in scheme, can also include: to be coated with other gluing on through step 3 treated first base material between step 3 and step 4 Agent.The other adhesive can be solventless adhesive or solvent adhesive.

Dry compound machine can be used to be prepared.Illustrative dry compound machine can consist of the following components: main Unreel, gluing portion (including such as anilox roll, dandy roll, scraper, smooth out roller component), drying tunnel or baking oven, pair unreels, composite part (including component such as pre- hot-rolling, compound hot-rolling, chill roll), cooling end, curing chamber.Illustrative preparation process can be as Under: on dry compound machine, master unreels placement first base material, and aqueous adhesive is coated in first base material；It is carried out after gluing It is dry；Pair unreel place the second substrate, make its with by gluing and dry after first base material under the action of compound hot-rolling into Row fitting, obtains semi-finished product film；Semi-finished product film is put into curing chamber and is cured, composite membrane is obtained.The main substrate unreeled is best With certain tensile strength, under certain tension and certain heating temperature, deformation is smaller.

The invention further relates to composite membranes prepared by the above method.

The method for preparing aqueous adhesive

On the other hand, this application provides the methods for preparing aqueous adhesive as described above, may include following step It is rapid:

Step 1: the barrier resin, pre-polymerization agent, crosslinking and curing agent and water are provided in proportion；

Step 2: barrier resin being dissolved in the water, semi-finished product are obtained；

Step 3: pre-polymerization agent being mixed with semi-finished product, optionally, to being added in the mixture of pre-polymerization agent and semi-finished product Nano-inorganic substance, heat stabilizer, light stabilizer, levelling tackifier, surfactant or any combination thereof, obtain aqueous adhesive Host agent；

Step 4: aqueous adhesive host agent being mixed with crosslinking and curing agent, obtains aqueous adhesive.

Preferably, the course of dissolution in step 2 can carry out under heating and stirring condition.In certain embodiments In, the temperature of heating can be about 40 DEG C-about 90 DEG C (for example, about 40 DEG C-about 50 DEG C, about 50 DEG C-about 60 DEG C, about 60 DEG C-about 70 DEG C, about 70 DEG C-about 80 DEG C, about 85 DEG C or about 80 DEG C-about 90 DEG C).In certain embodiments, heating can be small for about 12 When-about 24 hours.After the dissolution for completing barrier resin in a heated condition, it is preferable that it can cool down to semi-finished product, Such as it can be reduced to room temperature, such as about 35 DEG C-about 10 DEG C, about 20 DEG C-about 10 DEG C or about 30 DEG C-about 20 DEG C can be reduced to.

Preferably, the mixed process in step 3 can carry out under heating and stirring condition.In certain embodiments In, the temperature of heating can be about 10 DEG C-about 70 DEG C (for example, about 20 DEG C-about 40 DEG C, about 40 DEG C-about 45 DEG C, about 50 DEG C-about 70 DEG C or about 40 DEG C-about 60 DEG C).In certain embodiments, heating can be for about 1 hour-about 20 hours.It preferably, can be with Cool down to the mixture of pre-polymerization agent and semi-finished product by heating, such as room temperature can be reduced to, such as can be reduced to About 25 DEG C-about 15 DEG C, about 15 DEG C-about 10 DEG C or about 29 DEG C-about 20 DEG C.

In certain embodiments, the step 3 further comprises: carrying out to the mixture of pre-polymerization agent and semi-finished product Filter, to remove impurity.

It can according to need, stablize to nano-inorganic substance, heat stabilizer, light are added in the mixture of pre-polymerization agent and semi-finished product Agent, levelling tackifier, surfactant etc..The suitable time for adding these substances can be after cooling, and can be with Before filtration.

Aqueous adhesive host agent of the invention can have good stability, and 30 days are stored at about 5 DEG C-about 40 DEG C extremely Do not generate gelatin phenomenon within 70 days.

In step 4, barrier resin in aqueous adhesive host agent and pre- can be made by the way that crosslinking and curing agent is added Poly- agent is cured.Therefore, usually aqueous adhesive host agent is retained separately with crosslinking and curing agent, also, in aqueous adhesive Crosslinking and curing agent is added before use.Therefore, step 4 is preferably carried out before using the aqueous adhesive.Preferably, it walks Mixed process in rapid 4 can carry out under stirring conditions.

