WO2011157085A1 - 印刷用改性聚乙烯醇涂布薄膜及其制造方法 - Google Patents

印刷用改性聚乙烯醇涂布薄膜及其制造方法 Download PDF

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Publication number
WO2011157085A1
WO2011157085A1 PCT/CN2011/073685 CN2011073685W WO2011157085A1 WO 2011157085 A1 WO2011157085 A1 WO 2011157085A1 CN 2011073685 W CN2011073685 W CN 2011073685W WO 2011157085 A1 WO2011157085 A1 WO 2011157085A1
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Prior art keywords
polyvinyl alcohol
coating
modified polyvinyl
acrylic
coated film
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PCT/CN2011/073685
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English (en)
French (fr)
Inventor
黄宏存
Original Assignee
海南赛诺实业有限公司
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Priority to EP11795051.9A priority Critical patent/EP2583834B1/en
Priority to US13/581,669 priority patent/US9200173B2/en
Publication of WO2011157085A1 publication Critical patent/WO2011157085A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D129/00—Coating compositions 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2429/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31554—Next to second layer of polyamidoester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31576—Ester monomer type [polyvinylacetate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
    • Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31913—Monoolefin polymer

Definitions

  • the invention belongs to the field of novel environment-friendly polymer materials, and is a modified polyvinyl alcohol coated film for printing and a manufacturing method thereof. Background technique
  • Polyvinylidene chloride flexible packaging materials are widely used and occupy most of the market.
  • Polyvinylidene chloride has good symmetry and easy formation of crystals, and contains a large number of polar chlorine atoms. The presence of these polar chlorine atoms greatly enhances the attraction between molecules, and the molecules are closely arranged.
  • Vinyl chloride materials have high barrier properties. However, it is precisely because polyvinylidene chloride contains a large amount of chlorine atoms, which causes harmful gases to be generated during combustion treatment. In recent years, with the increasing pressure on environmental protection, it has become an irresistible trend to develop new high-barrier environmentally friendly materials to replace polyvinylidene chloride.
  • the polyvinyl alcohol product in the dry state has excellent oxygen barrier properties, and its barrier property is far superior to that of polyvinylidene chloride.
  • the polyvinyl alcohol molecule contains a large amount of strongly hydrophilic hydroxyl groups, which readily form hydrogen bonds with water in a wet state, and associates with water in the form of hydrogen bonds, and barrier properties of polyvinyl alcohol products associated with water. Will be greatly reduced, for example: At a relative humidity of 50%, the polyvinyl alcohol product will completely lose its original oxygen barrier properties, basically can not be used as a food packaging material.
  • the prior art mainly chemically modifies polyvinyl alcohol, and reduces the force of hydrogen bonding as much as possible while maintaining the high barrier property of its molecular structure.
  • the modified polyvinyl alcohol product still has good gas barrier properties in the high humidity state.
  • the moisture resistance of the modified polyvinyl alcohol product is greatly improved, its printing adaptability is too poor, because the adhesion of the modified polyvinyl alcohol coating to the ink is too low, so the printing time is good. It is prone to the phenomenon of ink and coating peeling off, and the modified polyvinyl alcohol is not particularly suitable for environmentally friendly inks such as water-based inks. Most of the packaging products need to be printed, which greatly limits the promotion and use of such products. Summary of the invention
  • the problem to be solved by the present invention is to provide a novel modified polyvinyl alcohol coated film for printing, which not only has excellent oxygen barrier property but also has Good heat sealing performance and excellent printing adaptability, especially for environmentally friendly inks such as water and alcohol.
  • the present invention provides a modified polyvinyl alcohol coated film for printing, comprising: a coating layer, a primer layer and a substrate, wherein the coating layer comprises an acrylic coating and a modification in sequence. a polyvinyl alcohol coating, the modified polyvinyl alcohol coating being in contact with the primer layer;
  • the modified polyvinyl alcohol coating is coated with a modified polyvinyl alcohol coating having the following composition after drying on the surface of the primer layer: 50 wt% to 100% modified polyvinyl alcohol solution, 0 to 40 wt % demineralized water, 0 ⁇ 10wt% slip agent and 0 ⁇ 4wt% anti-adhesive agent; the modified polyvinyl alcohol solution is cross-linked by 80wt% ⁇ 95wt antimony polyvinyl alcohol and 5wt% ⁇ 20wt antimony urea Form
  • the acrylic coating is applied to the surface of the modified polyvinyl alcohol coating by the acrylic coating of the following composition: 25wt% ⁇ 95wt ⁇ acrylic emulsion, 0 ⁇ 70wt% softened water, 2wt% ⁇ 15 a wt% slip agent and 0.1 wt% to 5 wt% of a release agent; the acrylic emulsion is formed from 10 wt% to 80 wt% of acrylic acid and 20 wt% to 90 wt% of a copolymer of methyl acrylate or ethyl acrylate;
  • the substrate is a biaxially oriented polypropylene film or a biaxially stretched polyurethane film
  • the primer layer is a coating formed of aqueous polyurethane or aqueous acrylic.
  • the make layer and the coating layer are present simultaneously on one side of the substrate or on both sides of the substrate.
  • the modified polyvinyl alcohol coating has a solid content of 5% to 20% of the modified polyvinyl alcohol solution, a solid content of the slip agent of 5% to 30%, and a solid content of the anti-adhesive agent of 3%. ⁇ 25%.
  • the acrylic emulsion has a solid content of 10% to 60%, a solid content of the slip agent of 10% to 30%, and a solid content of the anti-adhesive agent of 5% to 20%.
  • the slip agent is palm wax.
  • the release agent is silica.
  • the modified polyvinyl alcohol coating has a thickness of 0.3 ⁇ m to 1.5 ⁇ m.
  • the acrylic coating has a thickness of 0.1 ⁇ m - 2.0 ⁇ m.
  • the substrate has a thickness of from 10 ⁇ m to 100 ⁇ m.
  • the primer is applied in an amount of from 0.1 g/m 2 to 0.8 g/m 2 .
  • the present invention also provides a process for producing a modified polyvinyl alcohol coated film for printing.
