WO2023010602A1 - 一种高阻隔复合膜及其制备方法 - Google Patents

一种高阻隔复合膜及其制备方法 Download PDF

Info

Publication number
WO2023010602A1
WO2023010602A1 PCT/CN2021/112042 CN2021112042W WO2023010602A1 WO 2023010602 A1 WO2023010602 A1 WO 2023010602A1 CN 2021112042 W CN2021112042 W CN 2021112042W WO 2023010602 A1 WO2023010602 A1 WO 2023010602A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite film
barrier composite
monomer
layer
adhesive
Prior art date
Application number
PCT/CN2021/112042
Other languages
English (en)
French (fr)
Inventor
王恩飞
朱清梅
袁业兴
Original Assignee
海南赛诺实业有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 海南赛诺实业有限公司 filed Critical 海南赛诺实业有限公司
Publication of WO2023010602A1 publication Critical patent/WO2023010602A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/4865—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding containing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the invention belongs to the technical field of polymer materials, and in particular relates to a high-barrier composite film and a preparation method thereof.
  • the Chinese patent with the publication number CN203077750U discloses a coating composite film suitable for seasoning sauce packaging.
  • the method is to first coat a high-barrier PVDC coating on a PET substrate, then apply an adhesive on the coating and then follow it.
  • PE film is compounded into bags to meet the performance requirements of food packaging.
  • the PVDC coating film not only cannot be recycled and reused, but also the PE film compounded with it cannot be recycled and reused; moreover, when the waste is incinerated, it will also produce hydrogen chloride, dioxin, etc., which are toxic to the human body and the surrounding environment. hazardous substances.
  • countries such as Europe and the United States have replaced PVDC coatings with other environmentally friendly materials.
  • the Chinese patent with the publication number CN103264559A discloses a composite film for betel nut packaging and a preparation method thereof.
  • the method is to first coat an environmentally friendly high-barrier polyvinyl alcohol coating on the BOPP film, and then use the adhesive and the PE film Composite bags.
  • the packaging material of this structure can be completely burned or recycled and re-granulated after use; the production process is cumbersome, and both a coating machine and a compound machine are required, and a large amount of organic solvents are required for the coating of high-barrier coatings Make primer. Therefore, if the coating process can be saved, the production efficiency will be greatly improved and the production cost will be reduced.
  • the object of the present invention is to provide a high-barrier composite film and a preparation method thereof.
  • the high-barrier composite film provided by the present invention has better barrier properties.
  • the invention provides a high barrier composite film, comprising:
  • the adhesive layer includes:
  • the modifier is selected from one or more of montmorillonite and kaolin.
  • the thickness of the BOPE layer is 30-50 microns;
  • the thickness of the LDPE layer is 40-60 microns.
  • the hydrophilic monomer is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate and N-methylol acrylamide.
  • the functional monomer is selected from one or more of methacrylic acid and lauryl acrylate.
  • the crosslinking monomer is selected from one or more of aziridine and diisocyanate.
  • the emulsifier is selected from one or more of sodium secondary alkanesulfonate, sodium dodecylsulfonate and sodium dodecylbenzenesulfonate.
  • the initiator is selected from one or more of tert-butyl hydroperoxide and potassium persulfate.
  • the neutralizing agent is selected from one or more of triethylamine and ammonia water.
  • the present invention provides a method for preparing the high-barrier composite film described in the above technical solution, comprising:
  • Corona treatment is performed on one side of the BOPE substrate to obtain a corona surface
  • the adhesive layer and the LDPE film are hot-pressed to obtain a high-barrier composite layer.
  • the preparation method of described adhesive comprises:
  • the functional monomer, cross-linking monomer and emulsifier are first mixed to obtain pre-emulsified monomer;
  • the emulsion, the remaining pre-emulsified monomer and the remaining initiator solution are mixed for the third time and then kept warm to obtain a mixed solution;
  • the mixed liquid, the neutralizing agent and the modifying agent are mixed for the fourth time to obtain the adhesive.
  • the high-barrier water-based composite adhesive provided by the present invention is a one-component adhesive with strong adhesion, and the manufactured high-barrier composite film has excellent performance;
  • the lamellar structure precipitates on the surface of the coating, which promotes better barrier performance;
  • the preparation method provided by the invention has simple process, mild conditions, and is easy to control. After the emulsion is prepared, only one composite process is needed to achieve the traditional coating composite film The effect;
  • the inner/outer layer of the high barrier composite film provided by the present invention is made of polyethylene, and the packaging waste after use is conducive to recycling and reuse, so as to achieve the recycling of resources.
  • Fig. 1 is a schematic structural view of a high barrier composite film provided by an embodiment of the present invention.
  • the schematic diagram of the structure of the high-barrier composite film provided by the embodiment of the present invention is shown in Figure 1.
