WO2022267198A1 - Anti-scratch and anti-static coating film and preparation method therefor - Google Patents

Anti-scratch and anti-static coating film and preparation method therefor Download PDF

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Publication number
WO2022267198A1
WO2022267198A1 PCT/CN2021/112193 CN2021112193W WO2022267198A1 WO 2022267198 A1 WO2022267198 A1 WO 2022267198A1 CN 2021112193 W CN2021112193 W CN 2021112193W WO 2022267198 A1 WO2022267198 A1 WO 2022267198A1
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weight
parts
scratch
water
coating
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PCT/CN2021/112193
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French (fr)
Chinese (zh)
Inventor
王恩飞
朱清梅
袁业兴
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海南赛诺实业有限公司
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Publication of WO2022267198A1 publication Critical patent/WO2022267198A1/en

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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
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening 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
    • C08J7/0427—Coating with only one layer of a composition containing 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
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to the technical field of coating films for food packaging, in particular to an anti-scratch and antistatic coating film and a preparation method thereof.
  • BOPET film is a biaxially oriented polyester film.
  • BOPET film has the characteristics of high strength, good rigidity, transparency, and high gloss, as well as odorless, tasteless, colorless, non-toxic, and outstanding strength and toughness; but it also has shortcomings, not antistatic and anti-scratch.
  • BOPET film is a material with good insulating properties, so during the production process, due to friction, a large amount of static electricity will be generated on the surface of the film.
  • the generation of static electricity not only affects the normal operation of film producers, but also the film with static electricity is easy to absorb dust, which affects the cleanliness of the film and the later use of the film.
  • the film and the film are easily adsorbed together, which affects the winding effect; in the post-processing process with high concentrations of flammable and explosive solvents, static electricity can easily cause combustion and explosion.
  • the anti-scratch BOPET film used in industry has not been domestically produced.
  • the anti-scratch BOPET film materials required by the industry mainly rely on imports.
  • the imported anti-scratch PET film is mainly composed of four parts, which are hard coating, PET sheet, treatment layer and PE protective film.
  • the hardened coating in the middle is the key core component, which plays a key anti-scratch role, and is a research hotspot for the majority of scientific researchers.
  • the object of the present invention is to provide a kind of anti-scratch, antistatic type coating film and preparation method thereof, anti-scratch provided by the invention, antistatic type coating film has good anti-scratch performance and Antistatic properties.
  • the invention provides an anti-scratch, antistatic coating film, comprising:
  • a water-based functional coating compounded on the base film is A water-based functional coating compounded on the base film
  • the water-based functional coating is prepared from raw materials comprising the following components:
  • wetting agent 0.1 to 0.5 parts by weight of wetting agent
  • the crosslinking agent is N-methylolacrylamide.
  • the base film is a BOPET film.
  • the modifying agent is methyltriethoxysilane and/or vinyltrimethoxysilane.
  • the specific surface area of the nano silicon dioxide is 100m 2 /g-300m 2 /g, and the particle size is 10nm-15nm.
  • the nonionic antistatic agent is glycerol-stearate.
  • the wetting agent is ethanol or acetylene glycol.
  • the present invention also provides a method for preparing the anti-scratch and antistatic coating film described in the above technical solution, comprising the following steps:
  • step b) coating the water-based functional coating obtained in step a) on the base film, forming a water-based functional coating after drying, and obtaining an anti-scratch and antistatic coating film after winding.
  • said step a) is specifically:
  • urethane acrylate into the reaction kettle, add the modifier at 20°C ⁇ 30°C, 100r/min ⁇ 120r/min and continue stirring for 15min ⁇ 25min, then add crosslinking agent and soft water, continue stirring for 25min ⁇ 35min, and finally Add nano-silica, non-ionic antistatic agent, wetting agent and defoamer and stir evenly to obtain a water-based functional coating.
  • step b) before coating described in step b), it also includes:
  • Corona treatment is performed on the base film to make the surface tension of the base film reach 45dyn/cm-55dyn/cm.
  • the dry coating weight of the coating in step b) is 0.5 g/m 2 -1.0 g/m 2 .
  • the invention provides an anti-scratch and antistatic coating film, comprising: a base film; a water-based functional coating compounded on the base film; the water-based functional coating is prepared from raw materials comprising the following components Components: 20 to 35 parts by weight of polyurethane acrylate; 5 to 10 parts by weight of crosslinking agent; 5 to 10 parts by weight of modifier; 0.5 to 1.5 parts by weight of nano silicon dioxide; 2 to 4 parts by weight of static agent; 0.1 to 0.5 parts by weight of wetting agent; 0.1 to 0.5 parts by weight of defoamer; 35 to 70 parts by weight of soft water; Methacrylamide.
  • the anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film.
  • the water-based functional coating adopts specific content components to achieve The overall better interaction, so that the overall coating film has good anti-scratch performance and antistatic performance at the same time.
  • Experimental results show that the anti-scratch and antistatic coating film provided by the invention has a scratch resistance of no less than 60g, and the surface resistance of the coating film is below 10 9 ⁇ .
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the invention provides an anti-scratch, antistatic coating film, comprising:
  • a water-based functional coating compounded on the base film is A water-based functional coating compounded on the base film
  • the water-based functional coating is prepared from raw materials comprising the following components:
  • wetting agent 0.1 to 0.5 parts by weight of wetting agent
  • the crosslinking agent is N-methylolacrylamide.
  • the anti-scratch and antistatic coating film includes a base film and a water-based functional coating compounded on the base film, preferably a base film and a water-based functional coating compounded on the base film. layer composition.
  • the base film is preferably a BOPET film.
  • the source of the BOPET film there is no special limitation on the source of the BOPET film, and commercially available products well known to those skilled in the art can be used.
  • the water-based functional coating is prepared from raw materials comprising the following components:
  • wetting agent 0.1 to 0.5 parts by weight of wetting agent
  • the water-based functional coating is prepared from raw materials including polyurethane acrylate, crosslinking agent, modifier, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoamer and soft water , preferably prepared from polyurethane acrylate, cross-linking agent, modifier, nano-silica, non-ionic antistatic agent, wetting agent, defoamer and soft water.
  • the polyurethane acrylate is a fatty acid polyurethane hexafunctional acrylic resin.
  • the present invention has no special limitation on its source, and commercially available or self-made products well known to those skilled in the art can be used.
  • the polyurethane acrylate is WDS-6505.
  • the water-based functional coating includes 20 to 35 parts by weight of polyurethane acrylate.
  • the crosslinking agent is N-methylolacrylamide, which can be commercially available products well known to those skilled in the art.
  • the present invention innovatively introduces N-methylol acrylamide as a crosslinking agent, which has a double bond conjugated with a carbonyl group and a reactive methylol group in its molecule. Due to the introduction of a condensation-functional methylol group, the polyurethane
  • the acrylic resin is cross-linked to enhance the bonding properties of the functional coating.
  • the water-based functional coating includes 5 to 10 parts by weight of a crosslinking agent.
  • the modifying agent is preferably methyltriethoxysilane and/or vinyltrimethoxysilane, more preferably methyltriethoxysilane and vinyltrimethoxysilane.
  • the modifier is methyltriethoxysilane and vinyltrimethoxysilane with a mass ratio of 1:1.
