WO2022095399A1 - 一种保护印刷面的pvoh涂布膜及其制备方法 - Google Patents

一种保护印刷面的pvoh涂布膜及其制备方法 Download PDF

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WO2022095399A1
WO2022095399A1 PCT/CN2021/093253 CN2021093253W WO2022095399A1 WO 2022095399 A1 WO2022095399 A1 WO 2022095399A1 CN 2021093253 W CN2021093253 W CN 2021093253W WO 2022095399 A1 WO2022095399 A1 WO 2022095399A1
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pvoh
layer
coating
pvoh coating
self
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PCT/CN2021/093253
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English (en)
French (fr)
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李朝辉
冯韵
黎坛
王恩飞
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海南赛诺实业有限公司
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • 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
    • C08J2323/14—Copolymers of propene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • the invention belongs to the technical field of films, and in particular relates to a PVOH coating film for protecting a printing surface and a preparation method thereof.
  • BOPP film is coated with PVOH and then printed on the PVOH coating to achieve high barrier properties and packaging properties.
  • water-based inks due to the increasingly stringent environmental protection requirements, the use of water-based inks is the trend of the future printing industry. However, water-based ink printing after coating will seriously damage the coated surface. The moisture in the water-based ink will cause the PVOH surface to react reversibly, that is, curing The resulting PVOH is partially reversed into an emulsion PVOH, which seriously damages the PVOH surface, and the increase in moisture makes the entire film surface difficult to dry, consumes a lot of energy, and has low production efficiency, which further leads to several times lower barrier properties and a significant drop in transparency.
  • the invention provides a PVOH coating film for protecting the printing surface and a preparation method thereof.
  • the PVOH coating film in the present invention solves the problem of limited use of water-based ink, and the water-based ink does not react reversibly with the PVOH coating.
  • the invention provides a PVOH coating film for protecting the printing surface, which sequentially comprises a BOPP substrate layer, an ink layer and a PVOH coating layer;
  • the PVOH coating layer is made of a self-adhesive PVOH coating, and the self-adhesive PVOH coating includes the following components in mass fractions:
  • the degree of polymerization of the polyvinyl alcohol is 1500-2000, and the degree of alcoholysis is 99.5%.
  • the amino resin is methyl etherified melamine resin.
  • the catalyst is xylenesulfonic acid and/or dimethylcyclohexylamine.
  • the surfactant is sodium dodecyl sulfonate and/or sodium dodecyl sulfate;
  • the defoamer is a silicone defoamer.
  • the self-adhesive PVOH coating is prepared according to the following steps:
  • the BOPP film includes a heat-sealing layer, a middle layer and a smooth layer;
  • the heat-sealing layer comprises the following components in mass fraction: 94.5-98.5% of a mixture of copolymerized polypropylene and heat-sealing material and 1.5-4.5% of silica;
  • the middle layer comprises the following components by mass fraction: 94.5-96.5% homopolypropylene, 2.5-3.5% low stereoregularity polyolefin, 1-1.5% mixed antistatic agent;
  • the smooth surface layer comprises the following components in mass fraction: 85-97.5% of homopolypropylene, 1.5-2.5% of low stereoregularity polyolefin, and 1-2.5% of anti-blocking agent.
  • the thickness of the BOPP substrate layer is 8-60 ⁇ m
  • the thickness of the ink layer is 0.5-3.5 ⁇ m
  • the thickness of the PVOH coating layer is 0.3-1.5 ⁇ m.
  • the present invention provides a method for preparing a PVOH coating film for protecting a printing surface as described above, which comprises unwinding the BOPP film, printing a water-based ink layer, topcoating a self-adhesive PVOH coating, drying and winding;
  • the coating speed of the self-adhesive PVOH coating is 50-500 m/min, and the coating amount is 0.2-2.5 g/m 2 .
  • the drying is multi-stage drying, the drying temperature of the first stage is 80-130°C, and the drying time is 0.5-1.5s; the drying temperature of the remaining stages is 70-130°C, and the drying time is 70-130°C. for 5 to 15s.
  • the present invention provides a PVOH coating film for protecting a printing surface, which sequentially comprises a BOPP substrate layer, an ink layer and a PVOH coating layer; the PVOH coating layer is made of self-adhesive PVOH coating, and the self-adhesive PVOH coating It includes the following components in mass fractions: 3-10% polyvinyl alcohol, 0.4-0.8% N-methallylamine, 0.5-1.2% amino resin, 0.01-0.02% catalyst, 0.01-0.02% of surfactants, 0.003-0.005% defoamer, 87-96.6% deionized water.
  • one side of BOPP is a light film.
  • water-based ink is used to print and dry the light film surface of BOPP to form an ink layer, and then a PVOH coating is applied on the ink layer for curing to form the PVOH coating film of the present invention.
  • the self-adhesive PVOH water-based paint independently developed by the present invention will not cause reversible reaction of the water-based ink when the paint is applied on the dried water-based ink, so that the ink surface can maintain a good appearance and is easy to pass the machine.
  • the coating film of the invention has two functional layers, the outer layer is PVOH coating, one provides excellent oxygen barrier performance, and the other has good friction coefficient, which provides good conditions for fast food packaging of the coating film , and avoids ink damage to the printing layer during packaging operations.
  • the inner layer is the heat sealing layer of BOPP, which provides good characteristics for the packaging heat sealing performance of the product.
  • the method of the invention solves the problem that the moisture in the water-based ink after coating and then printing will damage the PVOH coating surface, because after drying and curing after printing, the printing surface has no moisture, and coating on the printing surface will not cause Printing faces the destruction of the coated surface, thus solving the limitation of the use of water-based inks.
  • Fig. 1 is the structural representation of PVOH coating film in the embodiment of the present invention.
  • 1 is the PVOH coating layer
  • 2 is the ink layer
  • 3 is the BOPP substrate layer.
  • the invention provides a PVOH coating film for protecting the printing surface, which sequentially comprises a BOPP base material layer, an ink layer and a PVOH coating layer;
  • the PVOH coating layer is made of a self-adhesive PVOH coating, and the self-adhesive PVOH coating includes the following components in mass fractions:
  • the BOPP substrate layer, the ink layer and the PVOH coating layer can be in direct contact or indirect contact, and those skilled in the art can add some conventional functional layers to achieve some specific Features.
  • the PVOH coating film having the three-layer structure of the BOPP base material layer, the ink layer and the PVOH coating layer contacted in sequence is used as an example for description.
  • the BOPP base material layer is a BOPP film with a three-layer structure, which are a heat-sealing layer, a middle layer and a smooth layer, respectively.
  • the thickness of the BOPP substrate layer is preferably 8 to 60 ⁇ m, more preferably 10 to 50 ⁇ m, and most preferably 20 to 40 ⁇ m.
  • the sealing layer is preferably 0.2-2.0 ⁇ m, more preferably 0.5-1.5 ⁇ m, and specifically, in the embodiment of the present invention, it may be 0.2 ⁇ m, 1.0 ⁇ m or 2.0 ⁇ m; the thickness of the middle layer is preferably 7.6-1.5 ⁇ m 56 ⁇ m, more preferably 10-45 ⁇ m, most preferably 20-40 ⁇ m, specifically, in the embodiment of the present invention, it can be 7.6 ⁇ m, 56 ⁇ m or 40 ⁇ m; the thickness of the smooth layer is preferably 0.2-2.0 ⁇ m, More preferably, it is 0.5 to 1.5 ⁇ m, and specifically, in the embodiments of the present invention, it may be 0.2 ⁇ m, 1.0 ⁇ m or 2.0 ⁇ m.
  • the heat-sealing layer as the inner layer of the food packaging bag, is in direct contact with the food and can ensure the heat-sealing performance of the packaging.
  • the heat sealing layer includes the following components:
  • the heat-sealing material may be a heat-sealing material known to those skilled in the art, and the silica may be synthetic silica or other inorganic silica.
  • the middle layer comprises the following components in mass fractions: 94.5-96.5% homopolypropylene, 2.5-3.5% low stereoregularity polyolefin, and 1-1.5% mixed antistatic agent;
  • the antistatic agent is an antistatic agent commonly used by those skilled in the art, which will not be repeated in the present invention.
  • Water-based ink is printed on the surface of the glossy layer, and the glossy layer includes the following components in mass fractions:
  • the low stereoregularity polyolefin is a polyolefin of the AV161 model provided by Sumitomo Group of Japan;
  • the anti-linking agent is an anti-linking agent commonly used by those skilled in the art, and the present invention will not repeat them here.
  • the ink layer is preferably an aqueous ink layer, and the thickness of the ink layer is preferably 0.5-3.5 ⁇ m, more preferably 1-3.0 ⁇ m, and most preferably 1.5-2.5 ⁇ m.
  • the thickness of the PVOH coating layer is preferably 0.5 ⁇ m; the PVOH coating layer is made by coating the self-adhesive PVOH coating independently developed by the present invention, and the PVOH coating includes the following components in mass fractions:
  • the mass fraction of the polyvinyl alcohol is preferably 3 to 10%, more preferably 4 to 9%, and most preferably 5 to 8%. Specifically, in the embodiment of the present invention, it may be 3 %, 6% and 10%; the degree of polymerization of the polyvinyl alcohol is 1500-2000, more preferably 1600-1900, most preferably 1700-1800; the alcoholysis degree is preferably 99.5%.
  • the polyvinyl alcohol in the range of polymerization degree and alcoholysis degree is more favorable for stable cross-linking reaction in the formulation.
  • the mass fraction of the N-methallylamine is preferably 0.4-0.8%, more preferably 0.5-0.7%, and specifically, in the embodiment of the present invention, may be 0.4%, 0.5% % or 0.8%.
  • the amino resin is preferably a methyl etherified melamine resin, and the methyl etherified melamine resin can better match the polyethylene with a degree of polymerization of 1800 and a degree of alcoholysis of 99.5% in the present invention
  • the alcohol undergoes a cross-linking reaction, which makes the reaction product more stable and more stable when it is coated on the dried water-based ink.
  • the mass fraction of the amino resin is preferably 0.5-1.2%, more preferably 0.6-1.0%, and most preferably 0.8-1.0%. Specifically, in the embodiment of the present invention, it may be 0.5%, 1.0% or 1.2% %.
  • the catalyst is preferably xylenesulfonic acid and/or dimethylcyclohexylamine, and the mass fraction of the catalyst is preferably 0.01-0.02%.
  • the catalyst is used for catalyzing the cross-linking reaction between polyvinyl alcohol, N-methallylamine and amino resin.
  • the surfactant is preferably sodium dodecyl sulfonate and/or sodium dodecyl sulfate, and the mass fraction of the surfactant is preferably 0.01-0.02%.
  • the defoamer is preferably a silicone defoamer, and the mass fraction of the defoamer is preferably 0.003-0.005%.
  • the balance is deionized water.
  • the self-adhesive PVOH coating is preferably prepared according to the following steps:
  • the raw materials such as the polyvinyl alcohol can be weighed according to the above-mentioned mass ratio, which is not repeated in the present invention.
  • polyvinyl alcohol is preferably first added to water, stirred and mixed at a speed of 50-150 rpm, then heated to 90-100° C., and then added at a constant temperature of 1-2 hours, defoaming agent and surfactant, and cooled to 40° C. ⁇ 65 °C, then slowly add N-methylallylamine dropwise, after the dropwise addition is completed, the temperature is raised to 70 ⁇ 75 °C, the constant temperature is 1 to 2 hours, the catalyst and the amino resin are added, and the cross-linking reaction is carried out. After the reaction is completed, the temperature is lowered to At room temperature, the material is finally filtered and discharged to obtain a self-adhesive PVOH coating.
  • the time of the cross-linking reaction is preferably 1.5-2.5 hours, more preferably 2 hours; the cross-linking reaction is preferably carried out under stirring conditions, and the stirring speed is preferably 80-160 revolutions/min , more preferably 90-150 revolutions/min, most preferably 100-120 revolutions/min.
  • the above-mentioned self-adhesive PVOH has several advantages: 1. No primer is needed, saving raw material cost and production cost, and improving production efficiency; 2. No solvent, production is safe and environmentally friendly; 3. Can be recycled and reused, and no harmful substances will be produced by incineration. , is an environmentally friendly and environmentally friendly packaging material.
  • the present invention also provides the above-mentioned preparation method of the PVOH coating film for protecting the printing surface, which includes unwinding the BOPP film, printing the water-based ink layer, topcoating the self-adhesive PVOH coating, drying and winding;
  • the coating speed of the self-adhesive PVOH coating is 50-500 m/min, and the coating amount is 0.2-2.5 g/m 2 .
  • the preparation method of the PVOH coating film includes the following steps:
  • the PVOH coating is coated on the ink of the printed layer of the BOPP film by the top coating equipment, and the coating speed is 50 ⁇ 500m/min, preferably 100 ⁇ 400m/min, more preferably 200 ⁇ 300m/min, specifically, in the embodiment of the present invention, it can be 50m/min, 300m/min or 500m/min;
  • the coating weight of the PVOH coating is preferably 0.2 ⁇ 2.5g/m 2 , more preferably It is 0.5-2 g/m 2 , most preferably 1-1.5 g/m 2 , and specifically, in the embodiment of the present invention, it may be 0.2 g/m 2 , 1 g/m 2 or 2.5 g/m 2 .
  • the film needs to have a certain tension control.
  • the principle of tension it can be straightened and flattened to meet the requirements of the film, and the control is: 30-150N.
  • the temperature and drying time of each section of the oven are different.
  • the infrared temperature of the first section is: 80-130°C, preferably 90-120°C, and more preferably 100-110°C.
  • the present invention in the implementation of the present invention, it can be 80°C, 100°C or 130°C; time: 0.5 to 1.5 seconds, or 1 second, and the temperature range of other sections of the electric oven is 70 to 130°C, preferably 80 to 120°C, more preferably is 90-110°C, specifically, in the embodiment of the present invention, it can be 70°C, 90°C or 130°C; time: 5-15 seconds, or 8 seconds;
  • Rewinding process The coated product needs to rewind the film. When rewinding, it is necessary to control the tension of the rewinding and the pressure of the pressing roller. When the rewinding changes from small to large, the tension and pressure are also The process of changing from large to small has an optimal decay rate. The process needs to be finely set according to the substrate film, coating amount, film width, film thickness, etc. The tension of the winding is 30-100N, and the pressure of the roller is 3.0 ⁇ 2kg.
  • the invention provides a PVOH coating film for protecting a printing surface, which sequentially includes a BOPP substrate layer, an ink layer and a PVOH coating layer; the PVOH coating layer is made of a self-adhesive PVOH coating, and the self-adhesive PVOH coating It includes the following components in mass fractions: 3-10% polyvinyl alcohol, 0.4-0.8% N-methallylamine, 0.5-1.2% amino resin, 0.01-0.02% catalyst, 0.01-0.02% of surfactants, 0.003-0.005% defoamer, 87-96.6% deionized water.
  • one side of BOPP is a light film.
  • water-based ink is used to print and dry the light film surface of BOPP to form an ink layer, and then a PVOH coating is applied on the ink layer for curing to form the PVOH coating film of the present invention.
  • the coating film produced by the BOPP printing and PVOH coating of the present invention has an oxygen transmission rate of ⁇ 5.0cc/m 2 /day, and the oxygen transmission rate of the traditional water-based ink after coating is 7.0 ⁇ 8.0cc/ m2 /day.
  • the coating film produced by the BOPP printing and PVOH coating of the present invention has a good friction coefficient, and the kinetic friction coefficient is 0.20-0.25, compared with the printing ink after BOPP coating PVOH coating
  • the friction coefficient of the layer is 0.50-0.65, the friction coefficient is greatly reduced, and the reduction of the friction coefficient provides favorable conditions for the rapid packaging of food.
  • the PVOH coating film of the present invention compared with the traditional BOPP film coating PVOH and then printing method, the PVOH coating protects the ink layer, and the ink on the printing surface will not be damaged in packaging production and product application. , The packaging grade of the product has been greatly improved.
  • the PVOH coating film of the present invention because the PVOH film layer is on the outer surface, has the characteristics of high transparency, good color and smooth hand feel, which greatly improves the texture of the packaged products and improves the use of customers. the comfort and enhance the customer experience.
  • PVOH coating film for protecting the printing surface provided by the present invention and its preparation method are described in detail below with reference to the examples, but it should not be construed as a limitation on the protection scope of the present invention.
  • the substrate layer is a BOPP film with a heat-sealing layer on one side and a glossy film on the other side;
  • the structure and formula of the BOPP film are as follows: the structure is divided into upper, middle and lower layers; the upper layer is prepared from the following raw materials by weight percentage: 98.5% Copolymerized polypropylene and known heat sealants and 1.5% synthetic silica or other inorganic silica.
  • the middle layer is prepared from the following raw materials by weight percentage: 95% of homopolypropylene, 3.5% of low stereoregularity polyolefin, and 1.5% of mixed antistatic agent.
  • the lower layer is prepared from the following raw materials by weight percentage: 95% of homopolypropylene, 2.5% of low stereoregularity polyolefin, and 2.5% of anti-blocking agent.
  • the total thickness of the BOPP substrate film is 8 ⁇ m; the thickness of the upper layer is 0.2 ⁇ m, the thickness of the middle layer is 7.6 ⁇ m, and the thickness of the lower layer is 0.2 ⁇ m.
  • the preparation method is as follows:
  • the self-adhesive PVOH coating layer is prepared from the following raw materials by weight: 3% polyvinyl alcohol (PVOH) main raw material, 0.4% N-methallylamine, 0.5% amino resin , 0.01% catalyst, 0.01% surfactant, 0.003% defoamer, 96.077% deionized water.
  • the degree of polymerization of polyvinyl alcohol was 1800, and the degree of alcoholysis was 99.5%.
  • the amino resin is a methyl etherified melamine resin.
  • the catalyst is any combination of xylenesulfonic acid and dimethylcyclohexylamine.
  • the surfactant is sodium lauryl fluoride.
  • the defoamer is a silicone defoamer.
  • the film needs to have a certain tension control.
  • the principle of tension the film can be straightened and flattened, and the control is: 30N.
  • the oven is divided into several sections, and each section of the oven The temperature and drying time of the oven are different.
  • the infrared temperature of the first section is: 80 °C, time: 0.5 seconds, and the temperature range of the other sections of the electric oven is 70 °C, time: 5 seconds;
  • Rewinding process The coated product needs to rewind the film. When rewinding, it is necessary to control the tension of the rewinding and the pressure of the pressing roller. There is an optimal decay rate in the process of changing from large to small. The process needs to be finely set according to the substrate film, coating amount, film width, film thickness, etc. The tension of the winding is 30N, and the pressure of the roller is 3.0kg.
  • the substrate layer is a BOPP film with a heat-sealing layer on one side and a glossy film on the other side;
  • the structure and formula of the BOPP film are as follows: the structure is divided into upper, middle and lower layers; the upper layer is prepared from the following raw materials by weight percentage: 98.5% Copolymerized polypropylene and known heat sealants and 1.5% synthetic silica or other inorganic silica.
  • the middle layer is prepared from the following raw materials by weight percentage: 96.5% homopolypropylene, 2.5% low stereoregularity polyolefin, and 1% mixed antistatic agent.
  • the lower layer is prepared from the following raw materials by weight percentage: 97.5% homopolypropylene, 1.5% low stereoregularity polyolefin, and 1% antiblocking agent.
  • the total thickness of the BOPP substrate film is 60 ⁇ m; the thickness of the upper layer is 2.0 ⁇ m, the thickness of the middle layer is 56 ⁇ m, and the thickness of the lower layer is 2.0 ⁇ m.
  • the preparation method is as follows:
  • the self-adhesive PVOH coating layer is prepared from the following raw materials by weight: 10% polyvinyl alcohol (PVOH) main raw material, 0.8% N-methallylamine, 1.2% amino resin , 0.02% catalyst, 0.02% surfactant, 0.004% defoamer, 87.956% deionized water.
  • the degree of polymerization of polyvinyl alcohol is 1800, and the degree of alcoholysis is 99.5%.
  • the amino resin is a methyl etherified melamine resin.
  • the catalyst is dimethylcyclohexylamine.
  • the surfactant is sodium lauryl fluoride.
  • the defoamer is a silicone defoamer.
  • the film needs to have a certain tension control.
  • the principle of tension the film can be straightened and flattened, and the control is: 150N.
  • the oven is divided into several sections. The temperature and drying time are different.
  • the infrared temperature of the first stage is: 130°C, time: 1.5 seconds, the temperature range of several sections of the electric oven is 130°C, time: 15 seconds;
  • Rewinding process The coated product needs to rewind the film. When rewinding, it is necessary to control the tension of the rewinding and the pressure of the pressing roller. There is an optimal decay rate in the process of changing from large to small. The process needs to be finely set according to the substrate film, coating amount, film width, film thickness, etc. The tension of the winding is 100N, and the pressure of the roller is 5.0kg.
  • the substrate layer is a BOPP film with a heat-sealing layer and a glossy film on the other side;
  • the structure and formula of the BOPP film are as follows: the structure is divided into upper, middle and lower layers; the upper layer is prepared from the following raw materials by weight: 97% copolymerization Polypropylene and known heat sealants and 3% synthetic silica or other inorganic silica.
  • the middle layer is prepared from the following raw materials by weight percentage: 96% homopolypropylene, 3% low stereoregularity polyolefin, and 1% mixed antistatic agent.
  • the lower layer is prepared from the following raw materials by weight percentage: 96% of homopolypropylene, 2% of low stereoregularity polyolefin, and 2% of anti-blocking agent.
  • the total thickness of the BOPP substrate film is 42 ⁇ m; the thickness of the upper heat sealing layer is 1 ⁇ m, the thickness of the middle layer is 40 ⁇ m, and the thickness of the lower layer is 1 ⁇ m.
  • the self-adhesive PVOH coating layer is prepared from the following raw materials by weight: 6% polyvinyl alcohol (PVOH) main raw material, 0.5% N-methallylamine, 1% amino resin , 0.02% catalyst, 0.02% surfactant, 0.005% defoamer, 92.455% deionized water.
  • the degree of polymerization of polyvinyl alcohol is 1800, and the degree of alcoholysis is 99.5%.
  • the amino resin is a methyl etherified melamine resin.
  • the catalyst is xylene sulfonic acid.
  • the surfactant was sodium lauryl sulfate.
  • the defoamer is a silicone defoamer.
  • the film needs to have a certain tension control.
  • the principle of tension the film can be straightened and flattened, and the control is: 100N.
  • the oven is divided into several sections. The temperature and drying time are different. The infrared temperature of the first section is: 100°C, time: 1 second, the temperature range of the other sections of the electric oven is 90°C, time: 8 seconds;
  • Rewinding process The coated product needs to rewind the film. When rewinding, it is necessary to control the tension of the rewinding and the pressure of the pressing roller. There is an optimal decay rate in the process of changing from large to small. The process needs to be finely set according to the substrate film, coating amount, film width, film thickness, etc. The tension of the winding is 60N, and the pressure of the roller is 1kg.
  • Embodiments 1 to 3 of the present invention all print the BOPP film and then coat the PVOH emulsion, so that a layer of coating is formed on the printing surface to protect the ink on the printing surface from being damaged, and the entire plastic film sequentially includes the adhered substrate layer. , printing layer and coating layer.
  • the coating film in the embodiment has two functional layers, the middle layer is PVOH coating, which provides excellent oxygen barrier performance, and the oxygen transmission rate is ⁇ 0.51cc/m 2 /day, while the traditional coating after printing The oxygen transmission rate of the aqueous ink is 7.0 to 8.0 cc/m 2 /day.
  • the peel strength of the coating film reaches 2.81N/15cm, while the traditional BOPP coated PVOH and then printed, the film peel strength is only 0.6-0.7N/15cm.
  • the inner and outer layers are BOPP heat sealing layer and PE or CPP film layer, which provide good functional characteristics for the packaging heat sealing performance of the product.
  • the heat sealing strength is 3.32N/15cm (120°C ⁇ 0.14MPa ⁇ 1S) , the coefficient of static friction is 0.32, and the coefficient of dynamic friction is 0.30.
  • the invention provides a new PVOH emulsion coating film, which has several important characteristics: firstly, it protects the ink from being damaged after BOPP printing; secondly, it provides a very low friction coefficient for the BOPP film, which is a The subsequent application of the film for rapid packaging provides greater possibilities; the third is to provide excellent barrier properties, so that water-based inks are widely used in the printing of coated films; the fourth is that the surface of the coating has high gloss and good texture. And feel smooth.

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Abstract

提供一种保护印刷面的PVOH涂布膜及其制备方法。该涂布膜依次包括BOPP基材层、油墨层和PVOH涂料层；PVOH涂料层由自粘型PVOH涂料制成，自粘型PVOH涂料包括以下质量分数的组分：3～10%的聚乙烯醇、0.4～0.8%的N-甲基烯丙基胺、0.5～1.2%的氨基树脂、0.01～0.02%的催化剂、0.01～0.02%的表面活性剂、0.003～0.005%的消泡剂、87～96.6%去离子水。自粘PVOH水性涂料在烘干的水性油墨上涂布不会使水性油墨起可逆反应，能使油墨面保持良好的呈现，且易于过机。外层PVOH涂层提供了极佳的阻氧性能，同时具有良好的摩擦系数，为涂布膜的食品快速包装提供了很好的条件，并且避免了包装操作时对印刷层的油墨破坏作用。内层BOPP的热封层为产品的包装热封性能提供了很好的特性。上述方法解决了涂布后再印刷时的水性油墨中的水分对PVOH涂料面破坏的问题，由于印刷后烘干固化，印刷面已经没有了水分，在印刷面上涂布就不会导致印刷面对涂布面的破坏，因此解决了水性油墨使用的局限性问题。

Description

一种保护印刷面的PVOH涂布膜及其制备方法
本申请要求于2020年11月03日提交中国专利局、申请号为202011209697.5、发明名称为“一种保护印刷面的PVOH涂布膜及其制备方法”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
本发明属于膜技术领域，尤其涉及一种保护印刷面的PVOH涂布膜及其制备方法。
背景技术
在目前要求高阻隔食品快速包装上，采用的是BOPP膜上涂布PVOH后，在PVOH涂层上印刷，以达到高的阻隔性能和包装性能。但是由于环保要求越来越严格，使用水性油墨是未来印刷行业的趋势，可是涂布后用水性油墨印刷会严重的破坏涂布面，水性油墨中的水分会导致PVOH面起可逆反应，即固化后的PVOH部分逆反成乳液PVOH，从而使PVOH面受到严重破坏，且水分增多后使整个膜面烘干困难、能耗大及生产效率低，从而进一步导致阻隔性呈几倍降低，透明度显著下降，而且在膜上涂布PVOH涂层上印刷后，由于油墨的附着力不够、耐磨性差，在使用食品快速包装或者搬运过程中时容易导致印刷脱落或刮花，从而影响到食品包装外观性能。而且为了提高产品生产效率，减低生产成本，需要提高生产设备的运行速度，达到快速包装的目的，但传统的涂布后印刷的工艺，印刷面上的摩擦系数比较大，设备快速运行时，会导致生产不顺畅，甚至断膜停机等问题出现，因此在高外观要求高阻隔要求的食品快速包装应用上受到了很大的限制。因此有必要对其进行改进，制出一种阻隔性能强、层与层之间的结合能力强及能够快速包装的环保型涂布膜成为了必备需求。
发明内容
本发明提供了一种保护印刷面的PVOH涂布膜及其制备方法，本发明中的PVOH涂布膜解决了水性油墨使用的局限性问题、水性油墨不会与PVOH涂层起可逆反应。
本发明提供一种保护印刷面的PVOH涂布膜，依次包括BOPP基材层、油墨层和PVOH涂料层；
所述PVOH涂料层由自粘型PVOH涂料制成，所述自粘型PVOH涂料包括以下质量分数的组分：
3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、87～96.6％去离子水。
优选的，所述聚乙烯醇的聚合度为1500～2000，醇解度为99.5％。
优选的，所述氨基树脂为甲醚化三氰氨树脂。
优选的，所述催化剂为二甲苯磺酸和/或二甲基环己胺。
优选的，所述表面活性剂为十二烷基磺酸钠和/或十二烷基硫酸钠；所述消泡剂为有机硅消泡剂。
优选的，所述自粘型PVOH涂料按照以下步骤制备得到：
将聚乙烯醇与水混合，加热至90～100℃，加入消泡剂和表面活性剂，降温至40～65℃，滴加N-甲基烯丙基胺，滴加完毕之后升温至70～75℃，加入催化剂和氨基树脂，进行交联反应，得到自粘型PVOH涂料。
优选的，所述BOPP薄膜包括热封层、中层和光面层；
所述热封层包括以下质量分数的组分：94.5～98.5％共聚聚丙烯与热封料的混合物以及1.5～4.5％硅石；
所述中层包括以下质量分数的组分：94.5～96.5％均聚聚丙烯、2.5～3.5％低立体规则性聚烯烃、1～1.5％混合抗静电剂；
所述光面层包括以下质量分数的组分：85～97.5％均聚聚丙烯、1.5～2.5％低立体规则性聚烯烃、1～2.5％抗连剂。
优选的，所述BOPP基材层的厚度为8～60μm，油墨层的厚度为0.5～3.5μm，PVOH涂料层的厚度为0.3～1.5μm。
本发明提供一种如上文所述的保护印刷面的PVOH涂布膜的制备方法，包括BOPP膜放卷、印刷水性油墨层、面涂自粘型PVOH涂料、烘干和收卷；
所述自粘型PVOH涂料的涂布速度为50～500m/min，涂布量为0.2～2.5g/m 2。
优选的，所述烘干为多段式烘干，第一段的烘干温度为80～130℃，烘干时间为0.5～1.5s；其余段数的烘干温度为70～130℃，烘干时间为5～15s。
本发明提供了一种保护印刷面的PVOH涂布膜，依次包括BOPP基材层、 油墨层和PVOH涂料层；所述PVOH涂料层由自粘型PVOH涂料制成，所述自粘型PVOH涂料包括以下质量分数的组分：3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、87～96.6％去离子水。本发明中的BOPP一面为光膜，生产时在BOPP的光膜面上使用水性油墨印刷烘干成油墨层后，在油墨层上涂布PVOH涂料固化，形成本发明中的PVOH涂布膜。
本发明自主研发了自粘PVOH水性涂料，该涂料在烘干的水性油墨上涂布不会使水性油墨起可逆反应，能使油墨面保持良好的呈现，且易于过机。本发明的涂布膜具有两个功能层，外层为PVOH涂层，一提供了极佳的阻氧性能，二具有良好的摩擦系数，为涂布膜的食品快速包装提供了很好的条件，并且避免了包装操作时对印刷层的油墨破坏作用。内层为BOPP的热封层，为产品的包装热封性能提供了很好的特性。本发明的方法解决了涂布后再印刷时的水性油墨中的水分对PVOH涂料面破坏的问题，因为印刷后烘干固化，印刷面已经没有了水分，在印刷面上涂布就不会导致印刷面对涂布面的破坏，因此解决了水性油墨使用的局限性问题。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。
图1为本发明实施例中PVOH涂布膜的结构示意图；
其中，1为PVOH涂料层，2为油墨层，3为BOPP基材层。
具体实施方式
本发明提供了一种保护印刷面的PVOH涂布膜，依次包括BOPP基材层、油墨层和PVOH涂料层；
所述PVOH涂料层由自粘型PVOH涂料制成，所述自粘型PVOH涂料包括以下质量分数的组分：
3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、 87～96.6％去离子水。
在本发明中，所述BOPP基材层、油墨层和PVOH涂料层之间可以是直接相接触，也可以间接接触，本领域技术人员可以在其中添加一些常规的功能层以实现某些特定的功能。在本发明的以下叙述中，均以具有依次接触的BOPP基材层、油墨层和PVOH涂料层三层结构的PVOH涂布膜为例进行说明。
在本发明中，所述BOPP基材层为具有三层结构的BOPP膜，分别为热封层、中层和光面层。所述BOPP基材层的厚度优选为8～60μm，更优选为10～50μm，最优选为20～40μm，具体的，在本发明的实施例中，可以是8μm、42μm或60μm；所述热封层的厚度优选为0.2～2.0μm，更优选为0.5～1.5μm，具体的，在本发明的实施例中，可以是0.2μm、1.0μm或2.0μm；所述中层的厚度优选为7.6～56μm，更优选为10～45μm，最优选为20～40μm，具体的，在本发明的实施例中，可以是7.6μm、56μm或40μm；所述光面层的厚度优选为0.2～2.0μm，更优选为0.5～1.5μm，具体的，在本发明的实施例中，可以是0.2μm、1.0μm或2.0μm。
所述热封层作为食品包装袋的内层，直接与食品相接触，能够保证包装的热封性能。所述热封层包括以下成分：
94.5～98.5％共聚聚丙烯与热封料的混合物；1.5～4.5％硅石；
在本发明中，所述热封料选用本领域技术人员所熟知的热封料即可，所述硅石可以是合成硅石或其他无机硅石。
所述中层包括以下质量分数的组分94.5～96.5％均聚聚丙烯、2.5～3.5％低立体规则性聚烯烃、1～1.5％混合抗静电剂；
在本发明中，所述抗静电剂为本领域技术人员常用的抗静电剂，本发明在此不再赘述。
所述光面层的表面上印刷水性油墨，所述光面层包括以下质量分数的组分：
85～97.5％均聚聚丙烯、1.5～2.5％低立体规则性聚烯烃、1～2.5％抗连剂。
在本发明中，所述低立体规则性聚烯烃为日本住友集团提供的AV161型号的聚烯烃；所述抗连剂为本领域技术人员常用的抗连剂，本发明在此不再赘 述。
在本发明中，所述油墨层优选为水性油墨层，所述油墨层的厚度优选为0.5～3.5μm，更优选为1～3.0μm，最优选为1.5～2.5μm。
在本发明中，所述PVOH涂料层的厚度优选为0.5μm；所述PVOH涂料层使用本发明自主研发的自粘型PVOH涂料涂布制成，所述PVOH涂料包括以下质量分数的组分：
3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、87～96.6％去离子水。
在本发明中，所述聚乙烯醇的质量分数优选为3～10％，更优选为4～9％，最优选为5～8％，具体的，在本发明的实施例中，可以是3％、6％和10％；所述聚乙烯醇的聚合度为1500～2000，更优选为1600～1900，最优选为1700～1800；所述醇解度优选为99.5％。该聚合度和醇解度范围下的聚乙烯醇在配方中更有利于发生稳定的交联反应。
在本发明中，所述N-甲基烯丙基胺的质量分数优选为0.4～0.8％，更优选为0.5～0.7％，具体的，在本发明的实施例中，可以是0.4％、0.5％或0.8％。
在本发明中，所述氨基树脂优选为甲醚化三氰氨树脂，所述甲醚化三氰胺树脂能更好的与本发明中聚合度为1800，醇解度为99.5％的聚乙烯醇发生交联反应，使反应产物更稳定，且涂布在烘干的水性油墨上更稳定。所述氨基树脂的质量分数优选为0.5～1.2％，更优选为0.6～1.0％，最优选为0.8～1.0％，具体的，在本发明的实施例中，可以是0.5％、1.0％或1.2％。
在本发明中，所述催化剂优选为二甲苯磺酸和/或二甲基环己胺，所述催化剂的质量分数优选为0.01～0.02％。所述催化剂用于催化聚乙烯醇、N-甲基烯丙基胺和氨基树脂之间的交联反应。
在本发明中，所述表面活性剂优选为十二烷基璜酸钠和/或十二烷基硫酸钠，所述表面活性剂的质量分数优选为0.01～0.02％。
在本发明中，所述消泡剂优选为有机硅消泡剂，所述消泡剂的质量分数优选为0.003～0.005％。
余量为去离子水。
在本发明中，所述自粘型PVOH涂料优选按照以下步骤制备得到：
将聚乙烯醇与水混合，加热至90～100℃，加入消泡剂和表面活性剂，降温至40～65℃，滴加N-甲基烯丙基胺，滴加完毕之后升温至70～75℃，加入催化剂和氨基树脂，进行交联反应，得到自粘型PVOH涂料。
在本发明中，所述聚乙烯醇等原料按照上文所述的质量比例称取即可，本发明在此不再赘述。
本发明优选先将聚乙烯醇加入水中，在50～150转/min的速度下搅拌混合，然后加热至90～100℃，恒温1～2小时之后加入消泡剂和表面活性剂，降温至40～65℃，然后缓慢滴加N-甲基烯丙基胺，滴加完毕之后升温至70～75℃，恒温1～2小时，加入催化剂和氨基树脂，进行交联反应，反应完毕后降温至室温，最后过滤出料，得到自粘型PVOH涂料。
在本发明中，所述交联反应的时间优选为1.5～2.5小时，更优选为2小时；所述交联反应优选在搅拌条件下进行，所述搅拌的速度优选为80～160转/min，更优选为90～150转/min，最优选为100～120转/min。
上述的自粘型的PVOH具有几大优点：①无需底胶，节约原料成本及生产成本，提高生产效率；②无溶剂，生产安全环保；③可以回收再利用，焚烧处理也不会产生有害物质，是一种环境友好、环保的包装材料。
本发明还提供了一种上文所述的保护印刷面的PVOH涂布膜的制备方法，包括BOPP膜放卷、印刷水性油墨层、面涂自粘型PVOH涂料、烘干和收卷；
所述自粘型PVOH涂料的涂布速度为50～500m/min，涂布量为0.2～2.5g/m 2。
具体的，所述PVOH涂布膜的制备方法包括以下工序：
(1)放卷工序：在60～130N的张力下，把制备的BOPP膜卷平整的展开，在此张力下，膜卷经过多个导辊连续向前运行，并采用两个相同工位相互交替工作，运用自动拼接，快速换膜，达到连续放卷的目的；
(2)印刷：经过预热后把薄膜的多余的水分烘干、电晕后通过油墨槽，在薄膜表面涂覆了一层油墨层；
(3)面涂工序：通过面涂涂布设备将PVOH涂料涂布在BOPP薄膜的印刷层的油墨上面，涂布速度为50～500m/min，优选为100～400m/min，更优选 为200～300m/min，具体的，在本发明的实施例中，可以是50m/min，300m/min或500m/min；所述PVOH涂料的涂布量优选为0.2～2.5g/m 2，更优选为0.5～2g/m 2，最优选为1～1.5g/m 2，具体的，在本发明的实施例中，可以是0.2g/m 2，1g/m 2或2.5g/m 2。
(4)面涂烘干工序：在烘干过程中，薄膜需要有一定张力控制，张力大小的原则：满足薄膜拉直拉平即可，控制在：30～150N，所述烘箱分为几段，每段的烘箱的温度和烘干的时间都不同，第一段的红外温度为：80～130℃，优选为90～120℃，更优选为100～110℃，具体的，在本发明的实施例中，可以是80℃、100℃或130℃；时间：0.5～1.5秒，还可以是1秒，电热烘箱其他几段的温度范围为70～130℃，优选为80～120℃，更优选为90～110℃，具体的，在本发明的实施例中，可以是70℃、90℃或130℃；时间：5～15秒，还可以是8秒；
(5)在线检测工序：采用相机在线图像扫描的工作原理，在生产线高速生产时，采用光源照射产品表面，同时通过相机实时扫描并采集光源照射处的产品图像，将采集的图像进行处理与分割，并记录标记，所述的相机为CCD工业相机，所述的光源为高亮度LED线性聚光光源，用于判定产品质量及烘干情况；
(6)收卷工序：涂布好的产品需要对薄膜进行收卷，收卷时需要控制收卷的张力及压辊的压力，收卷的由小变大时，所受的张力及压力也由大变小的过程有一最佳衰减率，工艺过程需要根据基材膜、涂布量、膜宽、膜厚等做精细的设定，收卷的张力在30～100N，压辊压力在3.0±2kg。
本发明提供了一种保护印刷面的PVOH涂布膜，依次包括BOPP基材层、油墨层和PVOH涂料层；所述PVOH涂料层由自粘型PVOH涂料制成，所述自粘型PVOH涂料包括以下质量分数的组分：3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、87～96.6％去离子水。本发明中的BOPP一面为光膜，生产时在BOPP的光膜面上使用水性油墨印刷烘干成油墨层后，在油墨层上涂布PVOH涂料固化，形成本发明中的PVOH涂布膜。
与现有传统BOPP涂布PVOH后再印刷方式的技术相比，本发明的有益 效果是：
1、本发明的BOPP印刷后与PVOH涂布制作成的涂布膜，其氧气透过率≤5.0cc/m 2/day，传统的涂布后印刷水性的油墨的氧气透过率为7.0～8.0cc/m 2/day。
2、本发明的BOPP印刷后与PVOH涂布制作成的涂布膜，该涂布膜具有良好的摩擦系数，动摩擦系数在0.20～0.25，相对比与BOPP涂布PVOH涂层后再印刷的油墨层的摩擦系数0.50～0.65，其摩擦系数大大降低，摩擦系数的降低给食品的快速包装提供了有利的条件。
3、本发明的PVOH涂布膜，与传统的BOPP膜涂布PVOH后再印刷的方法相比，PVOH涂层保护了油墨层，在包装生产及产品应用上印刷面的油墨都不会被破坏，对产品的包装档次有大的提升。
4、本发明的PVOH涂布膜，由于PVOH膜层在外表面，PVOH膜层的特性：透明度高、色泽好、手感滑爽，这给所包装产品的质感有很大的提高，提高了客户使用的舒适感，增加了客户的体验度。
为了进一步说明本发明，以下结合实施例对本发明提供的一种保护印刷面的PVOH涂布膜及其制备方法进行详细描述，但不能将其理解为对本发明保护范围的限定。
实施例1
基材层为一面热封层、另一面光膜的BOPP薄膜；BOPP薄膜的结构和配方如下：结构共分为上、中、下三层；上层由下述重量百分比原料配制而成：98.5％共聚聚丙烯及已知的热封料和1.5％合成硅石或其它无机硅石。中间层由下述重量百分比的原料配制而成：95％均聚聚丙烯、3.5％低立体规则性聚烯烃、1.5％混合抗静电剂。下层由下述重量百分比的原料配制而成：95％均聚聚丙烯、2.5％低立体规则性聚烯烃、2.5％抗连剂。BOPP基材膜总厚度为8μm；上层厚度为0.2μm，中间层厚度为7.6μm，下层厚度0.2μm。
制备方法如下：
(1)乳液配置：自粘型PVOH涂料层由下述重量含量的原料配制而成：3％的聚乙烯醇(PVOH)主体原料、0.4％N-甲基烯丙基胺、0.5％氨基树脂、0.01％催化剂、0.01％表面活性剂、0.003％消泡剂、96.077％去离子水。聚乙烯 醇聚合度为1800，醇解度为99.5％。氨基树脂为甲醚化三氰胺树脂。催化剂为二甲苯磺酸、二甲基环己胺的任意组合。表面活性剂为十二烷基璜酸钠。消泡剂为有机硅消泡剂。
根据重量份比称取聚乙烯醇与去离子水混合搅拌，搅拌速度50转/min，加热至90℃，恒温1h后加入消泡剂及表面活性剂，降温至40℃，缓慢滴加N-甲基烯丙基胺，滴加完毕后升温至70℃恒温1h，再次加入催化剂和氨基树脂，恒温1.5h，搅拌速度为80转/min充分搅拌均匀，后降至室温，最后过滤出料，制得PVOH涂料；
(2)放卷工序：在60N的张力下，把制备的BOPP膜卷平整的展开，在此张力下，膜卷经过多个导辊连续向前运行，并采用两个相同工位相互交替工作，运用自动拼接，快速换膜，达到连续放卷的目的；
(3)印刷：经过预热后把薄膜的多余的水分烘干、电晕后通过油墨槽，在薄膜表面涂覆了一层0.5μm厚的油墨层；
(4)面涂工序：通过面涂涂布设备将PVOH涂料涂布在BOPP薄膜的印刷层的油墨上面，涂布速度为50m/min；涂料层的涂布量为0.2g/m 2，厚度为0.5μm；
(5)面涂烘干工序：在烘干过程中，薄膜需要有一定张力控制，张力大小的原则：满足薄膜拉直拉平即可，控制在：30N，烘箱分为几段，每段的烘箱的温度和烘干的时间都不同，第一段的红外温度为：80℃，时间：0.5秒，电热烘箱其他几段的温度范围为70℃，时间：5秒；
(6)在线检测工序：采用相机在线图像扫描的工作原理，在生产线高速生产时，采用光源照射产品表面，同时通过相机实时扫描并采集光源照射处的产品图像，将采集的图像进行处理与分割，并记录标记，相机为CCD工业相机，光源为高亮度LED线性聚光光源，用于判定产品质量及烘干情况；
(7)收卷工序：涂布好的产品需要对薄膜进行收卷，收卷时需要控制收卷的张力及压辊的压力，收卷的由小变大时，所受的张力及压力也由大变小的过程有一最佳衰减率，工艺过程需要根据基材膜、涂布量、膜宽、膜厚等做精细的设定，收卷的张力在30N，压辊压力在3.0kg。
实施例2
基材层为一面热封层、另一面光膜的BOPP薄膜；BOPP薄膜的结构和配方如下：结构共分为上、中、下三层；上层由下述重量百分比原料配制而成：98.5％共聚聚丙烯及已知的热封料和1.5％合成硅石或其它无机硅石。中间层由下述重量百分比的原料配制而成：96.5％均聚聚丙烯、2.5％低立体规则性聚烯烃、1％混合抗静电剂。下层由下述重量百分比的原料配制而成：97.5％均聚聚丙烯、1.5％低立体规则性聚烯烃、1％抗连剂。BOPP基材膜总厚度为60μm；上层厚度为2.0μm，中间层厚度为56μm，下层厚度2.0μm。
制备方法如下：
(1)乳液配置：自粘型PVOH涂料层由下述重量含量的原料配制而成：10％的聚乙烯醇(PVOH)主体原料、0.8％N-甲基烯丙基胺、1.2％氨基树脂、0.02％催化剂、0.02％表面活性剂、0.004％消泡剂、87.956％去离子水。聚乙烯醇聚合度为1800，醇解度为99.5％。氨基树脂为甲醚化三氰胺树脂。催化剂为二甲基环己胺。表面活性剂为十二烷基璜酸钠。消泡剂为有机硅消泡剂。
根据重量份比称取聚乙烯醇与去离子水混合搅拌，搅拌速度150转/min，加热至100℃，恒温2h后加入消泡剂及表面活性剂，降温至65℃，缓慢滴加N-甲基烯丙基胺，滴加完毕后升温至75℃恒温2h，再次加入催化剂和氨基树脂，恒温2.5h，搅拌速度为160转/min充分搅拌均匀，后降至室温，最后过滤出料，制得PVOH涂料；
(2)放卷工序：在130N的张力下，把制备的BOPP膜卷平整的展开，在此张力下，膜卷经过多个导辊连续向前运行，并采用两个相同工位相互交替工作，运用自动拼接，快速换膜，达到连续放卷的目的；
(3)印刷：经过预热后把薄膜的多余的水分烘干、电晕后通过油墨槽，在薄膜表面涂覆了一层3.5μm厚的油墨层；
(4)面涂工序：通过面涂涂布设备将PVOH涂料涂布在BOPP薄膜的印刷层的油墨上面，涂布速度为500m/min；涂料层的涂布量为2.5g/m 2；厚度为0.5μm；
(5)面涂烘干工序：在烘干过程中，薄膜需要有一定张力控制，张力大小的原则：满足薄膜拉直拉平即可，控制在：150N，烘箱分为几段，每段的烘箱的温度和烘干的时间都不同，第一段的红外温度为：130℃，时间：1.5 秒，电热烘箱几段的温度范围为130℃，时间：15秒；