  • the present invention provides a high-barrier composite film, including:
  • An adhesive layer 2 disposed between the BOPE layer and the LDPE layer.
  • the thickness of the BOPE (biaxially oriented polyethylene film) layer is preferably 30-50 microns, more preferably 35-45 microns, most preferably 40 microns.
  • the thickness of the LDPE (low density polyethylene) layer is preferably 40-60 microns, more preferably 45-55 microns, most preferably 50 microns.
  • the thickness of the adhesive layer is preferably 3-5 microns, more preferably 3.5-4.5 microns, most preferably 4 microns.
  • the adhesive layer includes:
  • the mass content of the soft water is preferably 60-65%, more preferably 62-63%.
  • the present invention has no special limitation on the soft water, and the soft water well known to those skilled in the art can be used.
  • the mass content of the hydrophilic monomer is preferably 12-16%, more preferably 14%.
  • the hydrophilic monomer is preferably selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate and N-methylol acrylamide.
  • the mass content of the functional monomer is preferably 10-13%, more preferably 11-12%.
  • the functional monomer is preferably selected from one or more of methacrylic acid and lauryl acrylate.
  • the mass content of the crosslinking monomer is preferably 4-6%, more preferably 5%.
  • the crosslinking monomer is preferably selected from one or more of aziridine and diisocyanate.
  • the mass content of the emulsifier is preferably 1-3%, more preferably 2%.
  • the emulsifier is preferably selected from one or more of sodium secondary alkanesulfonate, sodium dodecylsulfonate and sodium dodecylbenzenesulfonate.
  • the mass content of the initiator is preferably 0.5-1.5%, more preferably 0.8-1.2%, most preferably 1%.
  • the initiator is preferably selected from one or more of tert-butyl hydroperoxide and potassium persulfate.
  • the mass content of the neutralizing agent is preferably 1-2%, more preferably 1.5%.
  • the neutralizing agent is preferably one or more selected from triethylamine and ammonia water.
  • the mass content of the modifier is preferably 1-3%, more preferably 2%.
  • the modifying agent is selected from one or more of montmorillonite and kaolin.
  • the present invention provides a method for preparing the high-barrier composite film described in the above technical solution, comprising:
  • Corona treatment is performed on one side of the BOPE substrate to obtain a corona surface
  • the adhesive layer and the LDPE film are hot-pressed to obtain a high-barrier composite layer.
  • the BOPE substrate may be a BOPE film, which is consistent with the BOPE layer described in the above technical solution, and will not be repeated here.
  • the BOPE substrate is preferably a product prepared according to the method disclosed in CN111452473A patent.
  • the corona preferably makes the surface tension of the BOPE substrate after corona be 40-45 dynes, more preferably 41-44 dynes, most preferably 42-43 dynes; Processing is preferably performed on a dry laminator.
  • the coating is preferably performed by a gravure coating roll; the coating amount of the coating is preferably 3-5 g/m 2 , more preferably 4 g/m 2 .
  • the preparation method of the adhesive preferably includes:
  • the functional monomer, cross-linking monomer and emulsifier are first mixed to obtain pre-emulsified monomer;
  • the emulsion, the remaining pre-emulsified monomer and the remaining initiator solution are mixed for the third time and then kept warm to obtain a mixed solution;
  • the mixed liquid, the neutralizing agent and the modifying agent are mixed for the fourth time to obtain the adhesive.
  • composition and mass content of the soft water, hydrophilic monomers, functional monomers, crosslinking monomers, emulsifiers, initiators, neutralizers and modifiers are consistent with those described in the above-mentioned technical solutions. This will not be repeated here.
  • the first mixing is preferably carried out under stirring conditions; the stirring speed is preferably 100-150 rpm, more preferably 110-140 rpm, most preferably 120-130 rpm minutes; the first mixing time is preferably 0.5-1 hour, more preferably 0.6-0.9 hour, most preferably 0.7-0.8 hour.
  • the part of soft water is preferably 25-35% of the total mass of soft water, more preferably 28-32%, most preferably 30%.
  • the part of the pre-emulsified monomer is preferably 3-5% of the total mass of the pre-emulsified monomer, more preferably 4%.
  • the part of the initiator solution is preferably 1-3% of the total mass of the initiator solution, more preferably 2%.
  • the reaction is preferably carried out in a reactor; the condition of the reaction is preferably a sealed vacuum negative pressure; the reaction is preferably carried out under stirring, and the stirring speed is preferably 150 to 200 rpm minutes, more preferably 160-190 rpm, most preferably 170-180 rpm; the temperature of the reaction is preferably 80-85°C, more preferably 81-84°C, most preferably 82-83°C; The reaction time is preferably 0.5-1 hour, more preferably 0.6-0.9 hour, most preferably 0.7-0.8 hour.
  • the emulsion is milky white bluish emulsion.
  • the third mixing method preferably includes:
  • the remaining pre-emulsified monomer and remaining initiator solution were added dropwise to the emulsion.
  • the time for the dropping is preferably 3-5 hours, more preferably 4 hours.
  • the temperature of the heat preservation is preferably 65-75°C, more preferably 68-72°C, most preferably 70°C;