  • the source of the modifying agent is not particularly limited, and commercially available products well known to those skilled in the art can be used.
  • the water-based functional coating includes 5 to 10 parts by weight of modifier.
  • the specific surface area of the nano-silica is preferably 100m 2 /g-300m 2 /g, more preferably 200m 2 /g; the particle size of the nano-silica is preferably 10nm-15nm, more preferably Preferably 12nm.
  • the silicon-oxygen bond in the nano-silica has strong polarity, and the surface of the silica particles often adsorbs certain combined water and hydroxyl groups, so the silica particles have relatively high surface energy, Bareness on the surface of the coating film helps to increase the polarity and interfacial tension of the surface of the pre-coating film, making the surface of the functional coating easy to wet; nano-silica particles form protrusions on the surface of the coating film, making the surface rough, Play a good anti-adhesion effect.
  • the present invention has no special limitation on the source of the nano-silica, and commercially available or self-made fumed silica well known to those skilled in the art can be used.
  • the water-based functional coating includes 0.5 to 1.5 parts by weight of nano silicon dioxide.
  • the nonionic antistatic agent is preferably glycerol-stearate.
  • the source of the nonionic antistatic agent there is no special limitation on the source of the nonionic antistatic agent, and commercially available products well known to those skilled in the art can be used.
  • the water-based functional coating includes 2 to 4 parts by weight of a nonionic antistatic agent.
  • the wetting agent is preferably ethanol or acetylene glycol, more preferably acetylene glycol.
  • the source of the wetting agent is not particularly limited, and commercially available products well known to those skilled in the art can be used.
  • the water-based functional coating includes 0.1 to 0.5 parts by weight of a wetting agent.
  • the defoamer is preferably a silicone defoamer.
  • the water-based functional coating includes 0.1 to 0.5 parts by weight of a defoamer.
  • the present invention has no special limitation on the source of the soft water.
  • the water-based functional coating includes 35 parts by weight to 70 parts by weight of soft water, more preferably 38.5 parts by weight to 67.3 parts by weight.
  • the anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film.
  • the water-based functional coating adopts specific content components to achieve overall better interaction, Therefore, the overall coating film has good anti-scratch performance and antistatic performance at the same time, and can be further applied to food packaging as a high-barrier antistatic coating film.
  • the present invention also provides a method for preparing the anti-scratch and antistatic coating film described in the above technical solution, comprising the following steps:
  • step b) coating the water-based functional coating obtained in step a) on the base film, forming a water-based functional coating after drying, and obtaining an anti-scratch and antistatic coating film after winding.
  • the polyurethane acrylate, crosslinking agent, modifying agent, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoaming agent and soft water are uniformly mixed to obtain the water-based functional coating.
  • urethane acrylate cross-linking agent, modifying agent, nano silicon dioxide, non-ionic antistatic agent, wetting agent, defoamer and soft water are the same as those in the above-mentioned technical scheme, do not mention here Let me repeat.
  • the invention adopts the method of "one-pot cooking” to firstly prepare the water-based functional coating.
  • the step a) is preferably specifically:
  • urethane acrylate into the reaction kettle, add the modifier at 20°C ⁇ 30°C, 100r/min ⁇ 120r/min and continue stirring for 15min ⁇ 25min, then add crosslinking agent and soft water, continue stirring for 25min ⁇ 35min, and finally Add nano-silica, non-ionic antistatic agent, wetting agent and defoamer and stir evenly to obtain a water-based functional coating;
  • a modifying agent is firstly added to the polyurethane acrylate, so that the cross-linking density formed after forming a film is high, thereby endowing the polyurethane acrylic resin with higher hardness and achieving good anti-scratch performance.
  • the present invention coats the obtained water-based functional coating on the base film, forms a water-based functional coating after drying, and obtains an anti-scratch and antistatic coating film after winding.
  • the base film is the same as that in the above technical solution, and will not be repeated here.
  • the coating before the coating, preferably also include:
  • Corona treatment is performed on the base film to make the surface tension of the base film reach 50 dyn/cm.
  • the dry coating amount of the coating is preferably 0.5g/m 2 to 1.0g/m 2 , preferably 0.8g/m 2 m 2 .
  • the drying temperature is preferably 90°C to 110°C, more preferably 95°C to 105°C.
  • the present invention has no special limitation on the drying method, and far-infrared or hot air drying well known to those skilled in the art can be used.
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the invention provides an anti-scratch and antistatic coating film, comprising: a base film; a water-based functional coating compounded on the base film; the water-based functional coating is prepared from raw materials comprising the following components Components: 20 to 35 parts by weight of polyurethane acrylate; 5 to 10 parts by weight of crosslinking agent; 5 to 10 parts by weight of modifier; 0.5 to 1.5 parts by weight of nano silicon dioxide; 2 to 4 parts by weight of static agent; 0.1 to 0.5 parts by weight of wetting agent; 0.1 to 0.5 parts by weight of defoamer; 35 to 70 parts by weight of soft water; Methacrylamide.
  • the anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film.
  • the water-based functional coating adopts specific content components to achieve The overall better interaction, so that the overall coating film has good anti-scratch performance and antistatic performance at the same time.
  • Experimental results show that the anti-scratch and antistatic coating film provided by the invention has a scratch resistance of not less than 60g, and the surface resistance of the coating film is below 10 9 ⁇ .
  • the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
  • the raw materials used in the following examples of the present invention are all commercially available; wherein, the polyurethane acrylate (aliphatic PUA) is WDS-6505, the crosslinking agent is N-methylolacrylamide, and the modifier is 1:1 mass ratio Methyltriethoxysilane and vinyltrimethoxysilane, nano silica is fumed silica with a specific surface area of 200m 2 /g and a particle size of 12nm, and the nonionic antistatic agent is glycerol-stearate , the wetting agent is acetylene glycol, and the defoamer is silicone defoamer.
  • the polyurethane acrylate aliphatic PUA
  • the crosslinking agent is N-methylolacrylamide
  • the modifier is 1:1 mass ratio Methyltriethoxysilane and vinyltrimethoxysilane
  • nano silica is fumed silica with a specific surface area of 200m 2 /g and a particle size
  • the anti-scratch, antistatic type coating film provided by the embodiment of the present invention 1 is tested for performance, wherein, the anti-scratch test method is: characterize the scratch resistance with the experimental method of the critical load that occurs scratches; During the test, Put the sandpaper on the surface of the film, load the sandpaper with a load of 0-100g, pull the sandpaper at a constant speed of about 10mm/s, and use the minimum mass with obvious scratches to indicate the scratch resistance of the coating; the antistatic performance
  • the test standard is GB/T 15662-1995.
  • test results are as follows: the test scratch resistance is 60 g, and the surface resistance of the coating film is 10 9 ⁇ .
  • Example 2 Using the preparation method provided in Example 1, the difference is: no modifier is added; a coated film is obtained; and its scratch resistance is 45 g.
  • Example 2 Using the preparation method provided in Example 2, the difference is: no non-ionic antistatic agent is added; a coating film is obtained; its surface resistance is 10 10 ⁇ .
  • Example 3 of the present invention A performance test was performed on the anti-scratch and antistatic coating film provided in Example 3 of the present invention.