  • the substrate is subjected to a corona treatment, and the substrate is a biaxially oriented polypropylene film or a biaxially stretched polyurethane film;
  • the acrylic paint is evenly coated on the surface of the modified polyvinyl alcohol coating layer and dried, and then dried at 40 ° C to 45 ° C for 36 h to 60 h to obtain a modified polyvinyl alcohol coated film for printing;
  • the modified polyvinyl alcohol coating is coated with a modified polyvinyl alcohol coating having the following composition after drying on the surface of the primer layer: 50 wt% to 100% modified polyvinyl alcohol solution, 0 to 40 wt % demineralized water, 0 ⁇ 10wt% slip agent and 0 ⁇ 4wt% anti-adhesive agent; the modified polyvinyl alcohol solution is cross-linked by 80wt% ⁇ 95wt antimony polyvinyl alcohol and 5wt% ⁇ 20wt antimony urea Form
  • the acrylic coating is applied to the surface of the modified polyvinyl alcohol coating by the acrylic coating of the following composition: 25wt% ⁇ 95wt ⁇ acrylic emulsion, 0 ⁇ 70wt% softened water, 2wt% ⁇ 15 a wt% slip agent and 0.1 wt% to 5 wt% of a release agent; the acrylic emulsion is formed of a copolymer of 10 wt% to 80 wt% of acrylic acid and 20 wt% to 90 wt% of methyl acrylate or ethyl acrylate.
  • the coating amount of the modified polyvinyl alcohol coating is 0.25 g/m 2 to 1.5 g/m 2 ; and the coating amount of the acrylic coating material is 0.1 g/m 2 to 2.0 g/m 2 .
  • the coating speed of the modified polyvinyl alcohol coating on the primer layer is from 60 m/min to 200 m/min; and the acrylic coating is uniformly applied to the modified polyvinyl alcohol coating.
  • the coating speed of the surface is 50 m/min ⁇ 220 m/min;
  • the drying mode is one or two of hot air drying and far infrared drying, wherein the drying temperature is 90 ° C ⁇ 140 ° C, and the drying time is 5 seconds to 20 seconds.
  • the coating is a reverse roll kiss coating.
  • the present invention provides a modified polyvinyl alcohol coated film for printing.
  • the coated film provided by the present invention is coated with an acrylic coating on the outer layer of the modified polyvinyl alcohol coating. Because acrylic acid has strong adhesion to ink, it can not only enhance the water resistance of modified polyvinyl alcohol, but also overcome the problem of poor adaptability of modified polyvinyl alcohol coating to ink, so that this product has high barrier. Sex and moisture resistance, and can be adapted to the printing of most inks currently in use. In addition, the coating film has the characteristics of production cost and recyclability.
  • the experiment proves that the modified polyvinyl alcohol coated film for printing has high barrier property at a relative humidity of 50%, and the oxygen permeation amount is about 0.6 ml / m 2.24 h ⁇ 2.5 ml / m 2.24 h. .
  • the polyamide ink, chlorinated polypropylene ink, polyurethane ink and acrylate ink have a bonding fastness of more than 95%, and have excellent printing adaptability.
  • the modified polyvinyl alcohol coated film for printing provided by the present invention can be directly used for packaging dried fruit products, and can also be packaged with other materials to package biscuit cake products. detailed description
  • the anti-blocking agents in the following examples are all silica anti-blocking agents supplied by Schulman, Belgium, and the product grade is ABPP05.
  • the palm wax slip agents are all supplied by Asahi Kasei Co., Ltd., and the product grade is KP9800;
  • the adhesive primer is supplied by Beijing Linshi Refined New Materials Co., Ltd., and the product grade is TCL-1.
  • the waterborne polyurethane adhesive primer is supplied by DSM, the Netherlands, and the product grade is R-610.
  • Example 1 The raw materials used in this example are as follows:
  • Substrate a biaxially oriented polypropylene film having a thickness of 18 ⁇ m;
  • Modified polyvinyl alcohol solution formed by cross-linking reaction of 90 wt% of polyvinyl alcohol and 10 wt% of urea, and the solid content is 7%;
  • Acrylic emulsion a copolymer of 70% by weight of acrylic acid and 30% by weight of methyl acrylate, having a solid content of 25%;
  • primer water-based acrylic adhesive
  • step 1 is prepared by reverse roll kiss coating.
  • the modified polyvinyl alcohol coating is uniformly coated on the substrate film to obtain a modified polyvinyl alcohol coated film which is not covered with the acrylic coating.
  • the reverse roller kiss coating method can solve the problem of adapting to the thickness deviation of the substrate.
  • the coating amount is 0.6 g/m 2 , and after coating, it is dried by far infrared ray and then wound up to form a film.
  • the coating speed was 160 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 10 seconds.
  • the biaxially oriented polypropylene film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-wound, and the acrylic paint prepared in the step 3 is uniformly coated on the modified polyethylene by reverse roll bonding.
  • the surface of the alcohol coating layer was coated with 0.7 g/m 2 , and after being coated, it was dried by far infrared ray and then wound up to form a film.
  • the control speed was 180 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 8 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 45 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 1.4 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially stretched polyester film with a thickness of 23 ⁇ m;
  • Modified polyvinyl alcohol solution from 92wt% polyvinyl alcohol and 8wt% urea Formation reaction, the solid content is 10%;
  • Acrylic emulsion a copolymer of 20% by weight of acrylic acid and 80% by weight of ethyl acrylate, having a solid content of 30%;
  • primer waterborne polyurethane adhesive.
  • step 2 The substrate biaxially stretched polyester film is unwound and corona treated, pre-coated with a primer, the amount of primer applied is 0.1 g/m 2 , and then step 1 is prepared by reverse roll bonding.
  • the modified polyvinyl alcohol coating is evenly coated on the substrate film, and the coating amount is 0.7 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a modified polyethylene. Alcohol coated film.
  • the coating speed was 110 m/min during coating, the drying temperature was 130 ° C during drying, and the drying time was 15 seconds.
  • the biaxially stretched polyester film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-wound, and the acrylic paint prepared in the step 3 is hook-coated by the reverse roll kiss coating method.