(6)在线检测工序：采用相机在线图像扫描的工作原理，在生产线高速生产时，采用光源照射产品表面，同时通过相机实时扫描并采集光源照射处的产品图像，将采集的图像进行处理与分割，并记录标记，相机为CCD工业相机，光源为高亮度LED线性聚光光源，用于判定产品质量及烘干情况；
(7)收卷工序：涂布好的产品需要对薄膜进行收卷，收卷时需要控制收卷的张力及压辊的压力，收卷的由小变大时，所受的张力及压力也由大变小的过程有一最佳衰减率，工艺过程需要根据基材膜、涂布量、膜宽、膜厚等做精细的设定，收卷的张力在100N，压辊压力在5.0kg。
实施例3
基材层为一面热封层另一面光膜的BOPP薄膜；BOPP薄膜的结构和配方如下：结构共分为上、中、下三层；上层由下述重量百分比原料配制而成：97％共聚聚丙烯及已知的热封料和3％合成硅石或其它无机硅石。中间层由下述重量百分比的原料配制而成：96％均聚聚丙烯、3％低立体规则性聚烯烃、1％混合抗静电剂。下层由下述重量百分比的原料配制而成：96％均聚聚丙烯、2％低立体规则性聚烯烃、2％抗连剂。BOPP基材膜总厚度为42μm；上层的热封层厚度为1μm，中间层厚度为40μm，下层厚度1μm。
其中包括以下工序：
(1)乳液配置：自粘型PVOH涂料层由下述重量含量的原料配制而成：6％的聚乙烯醇(PVOH)主体原料、0.5％N-甲基烯丙基胺、1％氨基树脂、0.02％催化剂、0.02％表面活性剂、0.005％消泡剂、92.455％去离子水。聚乙烯醇聚合度为1800，醇解度为99.5％。氨基树脂为甲醚化三氰胺树脂。催化剂为二甲苯磺酸。表面活性剂为十二烷基硫酸钠。消泡剂为有机硅消泡剂。
根据重量份比称取聚乙烯醇与去离子水混合搅拌，搅拌速度100转/min，加热至95℃，恒温1.5h后加入消泡剂及表面活性剂，降温至50℃，缓慢滴加N-甲基烯丙基胺，滴加完毕后升温至70℃恒温1.5h，再次加入催化剂和氨基树脂，恒温2h，搅拌速度为100转/min充分搅拌均匀，后降至室温，最后过滤出料，制得PVOH涂料；
(2)放卷工序：在100N的张力下，把制备的BOPP膜卷平整的展开， 在此张力下，膜卷经过多个导辊连续向前运行，并采用两个相同工位相互交替工作，运用自动拼接，快速换膜，达到连续放卷的目的；
(3)印刷：经过预热后把薄膜的多余的水分烘干、电晕后通过油墨槽，在薄膜表面涂覆了一层3μm厚的油墨层；
(4)面涂工序：通过面涂涂布设备将PVOH涂料涂布在BOPP薄膜的印刷层的油墨上面，涂布速度为300m/min；涂料层的涂布量为1g/m 2；厚度为0.5μm
(5)面涂烘干工序：在烘干过程中，薄膜需要有一定张力控制，张力大小的原则：满足薄膜拉直拉平即可，控制在：100N，烘箱分为几段，每段的烘箱的温度和烘干的时间都不同，第一段的红外温度为：100℃，时间：1秒，电热烘箱其他几段的温度范围为90℃，时间：8秒；
(6)在线检测工序：采用相机在线图像扫描的工作原理，在生产线高速生产时，采用光源照射产品表面，同时通过相机实时扫描并采集光源照射处的产品图像，将采集的图像进行处理与分割，并记录标记，相机为CCD工业相机，光源为高亮度LED线性聚光光源，用于判定产品质量及烘干情况；
(7)收卷工序：涂布好的产品需要对薄膜进行收卷，收卷时需要控制收卷的张力及压辊的压力，收卷的由小变大时，所受的张力及压力也由大变小的过程有一最佳衰减率，工艺过程需要根据基材膜、涂布量、膜宽、膜厚等做精细的设定，收卷的张力在60N，压辊压力在1kg。
本发明的实施例1～3均对BOPP膜印刷后再涂布PVOH乳液，使印刷面上形成了一层涂层用于保护印刷面油墨不被破坏，整个塑料薄膜依次包括粘连的基材层、印刷层和涂料层。实施例中的涂布膜具有两个功能层，中间层为PVOH涂层，其提供了极佳的阻氧性能，氧气透过率＜0.51cc/m 2/day，而传统的涂布后印刷水性的油墨的氧气透过率为7.0～8.0cc/m 2/day。涂布膜剥离强度达到2.81N/15cm，而传统的BOPP涂布PVOH后印刷，薄膜剥离强度只有0.6～0.7N/15cm。内、外层为BOPP的热封层和PE或CPP的薄膜层，为产品的包装热封性能提供了很好的功能特性，热封强度为3.32N/15cm(120℃×0.14MPa×1S)，静摩擦系数为0.32，动摩擦系数为0.30。
本发明提供了一种新的PVOH乳液涂布膜，其具有几个重要的特性：一 是保护了BOPP印刷后油墨不被破坏的作用；二是给BOPP薄膜提供了非常低的摩擦系数，为薄膜后续做快速包装应用提供了更大的可能性；三是提供了极佳阻隔特性，使水性油墨在涂布薄膜的印刷得到广泛应用；四是制成的涂层表面光泽度高、质感好及手感爽滑。
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. 一种保护印刷面的PVOH涂布膜，依次包括BOPP基材层、油墨层和PVOH涂料层；
    所述PVOH涂料层由自粘型PVOH涂料制成，所述自粘型PVOH涂料包括以下质量分数的组分：
    3～10％的聚乙烯醇、0.4～0.8％的N-甲基烯丙基胺、0.5～1.2％的氨基树脂、0.01～0.02％的催化剂、0.01～0.02％的表面活性剂、0.003～0.005％的消泡剂、87～96.6％去离子水。
  2. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述聚乙烯醇的聚合度为1500～2000，醇解度为99.5％。
  3. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述氨基树脂为甲醚化三氰氨树脂。
  4. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述催化剂为二甲苯磺酸和/或二甲基环己胺。
  5. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述表面活性剂为十二烷基磺酸钠和/或十二烷基硫酸钠；所述消泡剂为有机硅消泡剂。
  6. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述自粘型PVOH涂料按照以下步骤制备得到：
    将聚乙烯醇与水混合，加热至90～100℃，加入消泡剂和表面活性剂，降温至40～65℃，滴加N-甲基烯丙基胺，滴加完毕之后升温至70～75℃，加入催化剂和氨基树脂，进行交联反应，得到自粘型PVOH涂料。
  7. 根据权利要求1所述的PVOH涂布膜，其特征在于，所述BOPP薄膜包括热封层、中层和光面层；
    所述热封层包括以下质量分数的组分：94.5～98.5％共聚聚丙烯与热封料的混合物以及1.5～4.5％硅石；
    所述中层包括以下质量分数的组分：94.5～96.5％均聚聚丙烯、2.5～3.5％低立体规则性聚烯烃、1～1.5％混合抗静电剂；
    所述光面层包括以下质量分数的组分：85～97.5％均聚聚丙烯、1.5～2.5％低 立体规则性聚烯烃、1～2.5％抗连剂。
  8. 如权利要求1～7任意一项所述的PVOH涂布膜，其特征在于，所述BOPP基材层的厚度为8～60μm，油墨层的厚度为0.5～3.5μm，PVOH涂料层的厚度为0.3～1.5μm。
  9. 一种如权利要求1～7任意一项所述的保护印刷面的PVOH涂布膜的制备方法，包括BOPP膜放卷、印刷水性油墨层、面涂自粘型PVOH涂料、烘干和收卷；
    所述自粘型PVOH涂料的涂布速度为50～500m/min，涂布量为0.2～2.5g/m 2。
  10. 根据权利要求8所述的制备方法，其特征在于，所述烘干为多段式烘干，第一段的烘干温度为80～130℃，烘干时间为0.5～1.5s；其余段数的烘干温度为70～130℃，烘干时间为5～15s。
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