  • the scratch resistance was 65 g, and the surface resistance of the coating film was 10 8 ⁇ .

Abstract

An anti-scratch and anti-static coating film, comprising: a base film; a water-based functional coating compounded on the base film; the water-based functional coating is prepared from raw materials comprising the following components: 20 parts by weight to 35 parts by weight of urethane acrylate; 5 parts by weight to 10 parts by weight of a crosslinking agent; 5 parts by weight to 10 parts by weight of a modifier; 0.5 parts by weight to 1.5 parts by weight of nano-silicon dioxide; 2 parts by weight to 4 parts by weight of a nonionic anti-static agent; 0.1 parts by weight to 0.5 parts by weight of a wetting agent; 0.1 parts by weight to 0.5 parts by weight of a defoaming agent; and 35 parts by weight to 70 parts by weight of soft water; the crosslinking agent is N-methylol acrylamide.

Description

一种防刮伤、抗静电型涂布膜及其制备方法Anti-scratch, antistatic coating film and preparation method thereof
本申请要求于2021年6月23日提交中国专利局、申请号为202110700312.3、发明名称为“一种防刮伤、抗静电型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。This application claims the priority of the Chinese patent application submitted to the China Patent Office on June 23, 2021, with the application number 202110700312.3, and the title of the invention is "An anti-scratch, antistatic coating film and its preparation method". The entire contents are incorporated by reference in this application.
技术领域technical field
本发明涉及食品包装用涂布膜技术领域，更具体地说，是涉及一种防刮伤、抗静电型涂布膜及其制备方法。The invention relates to the technical field of coating films for food packaging, in particular to an anti-scratch and antistatic coating film and a preparation method thereof.
背景技术Background technique
BOPET薄膜是双向拉伸聚酯薄膜。BOPET薄膜具有强度高、刚性好、透明、光泽度高等特点，以及无嗅、无味、无色、无毒、突出的强韧性；但是它也有不足，不能抗静电和防刮伤。BOPET film is a biaxially oriented polyester film. BOPET film has the characteristics of high strength, good rigidity, transparency, and high gloss, as well as odorless, tasteless, colorless, non-toxic, and outstanding strength and toughness; but it also has shortcomings, not antistatic and anti-scratch.
BOPET薄膜是绝缘性能较好的材料，所以在生产的过程中，由于摩擦作用，薄膜表面将产生大量的静电。静电的产生不但影响薄膜生产者的正常操作，而且带静电的薄膜很容易吸附灰尘，影响薄膜的洁净度和薄膜后期的使用。当薄膜收卷时，薄膜和薄膜容易吸附在一起，影响收卷效果；在有高浓度易燃、易爆溶剂的后加工过程中，静电很容易引起燃烧和爆炸。BOPET film is a material with good insulating properties, so during the production process, due to friction, a large amount of static electricity will be generated on the surface of the film. The generation of static electricity not only affects the normal operation of film producers, but also the film with static electricity is easy to absorb dust, which affects the cleanliness of the film and the later use of the film. When the film is rolled, the film and the film are easily adsorbed together, which affects the winding effect; in the post-processing process with high concentrations of flammable and explosive solvents, static electricity can easily cause combustion and explosion.
目前尽管国内相关文献有报道可以制得铅笔硬度在3H以上且有较好抗划伤性能的BOPET表面抗划伤涂层，但是大多是集中于在聚碳酸酯(PC)和有机玻璃玻璃(PMMA)表面，工业上所用到的表面抗划伤BOPET薄膜并没有国产化。工业上所需抗划伤的BOPET薄膜材料还主要依赖于进口。进口防刮伤PET薄膜主要由四部分组成，分别为硬化涂层、PET片材、处理层以及PE保护膜所组成。在这中间硬化涂层是其中关键的核心组成，起着关键防刮伤的作用，是广大科研工作者研究的热点。At present, although there are reports in relevant domestic literature that the scratch-resistant coating on the surface of BOPET with a pencil hardness above 3H and good scratch resistance can be obtained, most of them are concentrated on polycarbonate (PC) and plexiglass (PMMA). ) surface, the anti-scratch BOPET film used in industry has not been domestically produced. The anti-scratch BOPET film materials required by the industry mainly rely on imports. The imported anti-scratch PET film is mainly composed of four parts, which are hard coating, PET sheet, treatment layer and PE protective film. The hardened coating in the middle is the key core component, which plays a key anti-scratch role, and is a research hotspot for the majority of scientific researchers.
发明内容Contents of the invention
有鉴于此，本发明的目的在于提供一种防刮伤、抗静电型涂布膜及其制备方法，本发明提供的防刮伤、抗静电型涂布膜同时具有良好的防刮伤性能和抗 静电性能。In view of this, the object of the present invention is to provide a kind of anti-scratch, antistatic type coating film and preparation method thereof, anti-scratch provided by the invention, antistatic type coating film has good anti-scratch performance and Antistatic properties.
本发明提供了一种防刮伤、抗静电型涂布膜，包括：The invention provides an anti-scratch, antistatic coating film, comprising:
基膜；basement membrane;
复合在所述基膜上的水性功能涂层；A water-based functional coating compounded on the base film;
所述水性功能涂层由包括以下组分的原料制备而成：The water-based functional coating is prepared from raw materials comprising the following components:
聚氨酯丙烯酸酯20重量份～35重量份；20 to 35 parts by weight of polyurethane acrylate;
交联剂5重量份～10重量份；5 to 10 parts by weight of crosslinking agent;
改性剂5重量份～10重量份；5 parts by weight to 10 parts by weight of modifier;
纳米二氧化硅0.5重量份～1.5重量份；0.5 parts by weight to 1.5 parts by weight of nano silicon dioxide;
非离子抗静电剂2重量份～4重量份；2 to 4 parts by weight of nonionic antistatic agent;
润湿剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of wetting agent;
消泡剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of defoamer;
软水35重量份～70重量份；35 parts by weight to 70 parts by weight of soft water;
所述交联剂为N-羟甲基丙烯酰胺。The crosslinking agent is N-methylolacrylamide.
优选的，所述基膜为BOPET膜。Preferably, the base film is a BOPET film.
优选的，所述改性剂为甲基三乙氧基硅烷和/或乙烯基三甲氧基硅烷。Preferably, the modifying agent is methyltriethoxysilane and/or vinyltrimethoxysilane.
优选的，所述纳米二氧化硅的比表面积为100m 2/g～300m 2/g，粒径为10nm～15nm。 Preferably, the specific surface area of the nano silicon dioxide is 100m 2 /g-300m 2 /g, and the particle size is 10nm-15nm.
优选的，所述非离子抗静电剂为甘油-硬脂酸酯。Preferably, the nonionic antistatic agent is glycerol-stearate.
优选的，所述润湿剂为乙醇或炔二醇。Preferably, the wetting agent is ethanol or acetylene glycol.