  • the surface of the polyvinyl alcohol coating was completely covered with a modified polyvinyl alcohol coating, and the coating amount was 1.0 g/m 2 . After coating, it was dried by far infrared ray and wound up to form a film.
  • the coating speed was 150 m/min during coating, the drying temperature was 130 ° C during drying, and the drying time was 10 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 40 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 0.8 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially oriented polypropylene film, thickness ⁇ ⁇ ⁇ ;
  • Modified polyvinyl alcohol solution formed by crosslinking reaction of 80 wt% of polyvinyl alcohol and 20 wt% of urea, and the solid content is 12%;
  • acrylic emulsion 10wt% acrylic acid and 90wt% methyl acrylate copolymerized, the solid content is 55%;
  • primer waterborne polyurethane adhesive.
  • step 1 is prepared by reverse roll kiss coating.
  • the modified polyvinyl alcohol coating is evenly coated on the substrate film, and the coating amount is 1.2 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a modified polyethylene. Alcohol coated film.
  • the coating speed was 120 m/min during coating, the drying temperature was 120 °C during drying, and the drying time was 18 seconds.
  • the biaxially oriented polypropylene film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-rolled, and the acrylic paint prepared in the step 3 is uniformly coated on the modified poly by reverse roll bonding.
  • the surface of the vinyl alcohol coating was completely covered with a modified polyvinyl alcohol coating, and the coating amount was 2.0 g/m 2 .
  • the coating speed was 220 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 6 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 42 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 0.7 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially stretched polyester film with a thickness of ⁇ ⁇ ⁇ ;
  • Modified polyvinyl alcohol solution formed by crosslinking reaction of 85 wt% of polyvinyl alcohol and 5 wt% of urea, and the solid content is 8.5%;
  • Acrylic emulsion a copolymer of 50% by weight of acrylic acid and 50% by weight of methyl acrylate, having a solid content of 20%;
  • primer water-based acrylic adhesive
  • step 1 is prepared by reverse roll kiss coating.
  • the modified polyvinyl alcohol coating is evenly coated on the substrate film, and the coating amount is 1.0 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a modified polyethylene. Alcohol coated film.
  • the control speed was 140 m/min during coating, the drying temperature was 130 ° C during drying, and the drying time was 13 seconds.
  • the biaxially stretched polyester film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-wound, and the acrylic paint prepared in the step 3 is hook-coated by the reverse roll kiss coating method.
  • the surface of the polyvinyl alcohol coating was completely covered with a modified polyvinyl alcohol coating, and the coating amount was 1.0 g/m 2 . After coating, it was dried by far infrared ray and wound up to form a film.
  • the coating speed was 170 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 9 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 45 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 1.0 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially oriented polypropylene film, thickness ⁇ ⁇ ⁇ ;
  • Modified polyvinyl alcohol solution formed by cross-linking reaction of 95 wt% of polyvinyl alcohol and 5 wt% of urea, and the solid content is 20%;
  • Acrylic emulsion a copolymer of 25 wt% acrylic acid and 75 wt% ethyl acrylate, having a solid content of 60%;
  • primer waterborne polyurethane adhesive.
  • the substrate biaxially stretched polypropylene film is unwound and corona treated, pre-coated with primer, bottom
  • the coating amount of the gel was 0.8 g/m 2
  • the modified polyvinyl alcohol coating prepared in the step 1 was uniformly coated on the substrate film by a reverse roll kiss coating method, and the coating amount was 1.5 g/m 2 .
  • After coating it is dried by far infrared ray and then wound up to form a film, thereby obtaining a modified polyvinyl alcohol coating film which is not covered with an acrylic coating.
  • the coating speed was 100 m/min during coating, the drying temperature was 140 °C during drying, and the drying time was 16 seconds.
  • the biaxially oriented polypropylene film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-rolled, and the acrylic paint prepared in the step 3 is uniformly coated on the modified poly by reverse roll bonding.
  • the surface of the vinyl alcohol coating was completely covered with a modified polyvinyl alcohol coating, and the coating amount was 2.0 g/m 2 .
  • the coating speed was 190 m/min during coating, the drying temperature was 125 ° C during drying, and the drying time was 8 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 40 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 0.6 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially stretched polyester film with a thickness of ⁇ ⁇ ⁇ ;
  • Modified polyvinyl alcohol solution formed by crosslinking reaction of 88 wt% of polyvinyl alcohol and 12 wt% of urea, and the solid content is 8%;
  • Acrylic emulsion a copolymer of 22% by weight of acrylic acid and 78% by weight of methyl acrylate, having a solid content of 25%;
  • primer water-based acrylic adhesive
  • step 2 The substrate biaxially stretched polyester film is unwound and corona treated, pre-coated with a primer, the amount of primer applied is 0.3 g/m 2 , and then step 1 is prepared by reverse roll kiss coating.
  • the modified polyvinyl alcohol coating is evenly coated on the substrate film, and the coating amount is 0.7 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a modified polyethylene. Alcohol coated film. Coating time control The drying speed was 120 m/min, the drying temperature was 140 ° C during drying, and the drying time was 14 seconds.
  • the biaxially stretched polyester film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-wound, and the acrylic paint prepared in the step 3 is hook-coated by the reverse roll kiss coating method.
  • the surface of the polyvinyl alcohol coating is completely covered with a modified polyvinyl alcohol coating, and the coating amount is 1.2 g/m 2 .
  • After coating it is dried by far infrared ray and then wound up to form a film.
  • the coating speed was 140 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 11 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 40 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 0.9 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially oriented polypropylene film with a thickness of 28 ⁇ m;
  • Modified polyvinyl alcohol solution formed by crosslinking reaction of 91 wt% of polyvinyl alcohol and 9 wt% of urea, and the solid content is 5%;
  • Acrylic emulsion a copolymer of 50% by weight of acrylic acid and 50% by weight of methyl acrylate, having a solid content of 33%;
  • primer waterborne polyurethane adhesive.
  • step 1 is prepared by reverse roll bonding.
  • the modified polyvinyl alcohol coating is coated on the base film, and the coating amount is 0.25 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a film, thereby obtaining a modified poly-coated acrylic coating. Vinyl alcohol coated film. The coating speed was 140 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 12 seconds.