The invention further relates to the purposes that the aqueous adhesive of any of the above-described is used to prepare composite membrane.

The purposes packed to article is used for the invention further relates to the composite membrane of any of the above-described.In certain embodiments In, the article can be food (such as liquid food or solid food).In certain embodiments, the article can be Non-food stuff (such as drug).

The invention further relates to a kind of packagings, contain any of the above-described composite membrane.

In the present invention, unless otherwise stated, Science and Technology noun used herein has art technology The normally understood meaning of personnel institute.Also, laboratory operation step involved in herein is to be widely used in corresponding field Conventional steps.Meanwhile for a better understanding of the present invention, the definition and explanation of relational language is provided below.

In the present invention, term " film " is also referred to as " film ", refers to thin and flexible thin slice made of polymer, thickness from About 1 micron is arrived several hundred microns (for example, about 1 micron to about 250 microns), including metal (such as aluminium) is passed through the plating of the methods of vapor deposition The metal coating (such as aluminium plated film) formed on polymer film.

In the present invention, term " composite membrane " refers to polymer film and paper, metal sheet (such as aluminium foil) or polymer film The multilayer film formed by the modes such as being bonded, being coextruded.The material for being used to form composite membrane is referred to as substrate.Compound mode packet It includes but is not limited to that dry type is compound, wet type is compound, extrusion is compound, coextrusion is compound, solvent-free compound.

Composite membrane for packaging is referred to as packaging film or composite packing film.Packaging film generally comprises sealant, function Layer and protective layer.Wherein, sealant is also referred to as internal layer, typically directly contacts with packed article, it is general select osmotic-pressure-tolerant and The preferable material of heat sealability, to prevent packed article from oozing out, and convenient for being sealed packaging film by modes such as heat-sealings；Function Ergosphere is a lot of to the effect for obstructing gas or shading；The effects of protective layer is also referred to as outer layer, plays support, shading is usually selected With good, heat-resisting, printing performance the is good material of mechanical strength.

In the present invention, certain layer " mainly by ... form " of composite membrane or " main component be ... " each mean and do not point out The content of component will not obviously or substantially influence the performance of itself of signified layer.

In the present invention, the barrier property of film is referred to micro-molecular gas (such as oxygen), liquid, water vapour or smell Screening ability.The barrier properties for gases of film can be using gas permeation rate as index, i.e., under steady temperature and unit pressure difference, in stabilization Through when, through the volume of the gas of the film of unit area in the unit time.

In the present invention, term " oligomer " refers to gathering as composed by the repetitive unit of less (such as 10-20) Object is closed, relative molecular mass is between small molecule and macromolecule.

In the present invention, term " about " should be readily appreciated by one skilled in the art, and will be with the context of place used in it And there is a degree of variation.If to those skilled in the art, using is not according to the context of term application Clearly, then mean no more than the certain number value or range positive and negative 10% of " about ".

Advantageous effect of the invention

Aqueous adhesive of the invention is used to prepare composite membrane, and high glue-joint strength and good barrier property may be implemented, With extraordinary processability and operability, the cost of high-barrier packaging material is greatly reduced, and not will cause VOC row It puts.

Compared with existing barrier material, have using composite membrane prepared by aqueous adhesive of the invention more excellent Oxygen barrier property.Such as compared with ethylene vinyl alcohol copolymer film (EVOH film), the oxygen-barrier property of composite membrane of the invention It is doubled, and cost is 1/10th of EVOH film.

Therefore, aqueous adhesive of the invention and composite membrane can assign packaging material with excellent barrier property, and The cost for advantageously reducing high-barrier packaging material meets the needs of varieties of food items, non-food stuff are to high-barrier packaging material.

Specific embodiment

Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is It can be with conventional products that are commercially available.

In following embodiment, all parts and percentage are based on weight；Oxygen transit dose is according to GB/T 1038-2000 It is tested, test pressure difference is 1MPa, and temperature is 23 DEG C, humidity 65%；Combined strength bination refers to the removing of composite membrane Intensity is tested according to GB 8808.