本发明还提供了一种上述技术方案所述的防刮伤、抗静电型涂布膜的制备方法，包括以下步骤：The present invention also provides a method for preparing the anti-scratch and antistatic coating film described in the above technical solution, comprising the following steps:
a)将聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水混合均匀，得到水性功能涂料；a) uniformly mix polyurethane acrylate, crosslinking agent, modifier, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoamer and soft water to obtain a water-based functional coating;
b)将步骤a)得到的水性功能涂料涂布在基膜上，经干燥后形成水性功能涂层，收卷后得到防刮伤、抗静电型涂布膜。b) coating the water-based functional coating obtained in step a) on the base film, forming a water-based functional coating after drying, and obtaining an anti-scratch and antistatic coating film after winding.
优选的，所述步骤a)具体为：Preferably, said step a) is specifically:
在反应釜中加入聚氨酯丙烯酸酯，在20℃～30℃、100r/min～120r/min转速下加入改性剂持续搅拌15min～25min，再加入交联剂和软水，继续搅拌 25min～35min，最后加入纳米二氧化硅、非离子抗静电剂、润湿剂和消泡剂搅拌均匀，得到水性功能涂料。Add urethane acrylate into the reaction kettle, add the modifier at 20°C~30°C, 100r/min~120r/min and continue stirring for 15min~25min, then add crosslinking agent and soft water, continue stirring for 25min~35min, and finally Add nano-silica, non-ionic antistatic agent, wetting agent and defoamer and stir evenly to obtain a water-based functional coating.
优选的，步骤b)中所述涂布前，还包括：Preferably, before coating described in step b), it also includes:
对基膜进行电晕处理，使基膜的表面张力达到45dyn/cm～55dyn/cm。Corona treatment is performed on the base film to make the surface tension of the base film reach 45dyn/cm-55dyn/cm.
优选的，步骤b)中所述涂布的干涂布量为0.5g/m 2～1.0g/m 2。 Preferably, the dry coating weight of the coating in step b) is 0.5 g/m 2 -1.0 g/m 2 .
本发明提供了一种防刮伤、抗静电型涂布膜，包括：基膜；复合在所述基膜上的水性功能涂层；所述水性功能涂层由包括以下组分的原料制备而成：聚氨酯丙烯酸酯20重量份～35重量份；交联剂5重量份～10重量份；改性剂5重量份～10重量份；纳米二氧化硅0.5重量份～1.5重量份；非离子抗静电剂2重量份～4重量份；润湿剂0.1重量份～0.5重量份；消泡剂0.1重量份～0.5重量份；软水35重量份～70重量份；所述交联剂为N-羟甲基丙烯酰胺。与现有技术相比，本发明提供的防刮伤、抗静电型涂布膜包括基膜和复合在所述基膜上的水性功能涂层，该水性功能涂层采用特定含量组分，实现整体较好的相互作用，从而使整体涂布膜同时具有良好的防刮伤性能和抗静电性能。实验结果表明，本发明提供的防刮伤、抗静电型涂布膜的抗划伤性不低于60g，涂布膜的表面电阻在10 9Ω以下。 The invention provides an anti-scratch and antistatic coating film, comprising: a base film; a water-based functional coating compounded on the base film; the water-based functional coating is prepared from raw materials comprising the following components Components: 20 to 35 parts by weight of polyurethane acrylate; 5 to 10 parts by weight of crosslinking agent; 5 to 10 parts by weight of modifier; 0.5 to 1.5 parts by weight of nano silicon dioxide; 2 to 4 parts by weight of static agent; 0.1 to 0.5 parts by weight of wetting agent; 0.1 to 0.5 parts by weight of defoamer; 35 to 70 parts by weight of soft water; Methacrylamide. Compared with the prior art, the anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film. The water-based functional coating adopts specific content components to achieve The overall better interaction, so that the overall coating film has good anti-scratch performance and antistatic performance at the same time. Experimental results show that the anti-scratch and antistatic coating film provided by the invention has a scratch resistance of no less than 60g, and the surface resistance of the coating film is below 10 9 Ω.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。In addition, the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
具体实施方式detailed description
下面将结合本发明实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提供了一种防刮伤、抗静电型涂布膜，包括：The invention provides an anti-scratch, antistatic coating film, comprising:
基膜；basement membrane;
复合在所述基膜上的水性功能涂层；A water-based functional coating compounded on the base film;
所述水性功能涂层由包括以下组分的原料制备而成：The water-based functional coating is prepared from raw materials comprising the following components:
聚氨酯丙烯酸酯20重量份～35重量份；20 to 35 parts by weight of polyurethane acrylate;
交联剂5重量份～10重量份；5 to 10 parts by weight of crosslinking agent;
改性剂5重量份～10重量份；5 parts by weight to 10 parts by weight of modifier;
纳米二氧化硅0.5重量份～1.5重量份；0.5 parts by weight to 1.5 parts by weight of nano silicon dioxide;
非离子抗静电剂2重量份～4重量份；2 to 4 parts by weight of nonionic antistatic agent;
润湿剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of wetting agent;
消泡剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of defoamer;
软水35重量份～70重量份；35 parts by weight to 70 parts by weight of soft water;
所述交联剂为N-羟甲基丙烯酰胺。The crosslinking agent is N-methylolacrylamide.
在本发明中，所述防刮伤、抗静电型涂布膜包括基膜和复合在所述基膜上的水性功能涂层，优选由基膜和复合在所述基膜上的水性功能涂层组成。In the present invention, the anti-scratch and antistatic coating film includes a base film and a water-based functional coating compounded on the base film, preferably a base film and a water-based functional coating compounded on the base film. layer composition.
在本发明中，所述基膜优选为BOPET膜。本发明对所述BOPET膜的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。In the present invention, the base film is preferably a BOPET film. In the present invention, there is no special limitation on the source of the BOPET film, and commercially available products well known to those skilled in the art can be used.
在本发明中，所述水性功能涂层由包括以下组分的原料制备而成：In the present invention, the water-based functional coating is prepared from raw materials comprising the following components:
聚氨酯丙烯酸酯20重量份～35重量份；20 to 35 parts by weight of polyurethane acrylate;
交联剂5重量份～10重量份；5 to 10 parts by weight of crosslinking agent;
改性剂5重量份～10重量份；5 parts by weight to 10 parts by weight of modifier;
纳米二氧化硅0.5重量份～1.5重量份；0.5 parts by weight to 1.5 parts by weight of nano silicon dioxide;
非离子抗静电剂2重量份～4重量份；2 to 4 parts by weight of nonionic antistatic agent;
润湿剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of wetting agent;
消泡剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of defoamer;
软水35重量份～70重量份。35 parts by weight to 70 parts by weight of soft water.
在本发明中，所述水性功能涂层由包括聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水的原料制备而成，优选由聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水制备而成。In the present invention, the water-based functional coating is prepared from raw materials including polyurethane acrylate, crosslinking agent, modifier, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoamer and soft water , preferably prepared from polyurethane acrylate, cross-linking agent, modifier, nano-silica, non-ionic antistatic agent, wetting agent, defoamer and soft water.
在本发明中，所述聚氨酯丙烯酸酯为脂肪酸聚氨酯六官能团丙烯酸树脂，本发明对其来源没有特殊限制，采用本领域技术人员熟知的市售商品或自制品均可。在本发明优选的实施例中，所述聚氨酯丙烯酸酯为WDS-6505。在本发明中，所述水性功能涂层包括20重量份～35重量份的聚氨酯丙烯酸酯。In the present invention, the polyurethane acrylate is a fatty acid polyurethane hexafunctional acrylic resin. The present invention has no special limitation on its source, and commercially available or self-made products well known to those skilled in the art can be used. In a preferred embodiment of the present invention, the polyurethane acrylate is WDS-6505. In the present invention, the water-based functional coating includes 20 to 35 parts by weight of polyurethane acrylate.