  • the coating speed was 130 m/min during coating, the drying temperature was 120 ° C during drying, and the drying time was 9 seconds.
  • the modified polyvinyl alcohol coated film for printing was obtained by curing at 40 ° C for two days.
  • the oxygen permeation amount was measured at a relative humidity of 50% of 2.5 ml/m 2 .24 h.
  • the raw materials used in this example are as follows:
  • Substrate Biaxially stretched polyester film with a thickness of 12 ⁇ m;
  • Modified polyvinyl alcohol solution formed by crosslinking reaction of 90 wt% of polyvinyl alcohol and 10 wt% of urea, and the solid content is 9%;
  • Acrylic emulsion a copolymer of 40% by weight of acrylic acid and 60% by weight of methyl acrylate, having a solid content of 25%;
  • primer water-based acrylic adhesive
  • step 2 The substrate biaxially stretched polyester film is unwound and corona treated, pre-coated with a primer, the amount of primer applied is 0.5 g/m 2 , and then step 1 is prepared by reverse roll kiss coating.
  • the modified polyvinyl alcohol coating is evenly coated on the substrate film, and the coating amount is 0.6 g/m 2 . After coating, it is dried by far infrared ray and then wound up to form a modified polyethylene. Alcohol coated film.
  • the coating speed was 120 m/min during coating, the drying temperature was 135 °C during drying, and the drying time was 14 seconds.
  • the biaxially stretched polyester film coated with the modified polyvinyl alcohol coating prepared in the step 2 is re-wound, and the acrylic paint prepared in the step 3 is hook-coated by the reverse roll kiss coating method.
  • the modified polyvinyl alcohol coating film obtained by the examples 1 to 8 was obtained without the acrylic coating, and the numbers were ⁇ , 2, 3, 4, 5, 6, 6, 7, 8'.
  • the modified polyvinyl alcohol-coated films for printing prepared in Examples 1 to 8 were numbered 1, 2, 3, 4, 5, 6, 7, and 8. According to the testing requirements of GB/T7707-2008. The bonding fastness of the different inks of the above coated film was tested, and the test results are shown in Table 1.
  • the adhesion of the coating film covered with an acrylic coating is obvious.
  • the modified polyvinyl alcohol coating film for printing provided by the invention has high bonding fastness to various types of inks, and has good printing adaptability.
  • the description of the examples is only intended to aid in understanding the method of the invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

Description

印刷用改性聚乙烯醇涂布薄膜及其制造方法
本申请要求于 2010 年 6 月 16 日提交中国专利局、 申请号为 201010208100.5、 发明名称为 "一种印刷用改性聚乙烯醇涂布薄膜及其制 造方法"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
本发明属于新型环保型高分子材料领域 ,是一种印刷用改性聚乙烯醇 涂布薄膜及其制造方法。 背景技术
传统的食品用阻隔性软包装材料主要包括两类产品：聚偏二氯乙烯类 和聚酰胺类。其中聚偏二氯乙烯类软包装材料使用较为广泛， 占据了大部 分市场。 聚偏二氯乙烯分子对称性好， 容易形成结晶， 且其中含有大量的 极性氯原子，这些极性氯原子的存在使得分子间的吸引力大大增强，分子 排列紧密， 由此使得聚偏二氯乙烯材料具有较高的阻隔性能。但也正因为 聚偏二氯乙烯中含有大量的氯原子， 使其在燃烧处理时会产生有害气体。 近年来， 随着环保压力的日益增大，开发新型高阻隔性环保材料以代替聚 偏二氯乙烯已成为大势所趋。
干态下的聚乙烯醇产品具有优异的阻氧性能，其阻隔性能远远优越于 聚偏二氯乙烯。但是， 聚乙烯醇分子中含有大量强亲水性的羟基， 湿态下 容易与水形成氢键，并以氢键的形式与水締合，与水締合后的聚乙烯醇产 品的阻隔性能将会大大降低， 例如： 在相对湿度在为 50%时， 聚乙烯醇 产品就会完全失去它原有的氧气阻隔性能，基本上不能作为食品用包装材 料使用。
为了解决聚乙烯醇的耐湿问题,现有技术主要是对聚乙烯醇进行化学 改性，在保持其分子结构所具有的高阻隔性能的条件下，尽可能减少氢键 的作用力，在耐水性方面寻求突破口，使改性后的聚乙烯醇产品在高湿态 下仍具有良好的气体阻隔性。