Embodiment 1

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 80 DEG C -90 DEG C.After temperature drops to 35 DEG C -10 DEG C, the mixture of epoxy resin and melamine resin is added (weight ratio of 0.3:1) after being thoroughly mixed, is heated to 40 DEG C of -45 DEG C of insulation reactions 8 hours, then drops to room temperature (25 DEG C -15 DEG C), obtain high-barrier aqueous adhesive host agent after filtering, it is existing which in 10 DEG C of -40 DEG C of storages does not generate gel for 70 days As storage stability is good.It is sufficiently stirred using preceding addition citric acid up to high-barrier aqueous adhesive.

Compound to BOPP film and the progress of PE film using high-barrier aqueous adhesive obtained, process is as follows: compound in dry type It is main to unreel the BOPP film placed with a thickness of 20 μm on machine, high-barrier aqueous adhesive is coated in BOPP film, glue-spread is often put down 3 grams of rice.It is dried after gluing, compounding machine oven temperature is respectively 60 DEG C, 70 DEG C, 75 DEG C, 75 DEG C.Pair unreel placement with a thickness of 50 μm of PE film is bonded it under the action of compound hot-rolling with by gluing and dry BOPP film, obtains semi-finished product Film.Compound heat roller temperature is 60 DEG C, and machine speed is 100 meters per minute.Obtained semi-finished product film is put into the curing that temperature is 60 DEG C Interior cures 48 hours, obtains composite membrane.

The combined strength bination for measuring the composite membrane is 3N, and oxygen transit dose is 1.5cm³/m²·24h·1MPa。

Embodiment 2

According to following proportions, polyvinyl alcohol -1788 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 60 DEG C -70 DEG C.After temperature drops to 20 DEG C -10 DEG C, saturated polyester is added, after being thoroughly mixed, is heated to 50 DEG C -70 DEG C, insulation reaction 12 hours, room temperature (15 DEG C -10 DEG C) is then dropped to, high-barrier aqueous adhesive master is obtained after filtering Agent, the host agent do not generate gelatin phenomenon in 70 days in 10 DEG C of -40 DEG C of storages, and storage stability is good.It is filled using preceding addition glyoxal Divide and stirs up to high-barrier aqueous adhesive.

Compound to BOPA film and the progress of PE film using high-barrier aqueous adhesive obtained, process is as follows: compound in dry type It is main to unreel the BOPA film placed with a thickness of 15 μm on machine, high-barrier aqueous adhesive is coated on BOPA film, glue-spread is often put down 8 grams.It is dried after gluing, compounding machine oven temperature is respectively 70 DEG C, 70 DEG C, 70 DEG C.Pair unreels placement with a thickness of 120 μm PE film is bonded it under the action of compound hot-rolling with by gluing and dry BOPA film, obtains semi-finished product film.It is compound Heat roller temperature is 65 DEG C, and machine speed is 90 meters per minute.Obtained semi-finished product film is put into the curing chamber that temperature is 45 DEG C, curing 72 hours, obtain composite membrane.

The combined strength bination for measuring the composite membrane is 2.5N, and oxygen transit dose is 2cm³/m²·24h·1MPa。

Embodiment 3

According to following proportions, the mixture (weight ratio of 1:0.5) and water of polyvinyl alcohol and polyvinylpyrrolidone are added Enter into heatable reaction vessel, and be heated to 80 DEG C -90 DEG C under stiring, is completely dissolved.Temperature drops to 30 DEG C -20 DEG C Afterwards, polyurethane is added, after being thoroughly mixed, is heated to 45 DEG C of insulation reactions 7 hours, then drops to room temperature (29 DEG C -20 DEG C), Aqueous adhesive host agent is obtained after filtering, which does not generate gelatin phenomenon in 30 days in 10 DEG C of -30 DEG C of storages, and storage stability is good It is good.It is sufficiently stirred using preceding addition oxazoline quasi polymer up to aqueous adhesive.