  • the time of heat preservation is preferably 0.5-1 hour, more preferably 0.6-0.9 hours, most preferably Preferably it is 0.7 to 0.8 hours.
  • the fourth mixing is preferably carried out under the condition of stirring, and the time for the fourth mixing is preferably 0.5-1 hour, more preferably 0.6-0.9 hour, most preferably 0.7-0.8 hour.
  • the drying temperature is preferably 60-80°C, more preferably 65-75°C, most preferably 70°C; the drying is preferably carried out in an oven; the drying method is preferably far-infrared or Hot air dry.
  • the LDPE film is consistent with the LDPE layer described in the above technical solution, and will not be repeated here.
  • the LDPE film is preferably a product prepared according to the method disclosed in CN111040363A patent.
  • the hot pressing is preferably carried out with a composite pressing roller; the temperature of the hot pressing is preferably 50-60°C, more preferably 52-58°C, most preferably 54-56°C; The pressure is preferably 0.1 to 0.3 MPa, more preferably 0.2 MPa.
  • the high-barrier composite film is preferably obtained by winding after the hot pressing.
  • the high-barrier water-based composite adhesive provided by the present invention is a one-component adhesive with strong adhesion, and the manufactured high-barrier composite film has excellent performance;
  • the lamellar structure precipitates on the surface of the coating, which promotes better barrier performance;
  • the preparation method provided by the invention has simple process, mild conditions, and is easy to control. After the emulsion is prepared, only one composite process is needed to achieve the traditional coating composite film The effect;
  • the inner/outer layer of the high barrier composite film provided by the present invention is made of polyethylene, and the packaging waste after use is conducive to recycling and reuse, so as to achieve the recycling of resources.
  • the BOPE substrate used in the following examples of the present invention is prepared according to the preparation method disclosed in Chinese Patent CN 110450490A Example 3, and the puncture resistance is 6-8N/mm; the LDPE film is prepared according to the preparation disclosed in Chinese Patent CN111040363A Example 1 Method prepared, the tensile strength of 20 ⁇ 25MPa.
  • the initiator of 0.5wt% is dissolved with part soft water (accounting for 30wt% of soft water total amount) and is made into initiator solution;
  • corona treatment is performed on the coated side of the 30 micron BOPE substrate with a puncture resistance of 6N/mm, so that the surface tension reaches 45 dynes; Coated on the corona surface of BOPE film, the coating amount is 5g/m 2 , the thickness is 5 microns; use far infrared or hot air to dry, the oven temperature is set at 80°C, after drying in the oven, use a composite pressure roller The adhesive layer on the BOPE is hot-pressed with a 60-micron LDPE film with a tensile strength of 25MPa, the hot-pressing temperature is 50°C, and the pressure is 0.3MPa; a new type of high-barrier composite film is obtained after winding.
  • the initiator of 0.3wt% is dissolved with part soft water (accounting for 30% of soft water total amount) and is made into initiator solution;
  • corona treatment is performed on the side of the BOPE substrate with a puncture resistance of 40 microns and a puncture strength of 7N/mm to make the surface tension reach 43 dynes; Coated on the corona surface of BOPE film, the coating amount is 4g/m 2 , the thickness is 4 microns; use far infrared or hot air to dry, the oven temperature is set at 70°C, after drying in the oven, use a composite pressure roller The adhesive layer on the BOPE is hot-pressed with a 50-micron LDPE film with a tensile strength of 23 MPa. The hot-pressing temperature is 55 ° C and the pressure is 0.2 MPa; after winding, a new type of high-barrier composite film is prepared.
  • corona treatment is performed on the side of the 50 micron BOPE substrate with a puncture resistance of 8N/mm to make the surface tension reach 40 dynes; the above-mentioned high barrier adhesive is coated with a gravure coating roller Coated on the corona surface of BOPE film, the coating amount is 3g/m 2 , the thickness is 3 microns; use far infrared or hot air to dry, the oven temperature is set at 60°C, after drying in the oven, use a composite pressure roller The adhesive layer on the BOPE was hot-pressed with a 40-micron LDPE film with a tensile strength of 20 MPa at a temperature of 60°C and a pressure of 0.1 MPa; a new type of high-barrier composite film was prepared after winding.
  • Peel strength, oxygen transmission rate and water vapor transmission rate detection are carried out to the composite film prepared by the embodiment of the present invention and comparative example, detection method and detection result are as follows:
  • the high-barrier water-based composite adhesive provided by the present invention is a one-component adhesive with strong adhesion, and the manufactured high-barrier composite film has excellent performance;
  • the lamellar structure precipitates on the surface of the coating, which promotes better barrier performance;
  • the preparation method provided by the invention has simple process, mild conditions, and is easy to control. After the emulsion is prepared, only one composite process is needed to achieve the traditional coating composite film The effect;
  • the inner/outer layer of the high barrier composite film provided by the present invention is made of polyethylene, and the packaging waste after use is conducive to recycling and reuse, so as to achieve the recycling of resources.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