改性后的聚乙烯醇产品的耐湿性能虽然大大提高，但是其印刷适应性 太差，这是因为改性聚乙烯醇涂层对油墨的附着力太低， 因此在印刷时容 易出现油墨和涂层脱落的现象，改性后的聚乙烯醇尤其不能适用于水性油 墨等环保型油墨。而包装类产品大多需要印刷， 因此大大限制了该类产品 的推广和使用。 发明内容
针对现有改性聚乙烯醇产品的印刷问题，本发明要解决的问题是：提 供一种新型印刷用改性聚乙烯醇涂布薄膜，该涂布薄膜不仅具有优异的氧 气阻隔性，而且具有艮好的热封性能及杰出的印刷适应性，尤其对水性和 醇系等环保型油墨具有极好的配合性。
为了解决以上技术问题，本发明提供一种印刷用改性聚乙烯醇涂布薄 膜， 依次包括： 涂料层、 底胶层和基材， 其特征在于， 所述涂料层依次包 括丙烯酸涂层和改性聚乙烯醇涂层，所述改性聚乙烯醇涂层与底胶层相接 触；
所述改性聚乙烯醇涂层为如下成分的改性聚乙烯醇涂料涂覆在所述 底胶层表面经烘干后形成： 50wt%~100%的改性聚乙烯醇溶液、 0~40wt% 的软化水、 0~10wt%的滑爽剂和 0~4wt%的防粘剂； 所述改性聚乙烯醇溶 液由 80wt%~95wt 々聚乙烯醇和 5wt%~20wt 々尿素发生交联反应形 成；
所述丙烯酸涂层为如下成分的丙烯酸涂料涂覆在所述改性聚乙烯醇 涂层表面经烘干后形成： 25wt%~95wt 々丙烯酸乳液、 0~70wt%的软化 水、 2wt%~15 wt%的滑爽剂和 0.1wt%~5wt%的防粘剂； 所述丙烯酸乳液 由 10wt%~80wt%的丙烯酸和 20wt%~90wt%的丙烯酸甲酯或丙烯酸乙酯 的共聚物形成；
所述基材为双向拉伸聚丙烯薄膜或双向拉伸聚氨酯薄膜；
所述底胶层为水性聚氨酯或水性丙烯酸形成的涂层。
优选的，所述底胶层和涂料层在基材的一个面或在基材的两个面同时 存在。
优选的， 所述改性聚乙烯醇涂料中改性聚乙烯醇溶液的固含量为 5%~20%, 滑爽剂的固含量为 5%~30% , 防粘剂的固含量为 3%~25%。 优选的， 所述丙烯酸涂料中丙烯酸乳液的固含量为 10%~60% , 滑爽 剂的固含量为 10%~30%, 防粘剂的固含量为 5%~20%。
优选的， 所述的滑爽剂是棕榈蜡。
优选的， 所述的防粘剂是二氧化硅。
优选的， 所述的改性聚乙烯醇涂层的厚度 0.3 μ m ~1.5 μ m。
优选的， 所述的丙烯酸涂层的厚度为 0.1 μ m -2.0 μ m。
优选的， 所述基材的厚度为 10 μ m -100 μ m。
优选的， 所述底胶的涂布量为 0.1 g/m2~0.8g/m2。
相应的， 本发明还提供一种印刷用改性聚乙烯醇涂布薄膜的制造方 法。
对基材进行电晕处理，所述基材为双向拉伸聚丙烯薄膜或双向拉伸聚 氨酯薄膜；
在所述基材的电晕面预涂底胶并进行烘干， 基材表面形成底胶层； 将改性聚乙烯醇涂料均匀涂布于所述底胶层表面并进行烘干，底胶层 表面形成改性聚乙烯醇涂层；
将丙烯酸涂料均匀涂布于所述改性聚乙烯醇涂层表面并进行烘干，烘 干后在 40°C ~45 °C固化 36h~60h, 得到印刷用改性聚乙烯醇涂布薄膜； 所述改性聚乙烯醇涂层为如下成分的改性聚乙烯醇涂料涂覆在所述 底胶层表面经烘干后形成： 50wt%~100%的改性聚乙烯醇溶液、 0~40wt% 的软化水、 0~10wt%的滑爽剂和 0~4wt%的防粘剂； 所述改性聚乙烯醇溶 液由 80wt%~95wt 々聚乙烯醇和 5wt%~20wt 々尿素发生交联反应形 成；
所述丙烯酸涂层为如下成分的丙烯酸涂料涂覆在所述改性聚乙烯醇 涂层表面经烘干后形成： 25wt%~95wt 々丙烯酸乳液、 0~70wt%的软化 水、 2wt%~15 wt%的滑爽剂和 0.1wt%~5wt%的防粘剂； 所述丙烯酸乳液 由 10wt%~80wt%的丙烯酸和 20wt%~90wt%的丙烯酸甲酯或丙烯酸乙酯 的共聚物形成。
优选的， 所述改性聚乙烯醇涂料的涂布量为 0.25 g/m2~1.5g/m2; 所述 丙烯酸涂料的涂布量为 0.1 g/m2~2.0g/ m2。 优选的， 将改性聚乙烯醇涂料均勾涂布于所述底胶层的涂布速度为 60 m/min ~200m/min; 将丙烯酸涂料均匀涂布于所述改性聚乙烯醇涂层表 面的涂布速度为 50 m/min~220m/min;
优选的，所述烘干方式为热风烘干和远红外烘干中的一种或两种同时 使用， 所述烘干温度为 90 °C ~140°C , 烘干时间 5秒~20秒。
优选的， 所述涂布为逆转辊吻式涂布。
本发明提供一种印刷用改性聚乙烯醇涂布薄膜，本发明提供的这种涂 布薄膜是在改性聚乙烯醇涂层外层再覆盖一层丙烯酸涂料。因丙烯酸对油 墨有很强的附着力，其既能增强改性聚乙烯醇的耐水性能，又能克服改性 聚乙烯醇涂层对油墨适应差的问题，使本产品既具有较高的阻隔性和耐湿 性，又能适应目前使用的大多数油墨的印刷。此外该涂布膜还具有生产成 本^ 和可回收降解的特点。
实验证明，本发明提供的印刷用改性聚乙烯醇涂布薄膜，在相对湿度 50%时仍具有较高的阻隔性能， 氧气透过量约为 0.6ml/ m2.24h ~2.5ml/ m2.24h。 对聚酰胺油墨、 氯化聚丙烯油墨、 聚氨酯油墨和丙烯酸酯油墨 结合牢度均大于 95% , 具有优良的印刷适应性。 本发明提供的印刷用改 性聚乙烯醇涂布薄膜既可直接用于包装干果类产品，也可以与其它材料复 合后包装饼干蛋糕类产品。 具体实施方式
为了进一步了解本发明，下面结合实施例对本发明优选实施方案进行 描述， 但是应当理解， 这些描述只是为进一步说明本发明的特征和优点， 而不是对本发明权利要求的限制。
以下实施例中的抗粘连剂均由比利时舒尔曼公司提供的二氧化硅抗 粘连剂， 商品牌号为 ABPP05; 棕榈蜡滑爽剂均是由日本旭化成公司提供 的， 商品牌号为 KP9800; 水性丙烯酸粘合剂底胶均由北京林氏精化新材 料有限公司公司提供， 商品牌号为 TCL-1 ; 水性聚氨酯粘合剂底胶均由荷 兰帝斯曼公司提供， 商品牌号为 R-610。
实施例 1 本实施例使用的原料如下：
①、 基材： 双向拉伸聚丙烯薄膜， 厚度为 18 μ ιη;
②、 改性聚乙烯醇溶液： 由 90wt%的聚乙烯醇和 10wt%的尿素发生 交联反应形成， 固含量为 7%;
③、 丙烯酸乳液： 由 70wt%的丙烯酸与 30wt%的丙烯酸甲酯共聚而 成， 固含量为 25%;
④、 底胶： 水性丙烯酸粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 200kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 1.3kg, 防粘剂 0.8kg和软化水 10kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚丙烯薄膜放卷后进行电晕处理， 预涂底胶， 底 胶涂布量为 0.3g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚 乙烯醇涂料均匀涂在基材薄膜上 ,得到未覆盖丙烯酸涂层的改性聚乙烯醇 涂布膜。 采用逆转辊吻式涂布方式可以解决对基材厚度偏差的适应性难 题， 涂布量为 0.6 g/ m2, 涂布后经远红外线烘干后收卷成膜。 涂布时控制 速度为 160m/min, 烘干时干燥温度为 120°C , 干燥时间为 10秒。
3、 称取 120kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 1.5kg, 防 粘剂 1.2kg和软化水 20kg, 搅拌均勾后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚丙烯薄膜重 新放卷，通过逆转辊吻式涂布方式将步骤 3配制的丙烯酸涂料均匀涂在改 性聚乙烯醇涂层表面， 涂布量为 0.7 g/ m2, 涂布后经过远红外线烘干后收 卷成膜。 涂布时控制速度为 180m/min, 干燥时干燥温度为 120°C , 干燥 时间为 8秒。 烘干完毕后， 经过 45 °C固化两天即制得印刷用改性聚乙烯 醇涂布薄膜。 在相对湿度 50%时测得其氧气透过量为 1.4ml/ m2.24h。