Compound to BOPP film and the progress of CPP film using high-barrier aqueous adhesive obtained, process is as follows: compound in dry type It is main to unreel the BOPP film placed with a thickness of 15 μm on machine, high-barrier aqueous adhesive is coated in BOPP film, glue-spread is often put down 5 grams of rice.It is dried after gluing, compounding machine oven temperature is respectively 60 DEG C, 75 DEG C, 80 DEG C.Pair unreels placement with a thickness of 40 μm CPP film, make its with by gluing and dry BOPP film be bonded under the action of compound hot-rolling, obtain semi-finished product film. Compound heat roller temperature is 50 DEG C, and machine speed is 130 meters per minute.Semi-finished product film is put into the curing chamber that temperature is 65 DEG C, curing 50 hours, obtain composite membrane.

The combined strength bination for measuring the composite membrane is 2N, and oxygen transit dose is 1cm³/m²·24h·1MPa。

Embodiment 4

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 85 DEG C.After temperature drops to 20 DEG C, melamine is added, after being thoroughly mixed, it is anti-to be heated to 40 DEG C of heat preservations It answers 7 hours, then drops to room temperature (15 DEG C), high-barrier aqueous adhesive host agent is obtained after filtering, which deposits at 5 DEG C -40 DEG C It puts 60 days and does not generate gelatin phenomenon, storage stability is good.It is sufficiently stirred using preceding addition formaldehyde up to the aqueous gluing of high-barrier Agent.

Compound to PET film and the progress of PE film using high-barrier aqueous adhesive obtained, process is as follows: in dry compound machine On, it is main to unreel the PET film placed with a thickness of 12 μm, on a pet film by the coating of high-barrier aqueous adhesive, the every square meter of glue-spread 0.3 gram.It is dried after gluing, compounding machine oven temperature is respectively 70 DEG C, 75 DEG C, 75 DEG C.Pair unreels placement with a thickness of 60 μm PE film, make its with by gluing and dry PET film be bonded under the action of compound hot-rolling, obtain semi-finished product film.It is multiple Closing heat roller temperature is 50 DEG C, and machine speed is 150 meters per minute.Semi-finished product film is put into the curing chamber that temperature is 45 DEG C, curing 48 Hour, obtain composite membrane.

The combined strength bination for measuring the composite membrane is 2.5N, and oxygen transit dose is 1.3cm³/m²·24h·1MPa。

Embodiment 5

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 80 DEG C.After temperature drops to 20 DEG C, polyethyleneimine is added, after being thoroughly mixed, is heated to 60 DEG C of heat preservations Reaction 20 hours, then drops to room temperature (20 DEG C), and nano aluminium oxide is added and ethyl alcohol is sufficiently stirred after filtering and obtains high resistant water proof Property adhesive host agent, which does not generate gelatin phenomenon in 60 days in 5 DEG C of -40 DEG C of storages, and storage stability is good.Use preceding addition Formic acid is sufficiently stirred up to high-barrier aqueous adhesive.

Compound to BOPP film and the progress of PE film using high-barrier aqueous adhesive obtained, process is as follows: compound in dry type It is main to unreel the BOPP film placed with a thickness of 18 μm on machine, high-barrier aqueous adhesive is coated in BOPP film, glue-spread is often put down 4 grams of rice.It is dried after gluing, compounding machine oven temperature is respectively 70 DEG C, 75 DEG C, 75 DEG C.Pair unreels placement with a thickness of 40 μm PE film, make its with by gluing and dry BOPP film be bonded under the action of compound hot-rolling, obtain semi-finished product film.It is multiple Closing heat roller temperature is 60 DEG C, and machine speed is 80 meters per minute.Semi-finished product film is put into the curing chamber that temperature is 60 DEG C, curing 24 is small When, obtain composite membrane.

The combined strength bination for measuring the composite membrane is 1.8N, and oxygen transit dose is 0.98cm³/m²·24h·1MPa。

Embodiment 6

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 85 DEG C.After temperature drops to 30 DEG C, polyamine epichlorohydrin resin is added, after being thoroughly mixed, heating To 45 DEG C insulation reaction 10 hours, then drop to 28 DEG C of room temperature, rare-earth stabilizer be added and hc-surfactant is sufficiently stirred, High-barrier aqueous adhesive host agent is obtained after filtering, which does not generate gelatin phenomenon for 60 days in 5 DEG C of -40 DEG C of storages, save steady It is qualitative good.It is sufficiently stirred using preceding addition isocyanates up to high-barrier aqueous adhesive.

Compound to BOPP film and the progress of PE film using high-barrier aqueous adhesive obtained, process is as follows: compound in dry type It is main to unreel the BOPP film placed with a thickness of 20 μm on machine, high-barrier aqueous adhesive is coated in BOPP film, glue-spread is often put down 8 grams of rice.It is dried after gluing, compounding machine oven temperature is respectively 75 DEG C, 75 DEG C, 75 DEG C.Pair unreels taking and placing and sets with a thickness of 40 μ The PE film of m is bonded it under the action of compound hot-rolling with by gluing and dry BOPP film, obtains semi-finished product film. Compound heat roller temperature is 60 DEG C, and machine speed is 100 meters per minute.Semi-finished product film is put into the curing chamber that temperature is 60 DEG C, curing 48 hours.

The combined strength bination for measuring the composite membrane is 3N, and oxygen transit dose is 1.1cm³/m²·24h·1MPa。

Embodiment 7

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 80 DEG C.After temperature drops to 20 DEG C, Polyurethane is added, after being thoroughly mixed, is heated to 20 DEG C of insulation reactions 2 hours, 15 DEG C of room temperature are then dropped to, rare-earth stabilizer is added, hc-surfactant (the two ratio is 1:0.5) sufficiently stirs It mixes, high-barrier aqueous adhesive host agent is obtained after filtering, which stores at 20 DEG C and do not generate within 60 days gelatin phenomenon, save and stablize Property is good.It is sufficiently stirred using preceding addition oxazoline quasi polymer up to high-barrier aqueous adhesive.

High-barrier aqueous adhesive obtained is applied on PE film using coating machine, 1 gram of every square metre of glue-spread, later It is dried, coating machine oven temperature is respectively 60 DEG C, 65 DEG C, 70 DEG C, and machine speed is 90 meters per minute.In solvent-free composite machine On, using solventless adhesive to BOPA film and compound, the curing for being later 45 DEG C in temperature by gluing and dry PE film Indoor curing 24 hours, obtains composite membrane.

The combined strength bination for measuring the composite membrane is 3N, and oxygen transit dose is 0.2cm³/m²·24h·1MPa。

Embodiment 8

According to following proportions, polyvinyl alcohol -1799 and water are added in heatable reaction vessel, and added under stiring Heat is completely dissolved to 80 DEG C.After temperature drops to 20 DEG C, polyester resin is added, after being thoroughly mixed, it is anti-to be heated to 15 DEG C of heat preservations It answers 4 hours, then drops to 15 DEG C of room temperature, rare-earth stabilizer is added and hc-surfactant is sufficiently stirred, height is obtained after filtering Aqueous adhesive host agent is obstructed, which stores 60 days at 15 DEG C and do not generate gelatin phenomenon, and storage stability is good.Added using preceding Enter maleic anhydride to be sufficiently stirred up to high-barrier aqueous adhesive.

High-barrier aqueous adhesive obtained is applied on CPP film using coating machine, 1 gram of every square metre of glue-spread, it After be dried, coating machine oven temperature is respectively 60 DEG C, 65 DEG C, 70 DEG C, and machine speed is 90 meters per minute.In dry compound machine On, it is compound to BOPA film and process gluing and dry CPP film progress using solvent borne polyurethane adhesive, be in temperature later Curing 24 hours, obtain composite membrane in 45 DEG C of curing chamber.

Although a specific embodiment of the invention has obtained detailed description, those skilled in the art will appreciate that root According to all introductions having disclosed, details can be carry out various modifications and be changed, and these change in guarantor of the invention Within the scope of shield.Full scope of the invention is given by the appended claims and any equivalents thereof.