在本发明中，所述交联剂为N-羟甲基丙烯酰胺，采用本领域技术人员熟知的市售商品即可。本发明创新性地引入N-羟甲基丙烯酰胺作为交联剂，其分子中具有与羰基共轭的双键和富有反应性的羟甲基，由于具有缩合功能的羟甲基引入，促进聚氨酯丙烯酸树脂发生交联，增强功能涂层的粘结性能。在本发明中，所述水性功能涂层包括5重量份～10重量份的交联剂。In the present invention, the crosslinking agent is N-methylolacrylamide, which can be commercially available products well known to those skilled in the art. The present invention innovatively introduces N-methylol acrylamide as a crosslinking agent, which has a double bond conjugated with a carbonyl group and a reactive methylol group in its molecule. Due to the introduction of a condensation-functional methylol group, the polyurethane The acrylic resin is cross-linked to enhance the bonding properties of the functional coating. In the present invention, the water-based functional coating includes 5 to 10 parts by weight of a crosslinking agent.
在本发明中，所述改性剂优选为甲基三乙氧基硅烷和/或乙烯基三甲氧基硅烷，更优选为甲基三乙氧基硅烷和乙烯基三甲氧基硅烷。在本发明优选的实施例中，所述改性剂为质量比为1：1的甲基三乙氧基硅烷和乙烯基三甲氧基硅烷。本发明对所述改性剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。在本发明中，所述水性功能涂层包括5重量份～10重量份的改性剂。In the present invention, the modifying agent is preferably methyltriethoxysilane and/or vinyltrimethoxysilane, more preferably methyltriethoxysilane and vinyltrimethoxysilane. In a preferred embodiment of the present invention, the modifier is methyltriethoxysilane and vinyltrimethoxysilane with a mass ratio of 1:1. In the present invention, the source of the modifying agent is not particularly limited, and commercially available products well known to those skilled in the art can be used. In the present invention, the water-based functional coating includes 5 to 10 parts by weight of modifier.
在本发明中，所述纳米二氧化硅的比表面积优选为100m 2/g～300m 2/g，更优选为200m 2/g；所述纳米二氧化硅的粒径优选为10nm～15nm，更优选为12nm。在本发明中，所述纳米二氧化硅中的硅氧键具有较强的极性，且二氧化硅颗粒表面常吸附有一定的化合水和羟基，因此二氧化硅颗粒具有较高表面能，裸露在涂布膜表面有助于增加预涂膜表面的极性及界面张力，使功能性涂层易于润湿其表面；纳米二氧化硅颗粒在涂布膜表面形成凸起，使表面粗糙，起到良好的防黏连效果。本发明对所述纳米二氧化硅的来源没有特殊限制，采用本领域技术人员熟知的满足上述参数要求的市售或自制气相二氧化硅均可。在本发明中，所述水性功能涂层包括0.5重量份～1.5重量份的纳米二氧化硅。 In the present invention, the specific surface area of the nano-silica is preferably 100m 2 /g-300m 2 /g, more preferably 200m 2 /g; the particle size of the nano-silica is preferably 10nm-15nm, more preferably Preferably 12nm. In the present invention, the silicon-oxygen bond in the nano-silica has strong polarity, and the surface of the silica particles often adsorbs certain combined water and hydroxyl groups, so the silica particles have relatively high surface energy, Bareness on the surface of the coating film helps to increase the polarity and interfacial tension of the surface of the pre-coating film, making the surface of the functional coating easy to wet; nano-silica particles form protrusions on the surface of the coating film, making the surface rough, Play a good anti-adhesion effect. The present invention has no special limitation on the source of the nano-silica, and commercially available or self-made fumed silica well known to those skilled in the art can be used. In the present invention, the water-based functional coating includes 0.5 to 1.5 parts by weight of nano silicon dioxide.
在本发明中，所述非离子抗静电剂优选为甘油-硬脂酸酯。本发明对所述非离子抗静电剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。在本发明中，所述水性功能涂层包括2重量份～4重量份的非离子抗静电剂。In the present invention, the nonionic antistatic agent is preferably glycerol-stearate. In the present invention, there is no special limitation on the source of the nonionic antistatic agent, and commercially available products well known to those skilled in the art can be used. In the present invention, the water-based functional coating includes 2 to 4 parts by weight of a nonionic antistatic agent.
在本发明中，所述润湿剂优选为乙醇或炔二醇，更优选为炔二醇。本发明对所述润湿剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。在本发明中，所述水性功能涂层包括0.1重量份～0.5重量份的润湿剂。In the present invention, the wetting agent is preferably ethanol or acetylene glycol, more preferably acetylene glycol. In the present invention, the source of the wetting agent is not particularly limited, and commercially available products well known to those skilled in the art can be used. In the present invention, the water-based functional coating includes 0.1 to 0.5 parts by weight of a wetting agent.
在本发明中，所述消泡剂优选为有机硅消泡剂。本发明对所述消泡剂的来源没有特殊限制，采用本领域技术人员熟知的市售商品即可。在本发明中，所述水性功能涂层包括0.1重量份～0.5重量份的消泡剂。In the present invention, the defoamer is preferably a silicone defoamer. In the present invention, there is no special limitation on the source of the defoamer, and commercially available products well known to those skilled in the art can be used. In the present invention, the water-based functional coating includes 0.1 to 0.5 parts by weight of a defoamer.
本发明对所述软水的来源没有特殊限制。在本发明中，所述水性功能涂层 包括35重量份～70重量份的软水，更优选为38.5重量份～67.3重量份。The present invention has no special limitation on the source of the soft water. In the present invention, the water-based functional coating includes 35 parts by weight to 70 parts by weight of soft water, more preferably 38.5 parts by weight to 67.3 parts by weight.
本发明提供的防刮伤、抗静电型涂布膜包括基膜和复合在所述基膜上的水性功能涂层，该水性功能涂层采用特定含量组分，实现整体较好的相互作用，从而使整体涂布膜同时具有良好的防刮伤性能和抗静电性能，进一步能够作为高阻隔抗静电型涂布膜应用于食品包装。The anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film. The water-based functional coating adopts specific content components to achieve overall better interaction, Therefore, the overall coating film has good anti-scratch performance and antistatic performance at the same time, and can be further applied to food packaging as a high-barrier antistatic coating film.
本发明还提供了一种上述技术方案所述的防刮伤、抗静电型涂布膜的制备方法，包括以下步骤：The present invention also provides a method for preparing the anti-scratch and antistatic coating film described in the above technical solution, comprising the following steps:
a)将聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水混合均匀，得到水性功能涂料；a) uniformly mix polyurethane acrylate, crosslinking agent, modifier, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoamer and soft water to obtain a water-based functional coating;
b)将步骤a)得到的水性功能涂料涂布在基膜上，经干燥后形成水性功能涂层，收卷后得到防刮伤、抗静电型涂布膜。b) coating the water-based functional coating obtained in step a) on the base film, forming a water-based functional coating after drying, and obtaining an anti-scratch and antistatic coating film after winding.