实施例 2
本实施例使用的原料如下：
①、 基材： 双向拉伸聚酯薄膜， 厚度为 23 μ ιη;
②、 改性聚乙烯醇溶液： 由 92wt%的聚乙烯醇和 8wt%的尿素发生交 联反应形成， 固含量为 10%;
③、 丙烯酸乳液： 由 20wt%的丙烯酸与 80wt%的丙烯酸乙酯共聚而 成， 固含量为 30%;
④、 底胶： 水性聚氨酯粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 180kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 2.5kg, 防粘剂 1.5kg和软化水 5kg,搅拌均勾后得到改 性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚酯薄膜放卷后进行电晕处理， 预涂底胶， 底胶 涂布量为 0.1g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚乙 烯醇涂料均匀涂在基材薄膜上， 涂布量为 0.7 g/ m2, 涂布后经远红外线烘 干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时控 制速度为 110m/min, 烘干时干燥温度为 130°C , 干燥时间为 15秒。
3、 称取 160kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 2.0kg, 防 粘剂 1.8kg和软化水 30kg, 搅拌均匀后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚酯薄膜重新 放卷,通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均勾涂在改性 聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 1.0 g/ m2, 涂 布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 150m/min, 干燥 时干燥温度为 130°C , 干燥时间为 10秒。 烘干完毕后， 经过 40°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 0.8ml/ m2.24h。
实施例 3
本实施例使用的原料如下：
①、 基材： 双向拉伸聚丙烯薄膜， 厚度为 ΙΟΟ μ ιη;
②、 改性聚乙烯醇溶液： 由 80wt%的聚乙烯醇和 20wt%的尿素发生 交联反应形成， 固含量为 12%;
③、 丙烯酸乳液： 由 10wt%的丙烯酸与 90wt%的丙烯酸甲酯共聚而 成， 固含量为 55%; ④、 底胶： 水性聚氨酯粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 300kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 1.2kg, 防粘剂 2.5kg和软化水 15kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚丙烯薄膜放卷后进行电晕处理， 预涂底胶， 底 胶涂布量为 0.5g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚 乙烯醇涂料均匀涂在基材薄膜上， 涂布量为 1.2 g/ m2, 涂布后经远红外线 烘干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时 控制速度为 120m/min, 烘干时干燥温度为 120 °C , 干燥时间为 18秒。
3、 称取 200kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 4.0kg, 防 粘剂 1.5kg和软化水 45kg, 搅拌均勾后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚丙烯薄膜重 新放卷，通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均匀涂在改 性聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 2.0 g/ m2, 涂布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 220m/min, 干 燥时干燥温度为 120°C , 干燥时间为 6秒。 烘干完毕后， 经过 42°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 0.7ml/ m2.24h。
实施例 4
本实施例使用的原料如下：
①、 基材： 双向拉伸聚酯薄膜， 厚度为 ΙΟ μ ιη;
②、 改性聚乙烯醇溶液： 由 85wt%的聚乙烯醇和 5wt%的尿素发生交 联反应形成， 固含量为 8.5%;
③、 丙烯酸乳液： 由 50wt%的丙烯酸与 50wt%的丙烯酸甲酯共聚而 成， 固含量为 20%;
④、 底胶： 水性丙烯酸粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 190kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 1.5kg, 防粘剂 1.2kg和软化水 12kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚酯薄膜放卷后进行电晕处理， 预涂底胶， 底胶 涂布量为 0.8g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚乙 烯醇涂料均匀涂在基材薄膜上， 涂布量为 1.0 g/ m2, 涂布后经远红外线烘 干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时控 制速度为 140m/min, 烘干时干燥温度为 130°C , 干燥时间为 13秒。
3、 称取 150kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 1.5kg, 防 粘剂 0.8kg和软化水 36kg, 搅拌均匀后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚酯薄膜重新 放卷,通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均勾涂在改性 聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 1.0 g/ m2, 涂 布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 170m/min, 干燥 时干燥温度为 120°C , 干燥时间为 9秒。 烘干完毕后， 经过 45 °C固化两天 即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气透 过量为 1.0ml/ m2.24h。
实施例 5
本实施例使用的原料如下：
①、 基材： 双向拉伸聚丙烯薄膜， 厚度为 ΙΟ μ ιη;
②、 改性聚乙烯醇溶液： 由 95wt%的聚乙烯醇和 5wt%的尿素发生交 联反应形成， 固含量为 20%;
③、 丙烯酸乳液： 由 25wt%的丙烯酸与 75wt%的丙烯酸乙酯共聚而 成， 固含量为 60%;
④、 底胶： 水性聚氨酯粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 250kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 3.0kg, 防粘剂 1.9kg和软化水 35kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚丙烯薄膜放卷后进行电晕处理， 预涂底胶， 底 胶涂布量为 0.8g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚 乙烯醇涂料均匀涂在基材薄膜上， 涂布量为 1.5 g/ m2, 涂布后经远红外线 烘干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时 控制速度为 100m/min, 烘干时干燥温度为 140 °C , 干燥时间为 16秒。
3、 称取 220kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 2.2kg, 防 粘剂 2.2kg和软化水 31kg, 搅拌均匀后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚丙烯薄膜重 新放卷，通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均匀涂在改 性聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 2.0 g/ m2, 涂布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 190m/min, 干 燥时干燥温度为 125 °C , 干燥时间为 8秒。 烘干完毕后， 经过 40°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 0.6ml/ m2.24h。
实施例 6
本实施例使用的原料如下：
①、 基材： 双向拉伸聚酯薄膜， 厚度为 ΙΟΟ μ ιη;
②、 改性聚乙烯醇溶液： 由 88wt%的聚乙烯醇和 12wt%的尿素发生 交联反应形成， 固含量为 8%;
③、 丙烯酸乳液： 由 22wt%的丙烯酸与 78wt%的丙烯酸甲酯共聚而 成， 固含量为 25%;
④、 底胶： 水性丙烯酸粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 280kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 2.8kg, 防粘剂 2.4kg和软化水 18kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚酯薄膜放卷后进行电晕处理， 预涂底胶， 底胶 涂布量为 0.3g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚乙 烯醇涂料均匀涂在基材薄膜上， 涂布量为 0.7 g/ m2, 涂布后经远红外线烘 干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时控 制速度为 120m/min, 烘干时干燥温度为 140°C , 干燥时间为 14秒。
3、 称取 150kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 2.0kg, 防 粘剂 2.6kg和软化水 27kg, 搅拌均勾后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚酯薄膜重新 放卷,通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均勾涂在改性 聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 1.2 g/ m2, 涂 布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 140m/min, 干燥 时干燥温度为 120°C , 干燥时间为 11秒。 烘干完毕后， 经过 40°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 0.9ml/ m2.24h。
实施例 7
本实施例使用的原料如下：
①、 基材： 双向拉伸聚丙烯薄膜， 厚度为 28 μ ιη;
②、 改性聚乙烯醇溶液： 由 91wt%的聚乙烯醇和 9wt%的尿素发生交 联反应形成， 固含量为 5%;
③、 丙烯酸乳液： 由 50wt%的丙烯酸与 50wt%的丙烯酸甲酯共聚而 成， 固含量为 33%;
④、 底胶： 水性聚氨酯粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 180kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 2.4kg, 防粘剂 1.8kg和软化水 10kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚丙烯薄膜放卷后进行电晕处理， 预涂底胶， 底 胶涂布量为 0.4g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚 乙烯醇涂料均勾涂在基材薄膜上， 涂布量为 0.25 g/ m2, 涂布后经远红外 线烘干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布 时控制速度为 140m/min, 烘干时干燥温度为 120°C , 干燥时间为 12秒。
3、 称取 100kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 1.6kg, 防 粘剂 1.2kg和软化水 42kg, 搅拌均勾后得到丙烯酸乳液。 4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚丙烯薄膜重 新放卷，通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均匀涂在改 性聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 0.7 g/ m2, 涂布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 130m/min, 干 燥时干燥温度为 120°C , 干燥时间为 9秒。 烘干完毕后， 经过 40°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 2.5ml/ m2.24h。
实施例 8
本实施例使用的原料如下：
①、 基材： 双向拉伸聚酯薄膜， 厚度为 12 μ ιη;
②、 改性聚乙烯醇溶液： 由 90wt%的聚乙烯醇和 10wt%的尿素发生 交联反应形成， 固含量为 9%;
③、 丙烯酸乳液： 由 40wt%的丙烯酸与 60wt%的丙烯酸甲酯共聚而 成， 固含量为 25%;
④、 底胶： 水性丙烯酸粘合剂。
本实施例提供的涂布膜制备方法如下：
1、 称取 200kg改性聚乙烯醇溶液加入不锈钢容器中， 一边搅拌一边 依次加入滑爽剂约 1.3kg, 防粘剂 0.9kg和软化水 15kg, 搅拌均匀后得到 改性聚乙烯醇涂料待下一道工序使用。