一种高阻隔复合膜及其制备方法，高阻隔复合膜包括：BOPE层；LDPE层；设置在所述BOPE层和LDPE层之间的胶黏剂层。所述胶黏剂层包括：55～70wt％的软水；10～18wt％的亲水单体；8～15wt％的功能单体；2～8wt％的交联单体；0.5～4wt％的乳化剂；0.3～2wt％的引发剂；0.5～3wt％的中和剂；0.8～4wt％的改性剂。该胶黏剂为单组份粘合剂，粘接力强，制造的高阻隔复合膜性能优异。由于在乳液制备中加入改性剂，涂布烘干后以微观片状结构析出在涂层表面，促进了更好的阻隔性能。

Description

一种高阻隔复合膜及其制备方法
本申请要求于2021年08月03日提交中国专利局、申请号为202110885312.5、发明名称为“一种高阻隔复合膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于高分子材料技术领域，尤其涉及一种高阻隔复合膜及其制备方法。
背景技术
目前市场上的食品包装，绝大部分使用高阻隔的涂布膜经胶黏剂与PE或者CPP复合制成袋子进行包装，以提供封口、阻隔氧气和水蒸汽等性能，达到延长食品保持期。因此，高阻隔复合膜占据绝大部分食品包装市场。
公开号为CN203077750U的中国专利公开了一种适合调味酱包装的涂布复合膜，其方法为先在PET基材上涂布高阻隔的PVDC涂层，然后在涂层上涂胶黏剂再跟PE膜复合制成袋子，以达到食品包装性能要求。但是，PVDC涂布膜不仅不能回收再生利用，而且还会使与其复合的PE膜也不能回收再利用；并且，废弃物在焚烧时还会产生氯化氢、二恶英等对人体和周围环境有毒、有害的物质。目前欧美等国家已经通过其它环保材料替代PVDC涂层。
随着社会大众对绿色健康需求的日益高涨及国家环保法规的日益严格，包装材料的环保化、无毒化、性能多元化将是必然趋势。如公开号为CN103264559A的中国专利公开了一种槟榔包装复合膜及其制备方法，其方法为先在BOPP膜上涂布环保的高阻隔聚乙烯醇涂层，然后再利用胶黏剂跟PE膜复合制袋。虽然此结构的包装材料使用后可以完全燃烧或者回收重新造粒；但是生产过程繁琐，既要配备涂布机，又要配备复合机，而且涂布高阻隔涂料过程还需要用到大量的有机溶剂做底胶。因此如果能节省掉涂布工序，将很大程度上提高生产效率和降低生产成本。
综上，开发出一款食品包装的新型高阻隔复合膜成为本领域技术人员亟待解决的技术问题。
发明内容
有鉴于此，本发明的目的在于提供一种高阻隔复合膜及其制备方法，本发明提供的高阻隔复合膜具有较好的阻隔性能。
本发明提供了一种高阻隔复合膜，包括：
BOPE层；
LDPE层；
设置在所述BOPE层和LDPE层之间的胶黏剂层；
所述胶黏剂层包括：
55～70wt％的软水；
10～18wt％的亲水单体；
8～15wt％的功能单体；
2～8wt％的交联单体；
0.5～4wt％的乳化剂；
0.3～2wt％的引发剂；
0.5～3wt％的中和剂；
0.8～4wt％的改性剂；所述改性剂选自蒙脱土和高岭土中的一种或几种。
优选的，所述BOPE层的厚度为30～50微米；
所述LDPE层的厚度为40～60微米。
优选的，所述亲水单体选自丙烯酸羟乙酯、丙烯酸羟丙酯和N-羟甲基丙烯酰胺中的一种或几种。
优选的，所述功能单体选自甲基丙烯酸和丙烯酸月桂脂中的一种或几种。
优选的，所述交联单体选自氮丙啶和二异氰酸酯中的一种或几种。
优选的，所述乳化剂选自仲链烷基磺酸钠、十二烷基磺酸钠和十二烷基苯磺酸钠中的一种或几种。
优选的，所述引发剂选自叔丁基过氧化氢和过硫酸钾的一种或几种。
优选的，所述中和剂选自三乙胺和氨水中的一种或几种。
本发明提供了一种上述技术方案所述的高阻隔复合膜的制备方法，包括：
将BOPE基材的一面进行电晕处理，得到电晕面；
将胶黏剂涂布在所述电晕面上后干燥，得到胶黏剂层；
将所述胶黏剂层和LDPE薄膜进行热压，得到高阻隔复合层。
优选的，所述胶黏剂的制备方法包括：
将功能单体、交联单体和乳化剂进行第一混合，得到预乳化单体；
将引发剂和部分软水进行第二混合，得到引发剂溶液；
将剩余的软水、亲水单体、部分预乳化单体和部分引发剂溶液进行反应，得到乳液；
将乳液、剩余的预乳化单体和剩余的引发剂溶液进行第三混合后保温，得到混合液；
将所述混合液、中和剂和改性剂进行第四混合，得到胶黏剂。
本发明提供的高阻隔水性复合胶黏剂为单组份粘合剂，粘接力强，制造的高阻隔复合膜性能优异；由于在乳液制备中加入改性剂，涂布烘干后以微观片状结构析出在涂层表面，促进了更好的阻隔性能；本发明提供的制备方法工艺简单，条件温和、易控，乳液制备完成后，只需要一道复合工序就能达到传统涂布复合膜的效果；本发明提供的高阻隔复合膜内/外层都是聚乙烯材质，使用后的包装废弃物有利于回收再利用，达到资源循环使用。
附图说明
图1为本发明实施例提供的高阻隔复合膜的结构示意图。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员经改进或润饰的所有其它实例，都属于本发明保护的范围。应理解，本发明实施例仅用于说明本发明的技术效果，而非用于限制本发明的保护范围。实施例中，所用方法如无特别说明，均为常规方法。
本发明实施例提供的高阻隔复合膜的结构示意图如图1所示，本发明提供了一种高阻隔复合膜，包括：
BOPE层1；
LDPE层3；