Claims

1. a kind of aqueous adhesive, it includes:

(1) barrier resin of 1%-30%；

(2) the pre-polymerization agent of 0.1%-20%；

(3) crosslinking and curing agent of 0.01%-20%；

(4) nano-inorganic substance of 0%-5%；

(5) heat stabilizer and/or light stabilizer of 0%-2%；

(6) the levelling tackifier of 0%-10%；

(7) surfactant of 0%-2%；With

(8) water of 11%-98.89%；

Wherein, each weight percent is the total weight based on the aqueous adhesive；

Preferably, the barrier resin is selected from: polyvinyl alcohol, polyvinylpyrrolidone and its mixture；

Preferably, the pre-polymerization agent is selected from: epoxy resin, saturated polyester, ethylene acrylic acid polymer, gathers polyurethane Ester resin, polyethyleneimine, urea, melamine, melamine resin, polyamine epichlorohydrin resin, ammonia-epoxychloropropane tree Rouge, water soluble alkyd resin open Pu Shi resin and any combination thereof；

Preferably, the crosslinking and curing agent is selected from: aliphatic carboxylic acid and its derivative (such as citric acid, formic acid, acetic acid, propylene Acid, maleic acid, sorbic acid, itaconic acid, acetic anhydride, maleic anhydride), aliphatic aldehyde (such as formaldehyde, acetaldehyde, glyoxal, first Acetal, paraformaldehyde, methacrylaldehyde, citral, valeral), oxazoline quasi polymer, isocyanates, triallyl isocyanurate And any combination thereof；

Preferably, the nano-inorganic substance is selected from: nano silicon oxide, nano-titanium oxide, nano zine oxide, is received nano aluminium oxide Rice silver oxide, graphene, nano montmorillonite, nano talc, nanometer calcium carbonate, nano clay and any combination thereof；

Preferably, the heat stabilizer and light stabilizer are independently selected from inorganic lead salt and organic lead-salt heat stabilizer, metallic soap Stablize with metal salt stabilizers, organic tin stabilizer, organic antimony stabilizer, rare-earth stabilizer, stearic acid, salicylic acid esters light Agent, benzoate light stabilizer, cyanoacrylate light stabilizer, benzophenone light stabilizer, hindered amines light are steady Determine agent, zinc class photomask agent class and its mixture and any combination thereof；

Preferably, the levelling tackifier are selected from: ethyl alcohol, methanol, isopropanol, butanol, glycol ether, propylene glycol, vinyl Pyrrolidones, polyalcohol, cellulose, chitosan, chitin, acrylamide, caprolactam and any combination thereof；

Preferably, it is living to be selected from alkyl phenol polyoxyethylene ether, dodecyldimethyl ammonium oxide, fluorocarbon surface for the surfactant Property agent, hc-surfactant, alkylbenzene sulfonate and any combination thereof；

It optionally, also include antioxidant, defoaming agent or colorant in the aqueous adhesive.

2. the aqueous adhesive of claim 1, it includes the barrier resin of: 1%-30%, 0.1%-20% pre-polymerization agent, The crosslinking and curing agent of 0.01%-20% and the water of 11%-98.89%；

Or comprising: the barrier resin of 1%-30%, the pre-polymerization agent of 0.1%-20%, 0.01%-20% crosslinking and curing agent, Nano-inorganic substance, the levelling tackifier of 0%-10% and the water of 11%-98.89% of 0%-5%；

Or comprising: the barrier resin of 1%-30%, the pre-polymerization agent of 0.1%-20%, 0.01%-20% crosslinking and curing agent, The heat stabilizer and/or light stabilizer of 0%-2%, the surfactant of 0%-2% and the water of 11%-98.89%.

3. the aqueous adhesive of claims 1 or 2, with one or more of following characteristics:

(1) barrier resin is selected from: the mixture of polyvinyl alcohol, polyvinyl alcohol and polyvinylpyrrolidone；

(2) the pre-polymerization agent is selected from: epoxy resin, melamine resin, saturated polyester, polyurethane, melamine, polyethyleneimine, Polyamine epichlorohydrin resin, polyester resin and any combination thereof；

(3) crosslinking and curing agent is selected from: citric acid, glyoxal, oxazoline quasi polymer, formaldehyde, formic acid, isocyanates, horse Come acid anhydrides and any combination thereof；

(4) nano-inorganic substance is nano aluminium oxide；

(5) heat stabilizer or light stabilizer are rare-earth stabilizer；

(6) the levelling tackifier are ethyl alcohol；

(7) surfactant is hc-surfactant.