本发明首先将聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水混合均匀，得到水性功能涂料。In the invention, the polyurethane acrylate, crosslinking agent, modifying agent, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoaming agent and soft water are uniformly mixed to obtain the water-based functional coating.
在本发明中，所述聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水与上述技术方案中的相同，在此不再赘述。In the present invention, described urethane acrylate, cross-linking agent, modifying agent, nano silicon dioxide, non-ionic antistatic agent, wetting agent, defoamer and soft water are the same as those in the above-mentioned technical scheme, do not mention here Let me repeat.
本发明采用“一锅煮”方法先制备水性功能涂料。在本发明中，所述步骤a)优选具体为：The invention adopts the method of "one-pot cooking" to firstly prepare the water-based functional coating. In the present invention, the step a) is preferably specifically:
在反应釜中加入聚氨酯丙烯酸酯，在20℃～30℃、100r/min～120r/min转速下加入改性剂持续搅拌15min～25min，再加入交联剂和软水，继续搅拌25min～35min，最后加入纳米二氧化硅、非离子抗静电剂、润湿剂和消泡剂搅拌均匀，得到水性功能涂料；Add urethane acrylate into the reaction kettle, add the modifier at 20°C~30°C, 100r/min~120r/min and continue stirring for 15min~25min, then add crosslinking agent and soft water, continue stirring for 25min~35min, and finally Add nano-silica, non-ionic antistatic agent, wetting agent and defoamer and stir evenly to obtain a water-based functional coating;
更优选为：More preferably:
在反应釜中加入聚氨酯丙烯酸酯，在20℃～30℃、110r/min转速下加入改性剂持续搅拌20min，再加入交联剂和软水，继续搅拌30min，最后加入纳米二氧化硅、非离子抗静电剂、润湿剂和消泡剂搅拌均匀，得到水性功能涂料。Add urethane acrylate to the reaction kettle, add modifier and continue stirring for 20 minutes at 20°C ~ 30°C, 110r/min, then add crosslinking agent and soft water, continue stirring for 30 minutes, and finally add nano-silica, non-ionic Stir the antistatic agent, wetting agent and defoamer evenly to obtain a water-based functional coating.
本发明首先在聚氨酯丙烯酸酯中加入改性剂，使其成膜后形成的交联密度高，从而赋予聚氨酯丙烯酸树脂较高的硬度，达到良好的防刮伤性能。In the present invention, a modifying agent is firstly added to the polyurethane acrylate, so that the cross-linking density formed after forming a film is high, thereby endowing the polyurethane acrylic resin with higher hardness and achieving good anti-scratch performance.
得到所述水性功能涂料后，本发明将得到的水性功能涂料涂布在基膜上， 经干燥后形成水性功能涂层，收卷后得到防刮伤、抗静电型涂布膜。After the water-based functional coating is obtained, the present invention coats the obtained water-based functional coating on the base film, forms a water-based functional coating after drying, and obtains an anti-scratch and antistatic coating film after winding.
在本发明中，所述基膜与上述技术方案中的相同，在此不再赘述。In the present invention, the base film is the same as that in the above technical solution, and will not be repeated here.
在本发明中，所述涂布前，优选还包括：In the present invention, before the coating, preferably also include:
对基膜进行电晕处理，使基膜的表面张力达到45dyn/cm～55dyn/cm；Carry out corona treatment on the base film to make the surface tension of the base film reach 45dyn/cm～55dyn/cm;
更优选为：More preferably:
对基膜进行电晕处理，使基膜的表面张力达到50dyn/cm。Corona treatment is performed on the base film to make the surface tension of the base film reach 50 dyn/cm.
然后使用凹版涂布辊将上述水性功能涂料涂布在基膜的电晕面上；所述涂布的干涂布量优选为0.5g/m 2～1.0g/m 2，优选为0.8g/m 2。 Then use a gravure coating roller to coat the above-mentioned water-based functional coating on the corona surface of the base film; the dry coating amount of the coating is preferably 0.5g/m 2 to 1.0g/m 2 , preferably 0.8g/m 2 m 2 .
在本发明中，所述干燥的温度优选为90℃～110℃，更优选为95℃～105℃。本发明对所述干燥的方式没有特殊限制，采用本领域技术人员熟知的远红外或热空气干燥均可。In the present invention, the drying temperature is preferably 90°C to 110°C, more preferably 95°C to 105°C. The present invention has no special limitation on the drying method, and far-infrared or hot air drying well known to those skilled in the art can be used.
本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。The preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
本发明提供了一种防刮伤、抗静电型涂布膜，包括：基膜；复合在所述基膜上的水性功能涂层；所述水性功能涂层由包括以下组分的原料制备而成：聚氨酯丙烯酸酯20重量份～35重量份；交联剂5重量份～10重量份；改性剂5重量份～10重量份；纳米二氧化硅0.5重量份～1.5重量份；非离子抗静电剂2重量份～4重量份；润湿剂0.1重量份～0.5重量份；消泡剂0.1重量份～0.5重量份；软水35重量份～70重量份；所述交联剂为N-羟甲基丙烯酰胺。与现有技术相比，本发明提供的防刮伤、抗静电型涂布膜包括基膜和复合在所述基膜上的水性功能涂层，该水性功能涂层采用特定含量组分，实现整体较好的相互作用，从而使整体涂布膜同时具有良好的防刮伤性能和抗静电性能。实验结果表明，本发明提供的防刮伤、抗静电型涂布膜的抗划伤性不低于60g，涂布膜的表面电阻在10 9Ω以下。 The invention provides an anti-scratch and antistatic coating film, comprising: a base film; a water-based functional coating compounded on the base film; the water-based functional coating is prepared from raw materials comprising the following components Components: 20 to 35 parts by weight of polyurethane acrylate; 5 to 10 parts by weight of crosslinking agent; 5 to 10 parts by weight of modifier; 0.5 to 1.5 parts by weight of nano silicon dioxide; 2 to 4 parts by weight of static agent; 0.1 to 0.5 parts by weight of wetting agent; 0.1 to 0.5 parts by weight of defoamer; 35 to 70 parts by weight of soft water; Methacrylamide. Compared with the prior art, the anti-scratch and antistatic coating film provided by the present invention includes a base film and a water-based functional coating compounded on the base film. The water-based functional coating adopts specific content components to achieve The overall better interaction, so that the overall coating film has good anti-scratch performance and antistatic performance at the same time. Experimental results show that the anti-scratch and antistatic coating film provided by the invention has a scratch resistance of not less than 60g, and the surface resistance of the coating film is below 10 9 Ω.
另外，本发明提供的制备方法工艺简单，条件温和、易控，具有广阔的应用前景。In addition, the preparation method provided by the invention has simple process, mild conditions and easy control, and has broad application prospects.
为了进一步说明本发明，下面通过以下实施例进行详细说明。本发明以下实施例所用原料均为市售；其中，聚氨酯丙烯酸酯(脂肪族PUA)为WDS-6505，交联剂为N-羟甲基丙烯酰胺，改性剂为质量比为1：1的甲基三乙氧基硅烷和乙烯基三甲氧基硅烷，纳米二氧化硅为比表面积在200m 2/g，粒径在12nm的气相 二氧化硅，非离子抗静电剂为甘油-硬脂酸酯，润湿剂为炔二醇，消泡剂为有机硅消泡剂。 In order to further illustrate the present invention, the following examples are described in detail below. The raw materials used in the following examples of the present invention are all commercially available; wherein, the polyurethane acrylate (aliphatic PUA) is WDS-6505, the crosslinking agent is N-methylolacrylamide, and the modifier is 1:1 mass ratio Methyltriethoxysilane and vinyltrimethoxysilane, nano silica is fumed silica with a specific surface area of 200m 2 /g and a particle size of 12nm, and the nonionic antistatic agent is glycerol-stearate , the wetting agent is acetylene glycol, and the defoamer is silicone defoamer.
实施例1Example 1
(1)在反应釜中加入20重量份聚氨酯丙烯酸酯，常温开启搅拌速度为110r/min加入5重量份改性剂，持续搅拌20min后加入5重量份交联剂和67.3重量份软水，常温继续搅拌30min后加入0.5重量份纳米二氧化硅、2重量份非离子抗静电剂、0.1重量份润湿剂和0.1重量份消泡剂搅拌均匀，得到水性功能涂料。(1) Add 20 parts by weight of urethane acrylate to the reaction kettle, start stirring at room temperature at a stirring speed of 110r/min, add 5 parts by weight of modifier, continue stirring for 20 minutes, add 5 parts by weight of crosslinking agent and 67.3 parts by weight of soft water, and continue at room temperature After stirring for 30 minutes, add 0.5 parts by weight of nano silicon dioxide, 2 parts by weight of nonionic antistatic agent, 0.1 part by weight of wetting agent and 0.1 part by weight of defoamer and stir evenly to obtain a water-based functional coating.
(2)用12U的普通BOPET膜为基材，先放卷进行电晕处理，使基膜的表面张力达到50dyn/cm，然后使用凹版涂布辊将上述水性功能涂料涂布在BOPET膜的电晕面上，干涂布量为0.8g/m 2，再使用远红外或热空气干燥，烘箱温度设定为100±5℃，经干燥后形成水性功能涂层，进行收卷，得到防刮伤、抗静电型涂布膜。 (2) Use 12U ordinary BOPET film as the base material, first unwind and perform corona treatment, so that the surface tension of the base film reaches 50dyn/cm, and then use the gravure coating roller to coat the above-mentioned water-based functional coating on the electrical surface of the BOPET film. On the halo surface, the dry coating amount is 0.8g/m 2 , then use far infrared or hot air to dry, and the oven temperature is set at 100±5°C. After drying, a water-based functional coating is formed, and it is rolled up to obtain a scratch-resistant coating. scratch, antistatic coating film.
对本发明实施例1提供的防刮伤、抗静电型涂布膜进行性能测试，其中，抗划伤测试方法是：以出现划痕的临界载荷的实验方法来表征抗划伤性；测试时，将砂纸放在薄膜表面，在砂纸上加载0-100g的载荷，以约为10mm/s的速度匀速拉动砂纸，以出现明显划痕的最小质量表示涂层的抗划伤性；抗静电性能的测试标准为GB/T 15662-1995。The anti-scratch, antistatic type coating film provided by the embodiment of the present invention 1 is tested for performance, wherein, the anti-scratch test method is: characterize the scratch resistance with the experimental method of the critical load that occurs scratches; During the test, Put the sandpaper on the surface of the film, load the sandpaper with a load of 0-100g, pull the sandpaper at a constant speed of about 10mm/s, and use the minimum mass with obvious scratches to indicate the scratch resistance of the coating; the antistatic performance The test standard is GB/T 15662-1995.
测试结果如下：测试抗划伤性为60g，涂布膜的表面电阻为10 9Ω。 The test results are as follows: the test scratch resistance is 60 g, and the surface resistance of the coating film is 10 9 Ω.
对比例1Comparative example 1
采用实施例1提供的制备方法，区别在于：不加改性剂；得到涂布膜；其抗划伤性为45g。Using the preparation method provided in Example 1, the difference is: no modifier is added; a coated film is obtained; and its scratch resistance is 45 g.
实施例2Example 2
(1)在反应釜中加入30重量份聚氨酯丙烯酸酯，常温开启搅拌速度为110r/min加入7重量份改性剂，持续搅拌20min后加入7重量份交联剂和50.4重量份软水，常温继续搅拌30min后加入1重量份纳米二氧化硅、4重量份非离子抗静电剂、0.3重量份润湿剂和0.3重量份消泡剂搅拌均匀，得到水性功能涂料。(1) Add 30 parts by weight of urethane acrylate to the reaction kettle, start stirring at room temperature at a stirring speed of 110r/min, add 7 parts by weight of modifier, continue stirring for 20 minutes, add 7 parts by weight of crosslinking agent and 50.4 parts by weight of soft water, and continue at room temperature After stirring for 30 minutes, add 1 part by weight of nano silicon dioxide, 4 parts by weight of nonionic antistatic agent, 0.3 part by weight of wetting agent and 0.3 part by weight of defoamer and stir evenly to obtain a water-based functional coating.
(2)用12U的普通BOPET膜为基材，先放卷进行电晕处理，使基膜的表面张力达到50dyn/cm，然后使用凹版涂布辊将上述水性功能涂料涂布在BOPET膜的电晕面上，干涂布量为0.8g/m 2，再使用远红外或热空气干燥，烘 箱温度设定为100±5℃，经干燥后形成水性功能涂层，进行收卷，得到防刮伤、抗静电型涂布膜。 (2) Use 12U ordinary BOPET film as the base material, first unwind and perform corona treatment, so that the surface tension of the base film reaches 50dyn/cm, and then use the gravure coating roller to coat the above-mentioned water-based functional coating on the electrical surface of the BOPET film. On the halo surface, the dry coating amount is 0.8g/m 2 , then use far infrared or hot air to dry, and the oven temperature is set at 100±5°C. After drying, a water-based functional coating is formed, and it is rolled up to obtain a scratch-resistant coating. scratch, antistatic coating film.
对本发明实施例2提供的防刮伤、抗静电型涂布膜进行性能测试，测试抗划伤性为70g，涂布膜的表面电阻为10 8Ω。 Performance tests were performed on the anti-scratch and antistatic coating film provided in Example 2 of the present invention. The scratch resistance was 70 g, and the surface resistance of the coating film was 10 8 Ω.
对比例2Comparative example 2
采用实施例2提供的制备方法，区别在于：不加非离子抗静电剂；得到涂布膜；其表面电阻为10 10Ω。 Using the preparation method provided in Example 2, the difference is: no non-ionic antistatic agent is added; a coating film is obtained; its surface resistance is 10 10 Ω.
实施例3Example 3
(1)在反应釜中加入35重量份聚氨酯丙烯酸酯，常温开启搅拌速度为110r/min加入10重量份改性剂，持续搅拌20min后加入10重量份交联剂和38.5重量份软水，常温继续搅拌30min后加入1.5重量份纳米二氧化硅、4重量份非离子抗静电剂、0.5重量份润湿剂和0.5重量份消泡剂搅拌均匀，得到水性功能涂料。(1) Add 35 parts by weight of urethane acrylate in the reaction kettle, start the stirring speed at room temperature at 110r/min, add 10 parts by weight of modifier, continue stirring for 20 minutes, then add 10 parts by weight of crosslinking agent and 38.5 parts by weight of soft water, continue at room temperature After stirring for 30 minutes, add 1.5 parts by weight of nano silicon dioxide, 4 parts by weight of nonionic antistatic agent, 0.5 parts by weight of wetting agent and 0.5 parts by weight of defoamer and stir evenly to obtain a water-based functional coating.
(2)用12U的普通BOPET膜为基材，先放卷进行电晕处理，使基膜的表面张力达到50dyn/cm，然后使用凹版涂布辊将上述水性功能涂料涂布在BOPET膜的电晕面上，干涂布量为0.8g/m 2，再使用远红外或热空气干燥，烘箱温度设定为100±5℃，经干燥后形成水性功能涂层，进行收卷，得到防刮伤、抗静电型涂布膜。 (2) Use 12U ordinary BOPET film as the base material, first unwind and perform corona treatment, so that the surface tension of the base film reaches 50dyn/cm, and then use the gravure coating roller to coat the above-mentioned water-based functional coating on the electrical surface of the BOPET film. On the halo surface, the dry coating amount is 0.8g/m 2 , then use far infrared or hot air to dry, and the oven temperature is set at 100±5°C. After drying, a water-based functional coating is formed, and it is rolled up to obtain a scratch-resistant coating. scratch, antistatic coating film.
对本发明实施例3提供的防刮伤、抗静电型涂布膜进行性能测试，测试抗划伤性为65g，涂布膜的表面电阻为10 8Ω。 A performance test was performed on the anti-scratch and antistatic coating film provided in Example 3 of the present invention. The scratch resistance was 65 g, and the surface resistance of the coating film was 10 8 Ω.
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。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种防刮伤、抗静电型涂布膜，包括：A scratch-resistant, antistatic coating film comprising:
    基膜；basement membrane;
    复合在所述基膜上的水性功能涂层；A water-based functional coating compounded on the base film;
    所述水性功能涂层由包括以下组分的原料制备而成：The water-based functional coating is prepared from raw materials comprising the following components:
    聚氨酯丙烯酸酯20重量份～35重量份；20 to 35 parts by weight of polyurethane acrylate;
    交联剂5重量份～10重量份；5 to 10 parts by weight of crosslinking agent;
    改性剂5重量份～10重量份；5 parts by weight to 10 parts by weight of modifier;
    纳米二氧化硅0.5重量份～1.5重量份；0.5 parts by weight to 1.5 parts by weight of nano silicon dioxide;
    非离子抗静电剂2重量份～4重量份；2 to 4 parts by weight of nonionic antistatic agent;
    润湿剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of wetting agent;
    消泡剂0.1重量份～0.5重量份；0.1 to 0.5 parts by weight of defoamer;
    软水35重量份～70重量份；35 parts by weight to 70 parts by weight of soft water;
    所述交联剂为N-羟甲基丙烯酰胺。The crosslinking agent is N-methylolacrylamide.
  2. 根据权利要求1所述的防刮伤、抗静电型涂布膜，其特征在于，所述基膜为BOPET膜。The anti-scratch and antistatic coating film according to claim 1, wherein the base film is a BOPET film.
  3. 根据权利要求1所述的防刮伤、抗静电型涂布膜，其特征在于，所述改性剂为甲基三乙氧基硅烷和/或乙烯基三甲氧基硅烷。The anti-scratch and antistatic coating film according to claim 1, characterized in that the modifier is methyltriethoxysilane and/or vinyltrimethoxysilane.
  4. 根据权利要求1所述的防刮伤、抗静电型涂布膜，其特征在于，所述纳米二氧化硅的比表面积为100m 2/g～300m 2/g，粒径为10nm～15nm。 The anti-scratch and antistatic coating film according to claim 1, characterized in that the specific surface area of the nano silicon dioxide is 100m 2 /g-300m 2 /g, and the particle size is 10nm-15nm.
  5. 根据权利要求1所述的防刮伤、抗静电型涂布膜，其特征在于，所述非离子抗静电剂为甘油-硬脂酸酯。The anti-scratch and antistatic coating film according to claim 1, wherein the nonionic antistatic agent is glycerol-stearate.
  6. 根据权利要求1所述的防刮伤、抗静电型涂布膜，其特征在于，所述润湿剂为乙醇或炔二醇。The anti-scratch and antistatic coating film according to claim 1, wherein the wetting agent is ethanol or acetylene glycol.
  7. 一种权利要求1～6任一项所述的防刮伤、抗静电型涂布膜的制备方法，包括以下步骤：A method for preparing the anti-scratch and antistatic coating film according to any one of claims 1 to 6, comprising the following steps:
    a)将聚氨酯丙烯酸酯、交联剂、改性剂、纳米二氧化硅、非离子抗静电剂、润湿剂、消泡剂和软水混合均匀，得到水性功能涂料；a) uniformly mix polyurethane acrylate, crosslinking agent, modifier, nano silicon dioxide, nonionic antistatic agent, wetting agent, defoamer and soft water to obtain a water-based functional coating;
    b)将步骤a)得到的水性功能涂料涂布在基膜上，经干燥后形成水性功能涂层，收卷后得到防刮伤、抗静电型涂布膜。b) coating the water-based functional coating obtained in step a) on the base film, forming a water-based functional coating after drying, and obtaining an anti-scratch and antistatic coating film after winding.
  8. 根据权利要求7所述的制备方法，其特征在于，所述步骤a)具体为：The preparation method according to claim 7, wherein said step a) is specifically:
    在反应釜中加入聚氨酯丙烯酸酯，在20℃～30℃、100r/min～120r/min转速下加入改性剂持续搅拌15min～25min，再加入交联剂和软水，继续搅拌25min～35min，最后加入纳米二氧化硅、非离子抗静电剂、润湿剂和消泡剂搅拌均匀，得到水性功能涂料。Add urethane acrylate into the reaction kettle, add the modifier at 20°C~30°C, 100r/min~120r/min and continue stirring for 15min~25min, then add crosslinking agent and soft water, continue stirring for 25min~35min, and finally Add nano-silica, non-ionic antistatic agent, wetting agent and defoamer and stir evenly to obtain a water-based functional coating.
  9. 根据权利要求7所述的制备方法，其特征在于，步骤b)中所述涂布前，还包括：The preparation method according to claim 7, wherein, before coating in step b), further comprising:
    对基膜进行电晕处理，使基膜的表面张力达到45dyn/cm～55dyn/cm。Corona treatment is performed on the base film to make the surface tension of the base film reach 45dyn/cm-55dyn/cm.
  10. 根据权利要求7所述的制备方法，其特征在于，步骤b)中所述涂布的干涂布量为0.5g/m 2～1.0g/m 2。 The preparation method according to claim 7, characterized in that the dry coating amount of the coating in step b) is 0.5g/m 2 -1.0g/m 2 .
PCT/CN2021/112193 2021-06-23 2021-08-12 Anti-scratch and anti-static coating film and preparation method therefor WO2022267198A1 (en)

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