设置在所述BOPE层和LDPE层之间的胶黏剂层2。
在本发明中，所述BOPE(双向拉伸聚乙烯薄膜)层的厚度优选为30～50微米，更优选为35～45微米，最优选为40微米。
在本发明中，所述LDPE(低密度聚乙烯)层的厚度优选为40～60微米，更优选为45～55微米，最优选为50微米。
在本发明中，所述胶黏剂层的厚度优选为3～5微米，更优选为3.5～4.5微米，最优选为4微米。
在本发明中，所述胶黏剂层包括：
55～70wt％的软水；
10～18wt％的亲水单体；
8～15wt％的功能单体；
2～8wt％的交联单体；
0.5～4wt％的乳化剂；
0.3～2wt％的引发剂；
0.5～3wt％的中和剂；
0.8～4wt％的改性剂。
在本发明中，所述软水的质量含量优选为60～65％，更优选为62～63％。本发明对所述软水没有特殊的限制，采用本领域技技术人员熟知的软水即可。
在本发明中，所述亲水单体的质量含量优选为12～16％，更优选为14％。
在本发明中，所述亲水单体优选选自丙烯酸羟乙酯、丙烯酸羟丙酯和N-羟甲基丙烯酰胺中的一种或几种。
在本发明中，所述功能单体的质量含量优选为10～13％，更优选为11～12％。
在本发明中，所述功能单体优选选自甲基丙烯酸和丙烯酸月桂脂中的一种或几种。
在本发明中，所述交联单体的质量含量优选为4～6％，更优选为5％。
在本发明中，所述交联单体优选选自氮丙啶和二异氰酸酯中的一种或几种。
在本发明中，所述乳化剂的质量含量优选为1～3％，更优选为2％。
在本发明中，所述乳化剂优选选自仲链烷基磺酸钠、十二烷基磺酸钠和十 二烷基苯磺酸钠中的一种或几种。
在本发明中，所述引发剂的质量含量优选为0.5～1.5％，更优选为0.8～1.2％，最优选为1％。
在本发明中，所述引发剂优选选自叔丁基过氧化氢和过硫酸钾的一种或几种。
在本发明中，所述中和剂的质量含量优选为1～2％，更优选为1.5％。
在本发明中，所述中和剂优选选自三乙胺和氨水中的一种或几种。
在本发明中，所述改性剂的质量含量优选为1～3％，更优选为2％。
在本发明中，所述改性剂选自蒙脱土和高岭土中的一种或几种。
本发明提供了一种上述技术方案所述的高阻隔复合膜的制备方法，包括：
将BOPE基材的一面进行电晕处理，得到电晕面；
将胶黏剂涂布在所述电晕面上后干燥，得到胶黏剂层；
将所述胶黏剂层和LDPE薄膜进行热压，得到高阻隔复合层。
在本发明中，所述BOPE基材可以为BOPE薄膜，与上述技术方案所述BOPE层一致，在此不再赘述。在本发明中，所述BOPE基材优选为按照CN111452473A专利公开的方法制备得到的产品。
在本发明中，所述电晕优选使电晕后的BOPE基材的表面张力为40～45达因，更优选为41～44达因，最优选为42～43达因；所述电晕处理优选在干式复合机上进行。
在本发明中，所述涂布优选采用凹版涂布辊进行涂布；所述涂布的涂布量优选为3～5g/m 2，更优选为4g/m 2。
在本发明中，所述胶黏剂的制备方法优选包括：
将功能单体、交联单体和乳化剂进行第一混合，得到预乳化单体；
将引发剂和部分软水进行第二混合，得到引发剂溶液；
将剩余的软水、亲水单体、部分预乳化单体和部分引发剂溶液进行反应，得到乳液；
将乳液、剩余的预乳化单体和剩余的引发剂溶液进行第三混合后保温，得到混合液；
将所述混合液、中和剂和改性剂进行第四混合，得到胶黏剂。
在本发明中，所述软水、亲水单体、功能单体、交联单体、乳化剂、引发剂、中和剂和改性剂的成分以及质量含量与上述技术方案所述一致，在此不再赘述。
在本发明中，所述第一混合优选在搅拌的条件下进行；所述搅拌的速度优选为100～150转/分，更优选为110～140转/分，最优选为120～130转/分；所述第一混合的时间优选为0.5～1小时，更优选为0.6～0.9小时，最优选为0.7～0.8小时。
在本发明中，所述部分软水优选为软水总质量的25～35％，更优选为28～32％，最优选为30％。
在本发明中，所述部分预乳化单体优选为预乳化单体总质量的3～5％，更优选为4％。
在本发明中，所述部分引发剂溶液优选为引发剂溶液总质量的1～3％，更优选为2％。
在本发明中，所述反应优选在反应釜中进行；所述反应的条件优选为密封真空负压；所述反应优选在搅拌的条件下进行，所述搅拌的速度优选为150～200转/分，更优选为160～190转/分，最优选为170～180转/分；所述反应的温度优选为80～85℃，更优选为81～84℃，最优选为82～83℃；所述反应的时间优选为0.5～1小时，更优选为0.6～0.9小时，最优选为0.7～0.8小时。在本发明中，所述乳液为乳白色泛蓝光乳液。
在本发明中，所述第三混合的方法优选包括：
将剩余的预乳化单体和剩余的引发剂溶液滴加到乳液中。
在本发明中，优选通过计量泵分别连续滴加剩余的预乳化单体和剩余的引发剂溶液；所述滴加的时间优选为3～5小时，更优选为4小时。
在本发明中，所述保温的温度优选为65～75℃，更优选为68～72℃，最优选为70℃；保温的时间优选为0.5～1小时，更优选为0.6～0.9小时，最优选为0.7～0.8小时。
在本发明中，所述第四混合优选在搅拌的条件下进行，所述第四混合的时间优选为0.5～1小时，更优选为0.6～0.9小时，最优选为0.7～0.8小时。
在本发明中，所述第四混合完成后优选还包括：