4. a kind of composite membrane, it includes the bonding barrier layers that the aqueous adhesive by any one of claim 1-3 is formed；

Preferably, the composite membrane successively includes first base material layer, the bonding barrier layer and the second substrate layer, first base Material layer is mainly made of polymer or paper, and second substrate layer is mainly made of polymer or paper；

Preferably, at least one of the first base material layer and the second substrate layer are mainly made of polymer；

Preferably, the polymer in the polymer and second substrate layer in the first base material layer is independently selected from poly- second Alkene, polypropylene, polyamide, polyethylene terephthalate and polystyrene；

Preferably, it is described bonding barrier layer with a thickness of 2 μm -6 μm；

Preferably, the overall thickness of the composite membrane is 30 μm -150 μm；

Preferably, the combined strength bination of the composite membrane is 1.5N-3N；

Preferably, the oxygen transit dose of the composite membrane is 0.2-2.5cm³/m²·24h·1MPa。

5. the composite membrane of claim 4 is packaging film, the first base material layer is protective layer, and second substrate layer is close Sealing；

Preferably, the protective layer is mainly made of polyamide, polypropylene or polyethylene terephthalate.

Preferably, the sealant is mainly made of polyethylene or polypropylene.

Preferably, the composite membrane also includes other layers, such as printing layer, additional adhesive layer or additional barrier layer.

6. the step of method for preparing composite membrane, the method includes the aqueous adhesive using any one of claim 1-3；

Preferably, the method is that dry type is compound；

Preferably, the method comprises the steps of:

Step 3: the first base material after coating is heated；

Step 4: under the conditions of being heated and pressurizeed, being bonded the second substrate with the first base material handled through step 3, obtain half Finished product；

Step 5: the semi-finished product that step 4 obtains are cured；

Preferably, the first base material and the second substrate are each independently selected from polymer film and paper；

Preferably, at least one of first base material and the second substrate are polymer films；

Preferably, the polymer film is selected from polyethylene film, polypropylene screen, PA membrane, polyethylene terephthalate film And polystyrene film；

Preferably, the first base material is from PA membrane, polypropylene screen, polyethylene terephthalate film；

Preferably, second substrate is selected from: polyethylene film, polypropylene screen；

Preferably, the first base material with a thickness of 10 μm -250 μm；

Preferably, second substrate with a thickness of 10 μm -250 μm；

Preferably, the first base material and the second substrate are respectively provided with 38 dynes or more of surface tension coefficient；

Optionally, between step 3 and step 4 further include: be coated with other gluing on through step 3 treated first base material Agent.

7. method for claim 6 has one or more of following characteristics:

(1) in step 2, aqueous adhesive is coated in first base material with 0.3 gram -8 grams of every square meter of amount；

(2) in step 3, three sections of progress of heating point, temperature is followed successively by 60 DEG C -75 DEG C, 65 DEG C -75 DEG C, 70 DEG C -85 DEG C, Huo Zhefen Four sections of progress, temperature are followed successively by 60 DEG C -70 DEG C, 70 DEG C -75 DEG C, 75 DEG C -80 DEG C, 75 DEG C -85 DEG C；

(3) temperature heated in step 4 is 50 DEG C -65 DEG C；

(4) in step 5, the temperature of curing is 40-80 DEG C；

(5) in step 5, the time of curing is 12-72 hours.

8. the method for preparing the aqueous adhesive of any one of claim 1-3, comprising the following steps:

Step 3: pre-polymerization agent being mixed with semi-finished product, optionally, to nanometer is added in the mixture of pre-polymerization agent and semi-finished product Inorganic matter, heat stabilizer, light stabilizer, levelling tackifier, surfactant or any combination thereof, obtain aqueous adhesive master Agent；

9. the purposes that the aqueous adhesive of any one of claim 1-3 is used to prepare composite membrane.

10. the composite membrane of claim 4 or 5 is used for the purposes packed to article.

11. a kind of packaging, the composite membrane containing claim 4 or 5.