2、 将基材双向拉伸聚酯薄膜放卷后进行电晕处理， 预涂底胶， 底胶 涂布量为 0.5g/m2,再通过逆转辊吻式涂布方式将步骤 1配制好的改性聚乙 烯醇涂料均匀涂在基材薄膜上， 涂布量为 0.6 g/ m2, 涂布后经远红外线烘 干后收卷成膜，得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜。涂布时控 制速度为 120m/min, 烘干时干燥温度为 135 °C , 干燥时间为 14秒。
3、 称取 160kg丙烯酸乳液， 一边搅拌一边依次加入滑爽剂 2.5kg, 防 粘剂 2.1kg和软化水 20kg, 搅拌均匀后得到丙烯酸乳液。
4、 将步骤 2制得的涂好改性聚乙烯醇涂层的双向拉伸聚酯薄膜重新 放卷,通过逆转辊吻式涂布方式将步骤 3制得的丙烯酸涂料均勾涂在改性 聚乙烯醇涂层表面， 彻底覆盖改性聚乙烯醇涂层， 涂布量为 0.7 g/ m2, 涂 布后经过远红外线烘干后收卷成膜。 涂布时控制速度为 130m/min, 干燥 时干燥温度为 120°C , 干燥时间为 11秒。 烘干完毕后， 经过 40°C固化两 天即制得印刷用改性聚乙烯醇涂布薄膜。 在相对湿度 50%时测得其氧气 透过量为 1.5ml/ m2.24h。
取实施例 1~8制得的得到未覆盖丙烯酸涂层的改性聚乙烯醇涂布膜， 编号依次为 Γ、 2，、 3，、 4，、 5，、 6，、 7，、 8'； 取实施例 1~8制得的印刷 用改性聚乙烯醇涂布薄膜， 编号依次为 1、 2、 3、 4、 5、 6、 7、 8。 根据 GB/T7707-2008的检测要求。 测试上述涂布薄膜不同油墨的结合牢度， 测 试结果列于表 1。
表 1 涂布膜对不同油墨的结合牢度测试结果
Figure imgf000013_0001
由上述结果可知，经过覆盖一层丙烯酸涂料的涂布膜油墨附着力明显 增强，本发明提供的印刷用改性聚乙烯醇涂布膜对多种类型的油墨均具有 较高的结合牢度， 印刷适应性好。 施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对 于本技术领域技术人员来说，在不脱离本发明原理的前提下，还可以对本 发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护 范围内。

Claims

权 利 要 求
1、 一种印刷用改性聚乙烯醇涂布薄膜， 依次包括： 涂料层、 底胶层 和基材，其特征在于，所述涂料层依次包括丙烯酸涂层和改性聚乙烯醇涂 层， 所述改性聚乙烯醇涂层与底胶层相接触；
所述改性聚乙烯醇涂层为如下成分的改性聚乙烯醇涂料涂覆在所述 底胶层表面经烘干后形成： 50wt%~100%的改性聚乙烯醇溶液、 0~40wt% 的软化水、 0~10wt%的滑爽剂和 0~4wt%的防粘剂； 所述改性聚乙烯醇溶 液由 80wt%~95wt 々聚乙烯醇和 5wt%~20wt 々尿素发生交联反应形 成；
所述丙烯酸涂层为如下成分的丙烯酸涂料涂覆在所述改性聚乙烯醇 涂层表面经烘干后形成： 25wt%~95wt 々丙烯酸乳液、 0~70wt%的软化 水、 2wt%~15 wt%的滑爽剂和 0.1wt%~5wt%的防粘剂； 所述丙烯酸乳液 由 10wt%~80wt%的丙烯酸和 20wt%~90wt%的丙烯酸甲酯或丙烯酸乙酯 的共聚物形成；
所述基材为双向拉伸聚丙烯薄膜或双向拉伸聚氨酯薄膜；
所述底胶层为水性聚氨酯或水性丙烯酸形成的涂层。
2、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述底胶层和涂料层在基材的一个面或在基材的两个面同时存在。
3、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述改性聚乙烯醇涂料中改性聚乙烯醇溶液的固含量为 5%~20%, 滑 爽剂的固含量为 5%~30%, 防粘剂的固含量为 3%~25%。
4、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述丙烯酸涂料中丙烯酸乳液的固含量为 10%~60%, 滑爽剂的固含 量为 10%~30% , 防粘剂的固含量为 5%~20%。
5、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述的滑爽剂是棕榈蜡。
6、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述的防粘剂是二氧化硅。
7、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述的改性聚乙烯醇涂层的厚度 0.3 μ m ~1.5 μ m。
8、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述的丙烯酸涂层的厚度为 0.1 μ ιη ~2.0 μ ιη。
9、 根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜， 其特征在 于， 所述基材的厚度为 10 μ ιη ~100 μ ιη。
10、根据权利要求 1所述的印刷用改性聚乙烯醇涂布薄膜，其特征在 于， 所述底胶的涂布量为 0.1 g/m2~0.8g/m2。
11、 一种印刷用改性聚乙烯醇涂布薄膜的制造方法， 其特征在于， 包 括：
对基材进行电晕处理，所述基材为双向拉伸聚丙烯薄膜或双向拉伸聚 氨酯薄膜；
在所述基材的电晕面预涂底胶并进行烘干， 基材表面形成底胶层； 将改性聚乙烯醇涂料均匀涂布于所述底胶层表面并进行烘干，底胶层 表面形成改性聚乙烯醇涂层；
将丙烯酸涂料均匀涂布于所述改性聚乙烯醇涂层表面并进行烘干，烘 干后在 40°C ~45 °C固化 36h~60h, 得到印刷用改性聚乙烯醇涂布薄膜； 所述改性聚乙烯醇涂层为如下成分的改性聚乙烯醇涂料涂覆在所述 底胶层表面经烘干后形成： 50wt%~100%的改性聚乙烯醇溶液、 0~40wt% 的软化水、 0~10wt%的滑爽剂和 0~4wt%的防粘剂； 所述改性聚乙烯醇溶 液由 80wt%~95wt 々聚乙烯醇和 5wt%~20wt 々尿素发生交联反应形 成；
所述丙烯酸涂层为如下成分的丙烯酸涂料涂覆在所述改性聚乙烯醇 涂层表面经烘干后形成： 25wt%~95wt 々丙烯酸乳液、 0~70wt%的软化 水、 2wt%~15 wt%的滑爽剂和 0.1wt%~5wt%的防粘剂； 所述丙烯酸乳液 由 10wt%~80wt%的丙烯酸和 20wt%~90wt%的丙烯酸甲酯或丙烯酸乙酯 的共聚物形成。
12、 根据权利要求 11所述的印刷用改性聚乙烯醇涂布薄膜的制造方 法， 其特征在于， 所述改性聚乙烯醇涂料的涂布量为 0.25 g/m2~1.5g/m2; 所述丙烯酸涂料的涂布量为 0.1 g/m2~2.0g/ m2。
13、 根据权利要求 11所述的印刷用改性聚乙烯醇涂布薄膜的制造方 法，其特征在于，将改性聚乙烯醇涂料均匀涂布于所述底胶层的涂布速度 为 60 m/min ~200m/min;将丙烯酸涂料均勾涂布于所述改性聚乙烯醇涂层 表面的涂布速度为 50 m/min~220m/min。
14、 根据权利要求 11所述的印刷用改性聚乙烯醇涂布薄膜的制造方 法，其特征在于，所述烘干方式为热风烘干和远红外烘干中的一种或两种 同时使用， 所述烘干温度为 90°C ~140°C , 烘干时间 5秒~20秒。
15、 根据权利要求 11所述的印刷用改性聚乙烯醇涂布薄膜的制造方 法， 其特征在于， 所述涂布为逆转辊吻式涂布。
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