将得到的混合物静置待冷却后，得到高阻隔水性复合胶黏剂。
在本发明中，所述干燥的温度优选为60～80℃，更优选为65～75℃，最优选为70℃；所述干燥优选在烘箱中进行；所述干燥的方法优选为远红外或热空气干燥。
在本发明中，所述LDPE薄膜与上述技术方案所述LDPE层一致，在此不再赘述。在本发明中，所述LDPE薄膜优选为按照CN111040363A专利公开的方法制备得到的产品。
在本发明中，所述热压优选采用复合压辊进行；所述热压的温度优选为50～60℃，更优选为52～58℃，最优选为54～56℃；所述热压的压力优选为0.1～0.3MPa，更优选为0.2MPa。
在本发明中，所述热压后优选经收卷得到高阻隔复合膜。
本发明提供的高阻隔水性复合胶黏剂为单组份粘合剂，粘接力强，制造的高阻隔复合膜性能优异；由于在乳液制备中加入改性剂，涂布烘干后以微观片状结构析出在涂层表面，促进了更好的阻隔性能；本发明提供的制备方法工艺简单，条件温和、易控，乳液制备完成后，只需要一道复合工序就能达到传统涂布复合膜的效果；本发明提供的高阻隔复合膜内/外层都是聚乙烯材质，使用后的包装废弃物有利于回收再利用，达到资源循环使用。
本发明以下实施例中所采用的BOPE基材按照中国专利CN 110450490A实施例3中公开的制备方法制得，抗穿刺强度6～8N/mm；LDPE薄膜按照中国专利CN111040363A实施例1中公开的制备方法制得，拉伸强度为20～25MPa。
比较例1
按照专利CN110861380A中实施例1的方法制备得到的产品。
实施例1
1、高阻隔复合胶原料重量配比及具体种类限定：
Figure PCTCN2021112042-appb-000001
Figure PCTCN2021112042-appb-000002
2、高阻隔复合胶的制备：
(1)将14wt％的功能单体、8wt％的交联单体、3wt％的乳化剂混合搅拌0.5小时，搅拌速度控制150转/分钟得到预乳化单体；
(2)将0.5wt％的引发剂用部分软水(占软水总量的30wt％)溶解配成引发剂溶液；
(3)将剩余的软水、18wt％的亲水单体、3wt％的部分预乳化单体、1wt％的部分引发剂溶液加入到反应釜中，密封后抽真空到-0.05MPa，搅拌速度控制在150转/分钟，升温至83℃反应约0.8小时得到乳白色泛蓝光乳液。
(4)通过计量泵分别连续加入剩余的预乳化单体、引发剂溶液，滴加时间控制为3小时。
(5)待加料完成后，继续保温67℃、0.7小时，然后加入0.5wt％的中和剂、1wt％的改性剂，充分搅拌0.5小时后，静置待冷却后即制得本发明高阻隔水性复合胶黏剂。
3、高阻隔复合膜的制造
在干式复合上机将30微米抗穿刺强度为6N/mm的BOPE基材要涂布的一面进行电晕处理，使表面张力达到45达因；使用凹版涂布辊将上述高阻隔胶黏剂涂布在BOPE膜的电晕面上，涂布量为5g/m 2，厚度为5微米；使用远红外或热空气干燥，烘箱温度设定为80℃，经烘箱干燥后，利用复合压辊将BOPE上的胶黏剂层跟60微米拉伸强度为25MPa的LDPE薄膜进行热压，热压温度为50℃，压力为0.3MPa；经收卷后得到新型高阻隔复合膜。
实施例2
1、高阻隔复合胶原料重量配比及具体种类限定：
Figure PCTCN2021112042-appb-000003
Figure PCTCN2021112042-appb-000004
2、高阻隔复合胶的制备
(1)将10wt％的功能单体、4wt％的交联单体、1.7wt％的乳化剂混合搅拌1小时，搅拌速度控制100转/分钟得到预乳化单体；
(2)将0.3wt％的引发剂用部分软水(占软水总量的30％)溶解配成引发剂溶液；
(3)将剩余的软水、12wt％的亲水单体、4wt％的部分预乳化单体、2wt％的部分引发剂溶液加入到反应釜中，密封后抽真空到-0.06MPa，搅拌速度控制在200转/分钟，升温至80℃反应约1小时得到乳白色泛蓝光乳液。
(4)通过计量泵分别连续加入剩余的预乳化单体、引发剂溶液；滴加时间控制为5小时。
(5)待加料完成后，继续保温65℃、1小时，然后加入3wt％的中和剂、4wt％的改性剂；充分搅拌0.8小时后，静置待冷却后即制得本发明高阻隔水性复合胶黏剂。
3、高阻隔复合膜的制造
在干式复合上机将40微米抗穿刺强度为7N/mm的BOPE基材要涂布的一面进行电晕处理，使表面张力达到43达因；使用凹版涂布辊将上述高阻隔胶黏剂涂布在BOPE膜的电晕面上，涂布量为4g/m 2，厚度为4微米；使用远红外或热空气干燥，烘箱温度设定为70℃，经烘箱干燥后，利用复合压辊将BOPE上的胶黏剂层跟50微米拉伸强度为23MPa的LDPE薄膜进行热压，热压温度为55℃，压力为0.2MPa；经收卷后制备得到新型高阻隔复合膜。
实施例3
1、高阻隔复合胶原料重量配比及具体种类限定：
Figure PCTCN2021112042-appb-000005
Figure PCTCN2021112042-appb-000006
2、高阻隔复合胶的制备
(1)将9wt％的功能单体、6wt％的交联单体、0.5wt％的乳化剂混合搅拌0.6小时，搅拌速度控制120转/分钟得到预乳化单体；
(2)将2wt％的引发剂用部分软水(占软水总量的30％)溶解配成引发剂溶液；
(3)将剩余的软水、11wt％的亲水单体、5wt％的部分预乳化单体、3wt％的部分引发剂溶液加入到反应釜中，密封后抽真空到-0.04MPa，搅拌速度控制在150转/分钟，升温至85℃反应约0.5小时得到乳白色泛蓝光乳液。
(4)通过计量泵分别连续加入剩余的预乳化单体、引发剂溶液；滴加时间控制为4小时。
(5)待加料完成后，继续保温75℃、0.5小时，然后加入0.7wt％的中和剂、0.8wt％的改性剂；充分搅拌1小时后，静置待冷却后得到本发明高阻隔水性复合胶黏剂。
3、高阻隔复合膜的制造
在干式复合上机将50微米抗穿刺强度为8N/mm的BOPE基材要涂布的一面进行电晕处理，使表面张力达到40达因；使用凹版涂布辊将上述高阻隔胶黏剂涂布在BOPE膜的电晕面上，涂布量为3g/m 2，厚度为3微米；使用远红外或热空气干燥，烘箱温度设定为60℃，经烘箱干燥后，利用复合压辊将BOPE上的胶黏剂层跟40微米拉伸强度为20MPa的LDPE薄膜进行热压，热压温度为60℃，压力为0.1MPa；经收卷后制备得到新型高阻隔复合膜。
性能检测
对本发明实施例和比较例制备的复合膜进行剥离强度、氧气透过率和水蒸气透过率检测，检测方法和检测结果如下：
  实施例1 实施例2 实施例3 比较例1 检测标准
剥离强度(N/15mm) 4 3 5 2.0 GB/T8808-1988
氧气透过率(cc/m 2·day) 1 3 2 114 GB/T 1038-2000
水蒸气透过率(g/m 2·day) 4 5 6 15 GB/T 1037-1998
本发明提供的高阻隔水性复合胶黏剂为单组份粘合剂，粘接力强，制造的高阻隔复合膜性能优异；由于在乳液制备中加入改性剂，涂布烘干后以微观片状结构析出在涂层表面，促进了更好的阻隔性能；本发明提供的制备方法工艺简单，条件温和、易控，乳液制备完成后，只需要一道复合工序就能达到传统涂布复合膜的效果；本发明提供的高阻隔复合膜内/外层都是聚乙烯材质，使用后的包装废弃物有利于回收再利用，达到资源循环使用。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种高阻隔复合膜，包括：
    BOPE层；
    LDPE层；
    设置在所述BOPE层和LDPE层之间的胶黏剂层；
    所述胶黏剂层包括：
    55～70wt％的软水；
    10～18wt％的亲水单体；
    8～15wt％的功能单体；
    2～8wt％的交联单体；
    0.5～4wt％的乳化剂；
    0.3～2wt％的引发剂；
    0.5～3wt％的中和剂；
    0.8～4wt％的改性剂；所述改性剂选自蒙脱土和高岭土中的一种或几种。
  2. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述BOPE层的厚度为30～50微米；
    所述LDPE层的厚度为40～60微米。
  3. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述亲水单体选自丙烯酸羟乙酯、丙烯酸羟丙酯和N-羟甲基丙烯酰胺中的一种或几种。
  4. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述功能单体选自甲基丙烯酸和丙烯酸月桂脂中的一种或几种。
  5. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述交联单体选自氮丙啶和二异氰酸酯中的一种或几种。
  6. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述乳化剂选自仲链烷基磺酸钠、十二烷基磺酸钠和十二烷基苯磺酸钠中的一种或几种。
  7. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述引发剂选自叔丁基过氧化氢和过硫酸钾的一种或几种。
  8. 根据权利要求1所述的高阻隔复合膜，其特征在于，所述中和剂选自 三乙胺和氨水中的一种或几种。
  9. 一种权利要求1所述的高阻隔复合膜的制备方法，包括：
    将BOPE基材的一面进行电晕处理，得到电晕面；
    将胶黏剂涂布在所述电晕面上后干燥，得到胶黏剂层；
    将所述胶黏剂层和LDPE薄膜进行热压，得到高阻隔复合层。
  10. 根据权利要求9所述的方法，其特征在于，所述胶黏剂的制备方法包括：
    将功能单体、交联单体和乳化剂进行第一混合，得到预乳化单体；
    将引发剂和部分软水进行第二混合，得到引发剂溶液；
    将剩余的软水、亲水单体、部分预乳化单体和部分引发剂溶液进行反应，得到乳液；
    将乳液、剩余的预乳化单体和剩余的引发剂溶液进行第三混合后保温，得到混合液；
    将所述混合液、中和剂和改性剂进行第四混合，得到胶黏剂。
PCT/CN2021/112042 2021-08-03 2021-08-11 一种高阻隔复合膜及其制备方法 WO2023010602A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110885312.5 2021-08-03
CN202110885312.5A CN113524843A (zh) 2021-08-03 2021-08-03 一种高阻隔复合膜及其制备方法

Publications (1)

Publication Number Publication Date
WO2023010602A1 true WO2023010602A1 (zh) 2023-02-09

Family

ID=78090193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/112042 WO2023010602A1 (zh) 2021-08-03 2021-08-11 一种高阻隔复合膜及其制备方法

Country Status (2)

Country Link
CN (1) CN113524843A (zh)
WO (1) WO2023010602A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114456747A (zh) * 2021-03-12 2022-05-10 海南必凯水性新材料有限公司 一种高阻隔水性复合胶黏剂及其制备方法
CN117141077A (zh) * 2023-11-01 2023-12-01 南通金丝楠膜材料有限公司 一种阻隔型聚乙烯基单一材质复合抗菌膜及制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5512338A (en) * 1991-12-23 1996-04-30 Mobil Oil Corp. Oxygen, flavor/odor, grease/oil and moisture barrier film structures
CN101580682A (zh) * 2008-05-16 2009-11-18 北京高盟燕山科技有限公司 水性复合粘合剂及其制备方法与应用
WO2011009800A1 (en) * 2009-07-21 2011-01-27 Basf Se Film-to-film laminate, made by using an aqueous polymer dispersion as adhesive agent
US20190016931A1 (en) * 2016-01-18 2019-01-17 Basf Se Use of a single-component laminating adhesive for composite film lamination
CN110861380A (zh) * 2019-11-22 2020-03-06 江阴升辉包装材料有限公司 一种单一材料复合可回收冷冻食品包装膜及其制备方法
CN111187593A (zh) * 2020-03-06 2020-05-22 上海都昱新材料科技有限公司 一种聚合物乳液胶粘剂及其制备方法和应用
CN111823683A (zh) * 2020-08-13 2020-10-27 河南银金达彩印股份有限公司 一种高阻隔复合膜及其制备方法和应用
CN113002100A (zh) * 2021-03-31 2021-06-22 海南必凯水性新材料有限公司 一种高阻隔复合膜及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358445A3 (en) * 1988-09-07 1990-11-14 Tonen Sekiyukagaku K.K. Polyethylene composite film and label
CN102876267B (zh) * 2012-09-21 2015-04-08 海南必凯水性涂料有限公司 一种双组分水性丙烯酸胶黏剂及其制备方法
CN103059784B (zh) * 2013-02-01 2014-10-08 东莞市星宇高分子材料有限公司 食品药品软包装用水性塑-塑复合胶粘剂及其制备方法
PL3317103T3 (pl) * 2015-06-30 2021-01-25 Dow Global Technologies Llc Struktury wielowarstwowe i zawierające je wyroby
CN106003938B (zh) * 2016-05-23 2018-10-02 深圳市八六三新材料技术有限责任公司 一种高阻隔性聚烯烃纳米复合薄膜及其制备方法
CN105969265A (zh) * 2016-05-26 2016-09-28 江阴市江泰高分子新材料有限公司 高性能水性压敏胶及其制备方法以及pe保护膜
CN109562865B (zh) * 2016-08-12 2021-07-30 太阳化学公司 增强阻隔的涂料
CN108003816A (zh) * 2017-11-16 2018-05-08 广东佰合新材料科技股份有限公司 一种镀铝膜复合专用水性胶水及其制备方法
CN108102025A (zh) * 2017-11-16 2018-06-01 广东佰合新材料科技股份有限公司 一种压花pe复合专用水性胶水及其制备方法
CN108544826A (zh) * 2018-05-07 2018-09-18 安徽大学 一种蒙脱土基高阻隔纳米复合薄膜及其制备方法
CN111286284A (zh) * 2020-03-30 2020-06-16 上海保立佳新材料有限公司 一种中粘保护膜乳液及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5512338A (en) * 1991-12-23 1996-04-30 Mobil Oil Corp. Oxygen, flavor/odor, grease/oil and moisture barrier film structures
CN101580682A (zh) * 2008-05-16 2009-11-18 北京高盟燕山科技有限公司 水性复合粘合剂及其制备方法与应用
WO2011009800A1 (en) * 2009-07-21 2011-01-27 Basf Se Film-to-film laminate, made by using an aqueous polymer dispersion as adhesive agent
US20190016931A1 (en) * 2016-01-18 2019-01-17 Basf Se Use of a single-component laminating adhesive for composite film lamination
CN110861380A (zh) * 2019-11-22 2020-03-06 江阴升辉包装材料有限公司 一种单一材料复合可回收冷冻食品包装膜及其制备方法
CN111187593A (zh) * 2020-03-06 2020-05-22 上海都昱新材料科技有限公司 一种聚合物乳液胶粘剂及其制备方法和应用
CN111823683A (zh) * 2020-08-13 2020-10-27 河南银金达彩印股份有限公司 一种高阻隔复合膜及其制备方法和应用
CN113002100A (zh) * 2021-03-31 2021-06-22 海南必凯水性新材料有限公司 一种高阻隔复合膜及其制备方法

Also Published As

Publication number Publication date
CN113524843A (zh) 2021-10-22

Similar Documents

Publication Publication Date Title
WO2023010602A1 (zh) 一种高阻隔复合膜及其制备方法
CN113002100B (zh) 一种高阻隔复合膜及其制备方法
EP2580254B1 (en) Multistage preparation of aqueous polymer dispersions for producing composite films
CN105189586A (zh) 混合水分散体、(聚)乙烯(甲基)丙烯酸共聚物复合胶乳乳液、混合(聚)乙烯(甲基)丙烯酸有机硅烷复合胶乳乳液和由其形成的涂料组合物
JP6131570B2 (ja) ガスバリア用コーティング液、その製造方法、ガスバリア性積層体の製造方法、包装材料の製造方法および加熱殺菌用包装材料の製造方法
CN108752514B (zh) 一种环氧改性丙烯酸乳液及其制备方法
CN108473820A (zh) 单组分层压胶粘剂用于复合膜层压的用途
US11072729B2 (en) Self-adsorbable foamed laminate sheet and composition for self-adsorbable foamed sheet
CN103554344A (zh) 透明耐水白聚丙烯酸酯乳液的合成方法
JPWO2018142997A1 (ja) 水分散体および積層体
WO2023000420A1 (zh) 功能型丙烯酸乳液及其制备方法、耐磨丙烯酸涂布膜、丙烯酸涂布bopp膜
WO2022205702A1 (zh) 一种纸张用的热封型丙烯酸乳液及其制备方法
CN110437368B (zh) 一种细粒径乳液树脂及其制备方法
JP2014205855A (ja) ガスバリア性樹脂層形成用組成物、並びにこれを用いてなるガスバリア性フィルム及びその製造方法
JP5695505B2 (ja) ガスバリア性フィルム及びその製造方法
CN103275260A (zh) 一种丙烯酸塑塑复合胶乳制备方法
CN113105581B (zh) 一种耐磨烟膜专用丙烯酸乳液及其制备方法，以及耐磨烟膜
KR20060130054A (ko) 중합성 조성물 및 (메타)아크릴계 열전도 시트의 제조 방법
CN107057616B (zh) 铝塑复合板用粘合层树脂的制备方法
CN103059193A (zh) 烟膜专用pvdc涂布胶乳及其制备方法和应用
JP4128376B2 (ja) 塩化ビニリデン系共重合体ラテックス
CN115636898B (zh) 一种可剥离丙烯酸乳液及其制备方法和可剥离保护膜
JPS6381184A (ja) ゴムと繊維との接着剤組成物
CN117069893A (zh) 一种羧基丁腈立体磨砂手套专用胶乳
TW201903100A (zh) 黏著劑組合物、黏著薄片及密封體

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21952473

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE