WO2021213113A1 - Self-repairing tpu protective film for 3d curved screen and preparation method therefor - Google Patents

Self-repairing tpu protective film for 3d curved screen and preparation method therefor Download PDF

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Publication number
WO2021213113A1
WO2021213113A1 PCT/CN2021/082268 CN2021082268W WO2021213113A1 WO 2021213113 A1 WO2021213113 A1 WO 2021213113A1 CN 2021082268 W CN2021082268 W CN 2021082268W WO 2021213113 A1 WO2021213113 A1 WO 2021213113A1
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Prior art keywords
optical
self
grade
tpu
healing
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PCT/CN2021/082268
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French (fr)
Chinese (zh)
Inventor
薛萌
丁敬德
庄永剑
朱丽萍
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广东邦固薄膜涂料创新研究院有限公司
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Publication of WO2021213113A1 publication Critical patent/WO2021213113A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/25Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00Presence of polyurethane
    • C09J2475/006Presence of polyurethane in the substrate

Definitions

  • This application relates to the technical field of screen protective films, and in particular to a self-repairing TPU protective film for 3D curved screens and a preparation method thereof.
  • the curvature of the 3D curved screen is getting larger and larger, and the traditional PET, PC, TAC, PMMA base film and the composite film with TPU cannot be attached to the 3D curved screen.
  • Only pure TPU film can be bent arbitrarily on the curved screen without bursting, but when the TPU base film is used alone, it is not resistant to scratches.
  • most of the current TPU films on the market are made by the casting method.
  • the screen protector mentioned in the patent CN110202901A uses a commercially available TPU base film.
  • the TPU film formed by this method is flat and transparent. The rate is lacking, and the base film is soft, and the smoothness of the surface coating in the later stage is difficult to control.
  • the surface of the 3D curved screen is generally treated with anti-fingerprints, and the water contact angle reaches 110-120°.
  • the surface energy of the 3D curved screen after anti-fingerprint treatment is lower.
  • the traditional protective film uses silicone pressure sensitive adhesive or acrylic Pressure-sensitive adhesives have relatively low adhesion. It is difficult for ordinary pressure-sensitive adhesives to automatically drain bubbles on the screen, and it is difficult to stick firmly to the screen. After being attached to the mobile phone screen, the curved surface is likely to rebound and warp.
  • the curved screen protective film mentioned in patent CN108116020A uses silicone pressure sensitive adhesive.
  • the main purpose of this application is to provide a self-repairing TPU protective film for a 3D curved screen and a preparation method thereof, which has the advantages of good fit of the curved screen, no warping, smooth surface, foldable and scratch-resistant. Moreover, the structure is simple, the manufacturing cost is low, and the TPU protective film suitable for 3D curved screens and with good protection effect can be quickly prepared.
  • the present application provides a self-healing TPU protective film for 3D curved screens, which includes a top-to-bottom release film A, an optical-grade self-healing coating, an optical-grade hard TPU resin film, and an optical Grade high-viscosity acrylic pressure-sensitive adhesive layer, release film B;
  • the optical-grade automatic repair coating is coated by an optical-grade self-healing paint, and the composition of the optical-grade self-healing paint includes: wherein the thickness of the optical-grade automatic repair coating ranges from 5 to 30 ⁇ m.
  • the self-healing resin 100 parts by weight of the self-healing resin, 60-150 parts by weight of the first solvent, 1-10 parts by weight of the slip aid, and 30-100 parts by weight of the first curing agent.
  • the self-healing resin is one or more of polyhydroxy acrylate, polyhydroxy urethane acrylate, polyhydroxy silicon modified acrylate, and polyhydroxy fluorine modified acrylate;
  • the first solvent is acetic acid One or more of ethyl ester, n-butyl acetate, toluene, propylene glycol methyl ether acetate, and methyl ethyl ketone;
  • the slip aid is a fluorine-containing leveling agent, a silicon-containing leveling agent, and a fluorosilicone leveling agent One or more of them;
  • the first curing agent is a dimer or trimer of hexamethylene diisocyanate.
  • the release film A and the release film B are both silicone oil release films of PET base material, and the thickness of the release film A and the release film B are both in the range of 20-60 ⁇ m.
  • the optical-grade hard TPU resin film layer is coated with optical-grade hard TPU glue, and the optical-grade hard TPU glue is made of polyisocyanate, polyester polyol and chain extender through the action of a catalyst. It is polymerized in the second solvent; the thickness of the optical-grade hard TPU resin film layer ranges from 50 to 200 ⁇ m.
  • the polyisocyanate is one or more of hexamethylene diisocyanate or its polymer, isophorone diisocyanate or its polymer;
  • the polyester polyol is a conventional polyester polyol One or more of alcohol, polycaprolactone polyol and polycarbonate diol;
  • the chain extender is ethylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, One or more of methylolpropane;
  • the catalyst is dibutyltin dilaurate;
  • the second solvent is one of ethyl acetate, toluene, butanone, and N,N-dimethylformamide Or several.
  • the optical-grade high-viscosity acrylic pressure-sensitive adhesive layer is coated with optical-grade high-viscosity acrylic pressure-sensitive adhesive, and the optical-grade high-viscosity acrylic pressure-sensitive adhesive is composed of 100 parts by weight of acrylic soft monomer, 10 ⁇ 30 parts by weight of hard acrylic monomer and 3-10 parts of hydroxy acrylic monomer are polymerized in the third solvent through the action of an initiator; the thickness of the optical-grade high-viscosity acrylic pressure-sensitive adhesive layer is in the range of 15-40 ⁇ m.
  • the acrylic soft monomer is two or more of n-butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, and lauryl methacrylate;
  • the acrylic hard monomer is acrylic acid, Two or more of methacrylic acid, methyl methacrylate, vinyl acetate, acrylamide, isobornyl acrylate, and glycidyl methacrylate;
  • the hydroxy acrylic monomer is hydroxy ethyl acrylate, hydroxy acrylate One or more of propyl ester, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate;
  • the initiator is azobisisobutyronitrile, azobisisoheptonitrile, peroxide One or more of dibenzoyl and lauroyl peroxide;
  • the third solvent is one or more of ethyl acetate, toluene,
  • 0.1 to 2% of a second curing agent is added to the optical-grade high-viscosity acrylic pressure-sensitive adhesive, and the second curing agent is a dimer or tripolymer of hexamethylene diisocyanate. Aggregate.
  • the light transmittance of the self-repairing TPU protective film of the 3D curved screen is greater than 90%, the haze is less than 1%, the water contact angle reaches 105° or more, and the dynamic friction coefficient is less than 0.2.
  • a preparation method of a self-repairing TPU protective film for a 3D curved screen includes the following steps:
  • TPU material As the base film, it has good optical performance, no rainbow pattern, interference pattern. Moreover, in this application, the commercially available TPU resin film layer made by the casting method is not used, but the optical-grade hard TPU glue is synthesized first, and then the TPU base film is coated with a coater.
  • the single-layer base film has a relatively simple structure, does not require a hot bending process, and has low preparation cost; and the thickness is adjustable, the hardness of the film material is adjustable, the surface flatness is high, the film material thickness is uniform, and flexibility and curved surface are taken into account. Screen fit.
  • One side of the protective film attached to the 3D curved screen is coated with optical-grade high-viscosity acrylic pressure-sensitive glue. Silicone pressure-sensitive glue is not used, which avoids the difficulty of direct coating of silica gel on the TPU base film.
  • the fingerprint-treated 3D curved screen is stronger; and it does not use expensive fluorine release film and acrylic pressure-sensitive adhesive to bond, and the cost is low.
  • the surface of the protective film is coated with optical-grade self-healing paint, which solves the problem that the TPU base film is not scratch-resistant when used alone. It can quickly repair itself even with small scratches, and the self-healing paint has good flexibility Any bending.
  • the slip additives added to the self-healing coating can make the outer surface of the protective film have good anti-fouling ability and anti-fingerprint performance.
  • the water contact angle can reach 105° or more, and the dynamic friction coefficient is less than 0.2 to achieve better sliding. Operational touch.
  • the preparation method is simple and easy to implement, and can quickly produce 3D curved screen self-repairing TPU protective film products with good protection effect and good comprehensive performance, and high production efficiency.
  • Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxy acrylate, 60 parts by weight of ethyl acetate, 1 part by weight of fluorine-containing leveling agent, and 30 parts by weight of dimer of hexamethylene diisocyanate;
  • Optical grade hard TPU glue is made by mixing hexamethylene diisocyanate, polyester polyol and ethylene glycol at a molar ratio of 1:0.9:0.1 and polymerizing in toluene through the catalysis of dibutyltin dilaurate;
  • Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 3 parts by weight of hydroxyethyl acrylate in acetone through the catalysis of azobisisobutyronitrile; adding 0.2 Parts by weight of the dimer of hexamethylene diisocyanate.
  • the preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
  • the viscous acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 °C to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive layer is covered with a release film B with a thickness of 25 ⁇ m; the release film C is removed, and the optical-grade self-healing coating is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110°C, an optical-grade self-repairing coating with a thickness of 25 ⁇ m is formed, and then the surface of the self-repairing coating is covered with a release film A with a thickness of 25 ⁇ m, rewinding, and then placed at 50°C for curing 72h, get 3D curved screen self-repairing TPU protective film.
  • Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxyurethane acrylate, 150 parts by weight of n-butyl acetate, 10 parts by weight of silicon-containing leveling agent, 100 parts by weight of dimerization of hexamethylene diisocyanate body;
  • Optical grade hard TPU glue is mixed with isophorone diisocyanate, polycaprolactone polyol and 1,4-butanediol at a molar ratio of 1:0.8:0.2 and is catalyzed by dibutyltin dilaurate in N, Polymerized from N-dimethylformamide;
  • Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of ethyl acrylate, 30 parts by weight of methacrylic acid, and 10 parts by weight of hydroxypropyl acrylate in cyclohexane through the catalytic action of azobisisoheptonitrile; 2 parts by weight of the dimer of hexamethylene diisocyanate was also added.
  • the preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
  • Adhesive acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 °C to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 30 ⁇ m.
  • the pressure-sensitive adhesive layer is covered with a release film B with a thickness of 25 ⁇ m; the release film C is removed, and the optical-grade self-healing coating is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110°C, an optical-grade self-repairing coating with a thickness of 15 ⁇ m is formed, and then the surface of the self-repairing coating is covered with a release film A with a thickness of 25 ⁇ m, wound up, and then placed at 50°C for curing 72h, get 3D curved screen self-repairing TPU protective film.
  • Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxy acrylate, 60 parts by weight of ethyl acetate, 1 part by weight of fluorine-containing leveling agent, and 30 parts by weight of dimer of hexamethylene diisocyanate;
  • Optical grade hard TPU glue is made by mixing hexamethylene diisocyanate, polyester polyol and ethylene glycol at a molar ratio of 1:0.85:0.15 and polymerizing in toluene through the catalysis of dibutyltin dilaurate;
  • Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 3 parts by weight of hydroxyethyl acrylate in acetone through the catalysis of azobisisobutyronitrile; adding 0.2 Parts by weight of the dimer of hexamethylene diisocyanate.
  • the preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
  • Adhesive acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 °C to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 40 ⁇ m.
  • the pressure-sensitive adhesive layer is covered with a release film B with a thickness of 50 ⁇ m; the release film C is removed, and the optical-grade self-healing paint is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110°C, an optical self-healing coating with a thickness of 30 ⁇ m is formed, and then a release film A with a thickness of 50 ⁇ m is covered on the surface of the self-healing coating, rewinding, and curing at 60°C after rewinding 48h, get 3D curved screen self-repairing TPU protective film.
  • Optical grade self-healing coating composition includes: 100 parts by weight of polyhydroxy urethane acrylate, 150 parts by weight of n-butyl acetate, 10 parts by weight of silicon-containing leveling agent, 100 parts by weight of dimerization of hexamethylene diisocyanate body;
  • Optical grade hard TPU glue is mixed with isophorone diisocyanate, polycaprolactone polyol and 1,4-butanediol at a molar ratio of 1:0.92:0.08 and is catalyzed by dibutyltin dilaurate in N, Polymerized from N-dimethylformamide;
  • Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of ethyl acrylate, 30 parts by weight of methacrylic acid, and 10 parts by weight of hydroxypropyl acrylate in cyclohexane through the catalytic action of azobisisoheptonitrile; 2 parts by weight of trimer of hexamethylene diisocyanate was also added.
  • the preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
  • the viscous acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 °C to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 35 ⁇ m.
  • the pressure-sensitive adhesive layer is covered with a release film B with a thickness of 38 ⁇ m; the release film C is removed, and the optical-grade self-healing paint is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110°C, an optical-grade self-repairing coating with a thickness of 30 ⁇ m is formed, and then a release film A with a thickness of 38 ⁇ m is covered on the surface of the self-repairing coating, rewinding, and curing at 60°C after rewinding 48h, get 3D curved screen self-repairing TPU protective film.
  • the self-repairing TPU protective film for 3D curved screens obtained in Examples 1 to 4 has a light transmittance of more than 90%, a haze of less than 1%, and a water contact angle of 105 Above °, the coefficient of dynamic friction is less than 0.2, which increases the touch of sliding operation.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

A self-repairing TPU protective film for a 3D curved screen, comprising a release film A, an optical-grade self-repairing coating layer, an optical-grade hard TPU resin film layer, an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer, and a release film B attached from top to bottom. The optical-grade self-repairing coating layer is formed by coating an optical-grade self-repairing coating, and the composition of the optical-grade self-repairing coating comprises 100 parts by weight of a self-repairing resin, 60 to 150 parts by weight of a first solvent, 1 to 10 parts by weight of a slip assistant, and 30 to 100 parts by weight of a first curing agent. The self-repairing TPU protective film for a 3D curved screen has good conformability to a curved screen, has no warping, has a smooth surface, and is foldable and scratch resistant.

Description

一种3D曲面屏自修复TPU保护膜及其制备方法Self-repairing TPU protective film for 3D curved screen and preparation method thereof 技术领域Technical field
本申请涉及屏幕保护膜的技术领域,特别涉及一种3D曲面屏自修复TPU保护膜及其制备方法。This application relates to the technical field of screen protective films, and in particular to a self-repairing TPU protective film for 3D curved screens and a preparation method thereof.
背景技术Background technique
现有智能手机已由直板触屏进入曲面屏、折叠屏时代,触摸屏对屏幕防摔碎和刮花等指标需求较为严格,而当屏幕变为曲面屏或折叠屏后,对于屏幕保护膜的性能也提出了更高的要求。Existing smart phones have entered the era of curved screens and folding screens from straight touch screens. Touch screens have strict requirements for screen shatter resistance and scratch resistance. When the screen becomes a curved screen or a folding screen, the performance of the screen protector is Also put forward higher requirements.
3D曲面屏的弯曲弧度越来越大,传统的PET、PC、TAC、PMMA基膜及与TPU的复合膜都无法与3D曲面屏很好的附贴。只有纯粹的TPU膜才有可能在曲面屏上做到任意弯曲而不爆裂,但单独使用TPU基膜时不耐刮花。并且,目前市面上的TPU膜大多是通过流延法做出的,如专利CN110202901A中提到的屏幕保护贴采用的是市售的TPU基膜,该方法成型的TPU膜在平整度和透光率方面有所欠缺,且该基膜偏软,后期表面涂层的爽滑度难以控制。The curvature of the 3D curved screen is getting larger and larger, and the traditional PET, PC, TAC, PMMA base film and the composite film with TPU cannot be attached to the 3D curved screen. Only pure TPU film can be bent arbitrarily on the curved screen without bursting, but when the TPU base film is used alone, it is not resistant to scratches. Moreover, most of the current TPU films on the market are made by the casting method. For example, the screen protector mentioned in the patent CN110202901A uses a commercially available TPU base film. The TPU film formed by this method is flat and transparent. The rate is lacking, and the base film is soft, and the smoothness of the surface coating in the later stage is difficult to control.
再者,3D曲面屏的表面一般都做了防指纹处理,水接触角达到110~120°,防指纹处理后的3D曲面屏的表面能较低,传统保护膜用的硅胶压敏胶或者丙烯酸压敏胶粘着力都比较低,普通压敏胶在屏幕上很难做到自动排泡效果,很难与屏幕贴得牢,贴合手机屏后容易出现弧面反弹起翘的现象。例如专利CN108116020A中提到的曲面屏保护膜采用的就是硅胶压敏胶。Moreover, the surface of the 3D curved screen is generally treated with anti-fingerprints, and the water contact angle reaches 110-120°. The surface energy of the 3D curved screen after anti-fingerprint treatment is lower. The traditional protective film uses silicone pressure sensitive adhesive or acrylic Pressure-sensitive adhesives have relatively low adhesion. It is difficult for ordinary pressure-sensitive adhesives to automatically drain bubbles on the screen, and it is difficult to stick firmly to the screen. After being attached to the mobile phone screen, the curved surface is likely to rebound and warp. For example, the curved screen protective film mentioned in patent CN108116020A uses silicone pressure sensitive adhesive.
另外,随着现在智能手机功能的逐渐强大,人们在手机上运行 大型游戏,实现指纹识别、屏下解锁等功能,需要手机保护膜的表面做到爽滑、耐刮、耐磨、防指纹。在平面屏时代,用UV固化涂料来做保护膜的表面硬化处理是比较常规的做法,但在3D曲面屏上,保护膜上做UV硬化涂料容易爆裂,更好的解决办法是做自修复涂层处理。In addition, as the functions of smart phones now become more powerful, people run large-scale games on their phones to achieve fingerprint recognition, under-screen unlocking and other functions. The surface of the phone’s protective film needs to be smooth, scratch-resistant, wear-resistant, and fingerprint-resistant. In the era of flat screens, it is a common practice to use UV curing coatings for the surface hardening treatment of the protective film, but on 3D curved screens, the UV hardening coating on the protective film is easy to burst. A better solution is to do self-repairing coating.层处理。 Layer processing.
为此,我们提出了一种3D曲面屏自修复TPU保护膜及其制备方法。To this end, we propose a 3D curved screen self-repairing TPU protective film and its preparation method.
申请内容Application content
本申请的主要目的在于提供一种3D曲面屏自修复TPU保护膜及其制备方法,具有曲面屏贴合性好、不起翘、表面爽滑、可折叠且耐刮花优点。且结构简单,制造成本低,能够快速地制备适合3D曲面屏、且保护效果好的TPU保护膜。The main purpose of this application is to provide a self-repairing TPU protective film for a 3D curved screen and a preparation method thereof, which has the advantages of good fit of the curved screen, no warping, smooth surface, foldable and scratch-resistant. Moreover, the structure is simple, the manufacturing cost is low, and the TPU protective film suitable for 3D curved screens and with good protection effect can be quickly prepared.
为实现上述目的,本申请提供了一种3D曲面屏自修复TPU保护膜,包括自上而下贴合的离型膜A、光学级自修复涂层、光学级硬质TPU树脂膜层、光学级高粘性丙烯酸压敏胶层、离型膜B;In order to achieve the above purpose, the present application provides a self-healing TPU protective film for 3D curved screens, which includes a top-to-bottom release film A, an optical-grade self-healing coating, an optical-grade hard TPU resin film, and an optical Grade high-viscosity acrylic pressure-sensitive adhesive layer, release film B;
所述光学级自动修复涂层由光学级自修复涂料涂布而成,所述光学级自修复涂料组成包括:其中,光学级自动修复涂层的厚度范围为5~30μm。The optical-grade automatic repair coating is coated by an optical-grade self-healing paint, and the composition of the optical-grade self-healing paint includes: wherein the thickness of the optical-grade automatic repair coating ranges from 5 to 30 μm.
100重量份的自修复树脂、60~150重量份的第一溶剂、1~10重量份的爽滑助剂、30~100重量份的第一固化剂。100 parts by weight of the self-healing resin, 60-150 parts by weight of the first solvent, 1-10 parts by weight of the slip aid, and 30-100 parts by weight of the first curing agent.
优选的,所述自修复树脂为多羟基丙烯酸酯、多羟基聚氨酯丙烯酸酯、多羟基硅改性丙烯酸酯、多羟基氟改性丙烯酸酯中的一种 或几种;所述第一溶剂为乙酸乙酯、乙酸正丁酯、甲苯、丙二醇甲醚醋酸酯、丁酮中的一种或几种;所述爽滑助剂为含氟流平剂、含硅流平剂、氟硅流平剂中的一种或几种;所述第一固化剂为六亚甲基二异氰酸酯的二聚体或三聚体。Preferably, the self-healing resin is one or more of polyhydroxy acrylate, polyhydroxy urethane acrylate, polyhydroxy silicon modified acrylate, and polyhydroxy fluorine modified acrylate; the first solvent is acetic acid One or more of ethyl ester, n-butyl acetate, toluene, propylene glycol methyl ether acetate, and methyl ethyl ketone; the slip aid is a fluorine-containing leveling agent, a silicon-containing leveling agent, and a fluorosilicone leveling agent One or more of them; the first curing agent is a dimer or trimer of hexamethylene diisocyanate.
优选的,所述离型膜A和离型膜B均为PET基材的硅油离型膜,所述离型膜A和离型膜B的厚度范围均为20~60μm。Preferably, the release film A and the release film B are both silicone oil release films of PET base material, and the thickness of the release film A and the release film B are both in the range of 20-60 μm.
优选的,所述光学级硬质TPU树脂膜层是由光学级硬质TPU胶水涂布而成,所述光学级硬质TPU胶水由多异氰酸酯、聚酯多元醇和扩链剂通过催化剂的作用在第二溶剂中聚合而成;所述光学级硬质TPU树脂膜层的厚度范围为50~200μm。Preferably, the optical-grade hard TPU resin film layer is coated with optical-grade hard TPU glue, and the optical-grade hard TPU glue is made of polyisocyanate, polyester polyol and chain extender through the action of a catalyst. It is polymerized in the second solvent; the thickness of the optical-grade hard TPU resin film layer ranges from 50 to 200 μm.
优选的,所述多异氰酸酯为六亚甲基二异氰酸酯或其多聚体、异佛尔酮二异氰酸酯或其多聚体中的一种或几种;所述聚酯多元醇为常规聚酯多元醇、聚己内酯多元醇和聚碳酸酯二醇中的一种或几种;所述扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、甘油、三羟甲基丙烷中的一种或几种;所述催化剂为二月桂酸二丁基锡;所述第二溶剂为乙酸乙酯、甲苯、丁酮、N,N-二甲基甲酰胺中的一种或几种。Preferably, the polyisocyanate is one or more of hexamethylene diisocyanate or its polymer, isophorone diisocyanate or its polymer; the polyester polyol is a conventional polyester polyol One or more of alcohol, polycaprolactone polyol and polycarbonate diol; the chain extender is ethylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, One or more of methylolpropane; the catalyst is dibutyltin dilaurate; the second solvent is one of ethyl acetate, toluene, butanone, and N,N-dimethylformamide Or several.
优选的,所述光学级高粘性丙烯酸压敏胶层是由光学级高粘性丙烯酸压敏胶水涂布而成,所述光学级高粘性丙烯酸压敏胶水由100重量份丙烯酸软单体、10~30重量份丙烯酸硬单体、3~10份羟基丙烯酸单体通过引发剂的作用在第三溶剂中聚合而成;所述光学级高粘性丙烯酸压敏胶层的厚度范围为15~40μm。Preferably, the optical-grade high-viscosity acrylic pressure-sensitive adhesive layer is coated with optical-grade high-viscosity acrylic pressure-sensitive adhesive, and the optical-grade high-viscosity acrylic pressure-sensitive adhesive is composed of 100 parts by weight of acrylic soft monomer, 10~ 30 parts by weight of hard acrylic monomer and 3-10 parts of hydroxy acrylic monomer are polymerized in the third solvent through the action of an initiator; the thickness of the optical-grade high-viscosity acrylic pressure-sensitive adhesive layer is in the range of 15-40 μm.
优选的,所述丙烯酸软单体为丙烯酸正丁酯、丙烯酸乙酯、丙 烯酸异辛酯、丙烯酸月桂酯、甲基丙烯酸月桂酯中的两种或几种;所述丙烯酸硬单体为丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、醋酸乙烯酯、丙烯酰胺、丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯中的两种或几种;所述羟基丙烯酸单体为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种或几种;所述引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化月桂酰中的一种或几种;所述第三溶剂为乙酸乙酯、甲苯、丙酮、环己烷中的一种或几种。Preferably, the acrylic soft monomer is two or more of n-butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, and lauryl methacrylate; the acrylic hard monomer is acrylic acid, Two or more of methacrylic acid, methyl methacrylate, vinyl acetate, acrylamide, isobornyl acrylate, and glycidyl methacrylate; the hydroxy acrylic monomer is hydroxy ethyl acrylate, hydroxy acrylate One or more of propyl ester, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; the initiator is azobisisobutyronitrile, azobisisoheptonitrile, peroxide One or more of dibenzoyl and lauroyl peroxide; the third solvent is one or more of ethyl acetate, toluene, acetone, and cyclohexane.
优选的,在涂布过程中,所述光学级高粘性丙烯酸压敏胶水中添加0.1~2%的第二固化剂,所述第二固化剂为六亚甲基二异氰酸酯的二聚体或三聚体。Preferably, during the coating process, 0.1 to 2% of a second curing agent is added to the optical-grade high-viscosity acrylic pressure-sensitive adhesive, and the second curing agent is a dimer or tripolymer of hexamethylene diisocyanate. Aggregate.
优选的,所述3D曲面屏自修复TPU保护膜的透光率大于90%,雾度小于1%,水接触角达到105°以上,动摩擦系数<0.2。Preferably, the light transmittance of the self-repairing TPU protective film of the 3D curved screen is greater than 90%, the haze is less than 1%, the water contact angle reaches 105° or more, and the dynamic friction coefficient is less than 0.2.
一种3D曲面屏自修复TPU保护膜的制备方法,包括如下步骤:A preparation method of a self-repairing TPU protective film for a 3D curved screen includes the following steps:
(1)将光学级硬质TPU胶水涂布在PET离型膜C上,在90-120℃温度下烘干固化后形成光学级硬质TPU树脂膜层;通过刮刀涂布或狭缝涂布方式。(1) Coat optical grade hard TPU glue on PET release film C, dry and cure at 90-120℃ to form optical grade hard TPU resin film layer; coating by doctor blade or slit coating Way.
(2)将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层离型膜B;(2) Coat optical-grade high-viscosity acrylic pressure-sensitive adhesive on the optical-grade hard TPU resin film layer, and dry and cure at 80-120℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer. A layer of release film B is covered on the high-viscosity acrylic pressure-sensitive adhesive layer;
(3)撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成光学级自修复涂层,再在自修复涂层表面覆盖离型膜A,收卷,收卷后 放置于50~60℃条件下熟化48~72h,得到3D曲面屏自修复TPU保护膜。(3) Tear off the release film C, apply an optical-grade self-healing coating on the other side of the optical-grade hard TPU resin film layer, and dry and cure at a temperature of 80-110°C to form an optical-grade self-healing coating Then cover the release film A on the surface of the self-healing coating, rewind, and place it at 50-60°C after rewinding and curing for 48-72h to obtain a 3D curved screen self-repairing TPU protective film.
现有技术相比,本申请具有如下有益效果:Compared with the prior art, this application has the following beneficial effects:
1.采用TPU材质作为基膜,具有较好的光学性能,没有彩虹纹、干涉纹。且本申请中并不采用市售的流延法制作的TPU树脂膜层,而是先合成光学级硬质TPU胶水,再用涂布机涂出该种TPU基膜。该单层基膜的结构比较简单,不需经过热弯工艺,制备成本低;且厚度可调、膜材硬度可调、表面平整度高、膜材厚度均匀性好,兼顾了柔韧性和曲面屏贴合性。1. Using TPU material as the base film, it has good optical performance, no rainbow pattern, interference pattern. Moreover, in this application, the commercially available TPU resin film layer made by the casting method is not used, but the optical-grade hard TPU glue is synthesized first, and then the TPU base film is coated with a coater. The single-layer base film has a relatively simple structure, does not require a hot bending process, and has low preparation cost; and the thickness is adjustable, the hardness of the film material is adjustable, the surface flatness is high, the film material thickness is uniform, and flexibility and curved surface are taken into account. Screen fit.
2.保护膜贴3D曲面屏的一面涂覆光学级高粘性丙烯酸压敏胶水,不使用硅胶压敏胶水,避免了硅胶在TPU基膜上直涂难的问题,可使得保护膜与做过防指纹处理的3D曲面屏更加牢固;且不使用造价昂贵的氟素离型膜与丙烯酸压敏胶水贴合,成本低。2. One side of the protective film attached to the 3D curved screen is coated with optical-grade high-viscosity acrylic pressure-sensitive glue. Silicone pressure-sensitive glue is not used, which avoids the difficulty of direct coating of silica gel on the TPU base film. The fingerprint-treated 3D curved screen is stronger; and it does not use expensive fluorine release film and acrylic pressure-sensitive adhesive to bond, and the cost is low.
3.保护膜表面涂覆光学级自修复涂料,解决了TPU基膜在单独使用时不耐刮花的问题,即使有小的划痕也能够快速自我修复,且自修复涂料柔韧性好,可任意折弯。另外,自修复涂料中添加的爽滑助剂可使保护膜的外表面具有很好的抗污能力、防指纹性能,水接触角达到105°以上,动摩擦系数<0.2,来取得较佳的滑动操作触感。3. The surface of the protective film is coated with optical-grade self-healing paint, which solves the problem that the TPU base film is not scratch-resistant when used alone. It can quickly repair itself even with small scratches, and the self-healing paint has good flexibility Any bending. In addition, the slip additives added to the self-healing coating can make the outer surface of the protective film have good anti-fouling ability and anti-fingerprint performance. The water contact angle can reach 105° or more, and the dynamic friction coefficient is less than 0.2 to achieve better sliding. Operational touch.
4.该制备方法简洁、易实现,能快速生产出保护效果好、综合性能佳的3D曲面屏自修复TPU保护膜产品,生产效率高。4. The preparation method is simple and easy to implement, and can quickly produce 3D curved screen self-repairing TPU protective film products with good protection effect and good comprehensive performance, and high production efficiency.
具体实施方式Detailed ways
为使本申请实现的技术手段、创作特征、达成目的与功效易于 明白了解,下面结合具体实施方式,进一步阐述本申请。In order to make the technical means, creative features, goals and effects achieved by this application easy to understand, the application will be further elaborated below in conjunction with specific implementations.
实施例1Example 1
光学级自修复涂料组成包括:100重量份的多羟基丙烯酸酯、60重量份的乙酸乙酯、1重量份的含氟流平剂、30重量份的六亚甲基二异氰酸酯的二聚体;Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxy acrylate, 60 parts by weight of ethyl acetate, 1 part by weight of fluorine-containing leveling agent, and 30 parts by weight of dimer of hexamethylene diisocyanate;
光学级硬质TPU胶水由六亚甲基二异氰酸酯、聚酯多元醇及乙二醇按摩尔比1:0.9:0.1混合并通过二月桂酸二丁基锡的催化作用在甲苯中聚合而成;Optical grade hard TPU glue is made by mixing hexamethylene diisocyanate, polyester polyol and ethylene glycol at a molar ratio of 1:0.9:0.1 and polymerizing in toluene through the catalysis of dibutyltin dilaurate;
光学级高粘性丙烯酸压敏胶水由由100重量份丙烯酸正丁酯、10重量份丙烯酸、3重量份丙烯酸羟乙酯通过偶氮二异丁腈的催化作用在丙酮中聚合而成;还加入0.2重量份的六亚甲基二异氰酸酯的二聚体。Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 3 parts by weight of hydroxyethyl acrylate in acetone through the catalysis of azobisisobutyronitrile; adding 0.2 Parts by weight of the dimer of hexamethylene diisocyanate.
该3D曲面屏自修复TPU保护膜的制备方法如下:The preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
将光学级硬质TPU胶水涂布在厚度为25μm的PET离型膜C上,在90-120℃温度下烘干固化后形成厚度为50μm的光学级硬质TPU树脂膜层;将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成厚度为25μm的光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层厚度为25μm的离型膜B;撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成厚度为25μm的光学级自修复涂层,再在自修复涂层表面覆盖厚度为25μm的离型膜A,收卷,收卷后放置于50℃条件下熟化72h,得到3D曲面屏自修复TPU保护膜。Coat the optical grade hard TPU glue on the PET release film C with a thickness of 25μm, and dry and cure it at 90-120℃ to form an optical grade hard TPU resin film layer with a thickness of 50μm; The viscous acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 ℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 25μm. The pressure-sensitive adhesive layer is covered with a release film B with a thickness of 25μm; the release film C is removed, and the optical-grade self-healing coating is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110℃, an optical-grade self-repairing coating with a thickness of 25μm is formed, and then the surface of the self-repairing coating is covered with a release film A with a thickness of 25μm, rewinding, and then placed at 50℃ for curing 72h, get 3D curved screen self-repairing TPU protective film.
实施例2Example 2
光学级自修复涂料组成包括:100重量份的多羟基聚氨酯丙烯酸酯、150重量份的乙酸正丁酯、10重量份的含硅流平剂、100重量份的六亚甲基二异氰酸酯的二聚体;Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxyurethane acrylate, 150 parts by weight of n-butyl acetate, 10 parts by weight of silicon-containing leveling agent, 100 parts by weight of dimerization of hexamethylene diisocyanate body;
光学级硬质TPU胶水由异佛尔酮二异氰酸酯、聚己内酯多元醇及1,4-丁二醇按摩尔比1:0.8:0.2混合并通过二月桂酸二丁基锡的催化作用在N,N-二甲基甲酰胺中聚合而成;Optical grade hard TPU glue is mixed with isophorone diisocyanate, polycaprolactone polyol and 1,4-butanediol at a molar ratio of 1:0.8:0.2 and is catalyzed by dibutyltin dilaurate in N, Polymerized from N-dimethylformamide;
光学级高粘性丙烯酸压敏胶水由由100重量份丙烯酸乙酯、30重量份甲基丙烯酸、10质量份丙烯酸羟丙酯通过偶氮二异庚腈的催化作用在环己烷中聚合而成;还加入2重量份的六亚甲基二异氰酸酯的二聚体。Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of ethyl acrylate, 30 parts by weight of methacrylic acid, and 10 parts by weight of hydroxypropyl acrylate in cyclohexane through the catalytic action of azobisisoheptonitrile; 2 parts by weight of the dimer of hexamethylene diisocyanate was also added.
该3D曲面屏自修复TPU保护膜的制备方法如下:The preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
将光学级硬质TPU胶水涂布在厚度为25μm的PET离型膜C上,在90-120℃温度下烘干固化后形成厚度为50μm的光学级硬质TPU树脂膜层;将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成厚度为30μm的光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层厚度为25μm的离型膜B;撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成厚度为15μm的光学级自修复涂层,再在自修复涂层表面覆盖厚度为25μm的离型膜A,收卷,收卷后放置于50℃条件下熟化72h,得到3D曲面屏自修复TPU保护膜。Coat the optical grade hard TPU glue on the PET release film C with a thickness of 25μm, and dry and cure it at 90-120℃ to form an optical grade hard TPU resin film layer with a thickness of 50μm; Adhesive acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 ℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 30μm. In the optical-grade high-viscosity acrylic The pressure-sensitive adhesive layer is covered with a release film B with a thickness of 25μm; the release film C is removed, and the optical-grade self-healing coating is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110℃, an optical-grade self-repairing coating with a thickness of 15μm is formed, and then the surface of the self-repairing coating is covered with a release film A with a thickness of 25μm, wound up, and then placed at 50℃ for curing 72h, get 3D curved screen self-repairing TPU protective film.
实施例3Example 3
光学级自修复涂料组成包括:100重量份的多羟基丙烯酸酯、60重量份的乙酸乙酯、1重量份的含氟流平剂、30重量份的六亚甲基二异氰酸酯的二聚体;Optical-grade self-healing coating composition includes: 100 parts by weight of polyhydroxy acrylate, 60 parts by weight of ethyl acetate, 1 part by weight of fluorine-containing leveling agent, and 30 parts by weight of dimer of hexamethylene diisocyanate;
光学级硬质TPU胶水由六亚甲基二异氰酸酯、聚酯多元醇及乙二醇按摩尔比1:0.85:0.15混合并通过二月桂酸二丁基锡的催化作用在甲苯中聚合而成;Optical grade hard TPU glue is made by mixing hexamethylene diisocyanate, polyester polyol and ethylene glycol at a molar ratio of 1:0.85:0.15 and polymerizing in toluene through the catalysis of dibutyltin dilaurate;
光学级高粘性丙烯酸压敏胶水由由100重量份丙烯酸正丁酯、10重量份丙烯酸、3质量份丙烯酸羟乙酯通过偶氮二异丁腈的催化作用在丙酮中聚合而成;还加入0.2重量份的六亚甲基二异氰酸酯的二聚体。Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of n-butyl acrylate, 10 parts by weight of acrylic acid, and 3 parts by weight of hydroxyethyl acrylate in acetone through the catalysis of azobisisobutyronitrile; adding 0.2 Parts by weight of the dimer of hexamethylene diisocyanate.
该3D曲面屏自修复TPU保护膜的制备方法如下:The preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
将光学级硬质TPU胶水涂布在厚度为50μm的PET离型膜C上,在90-120℃温度下烘干固化后形成厚度为200μm的光学级硬质TPU树脂膜层;将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成厚度为40μm的光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层厚度为50μm的离型膜B;撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成厚度为30μm的光学级自修复涂层,再在自修复涂层表面覆盖厚度为50μm的离型膜A,收卷,收卷后放置于60℃条件下熟化48h,得到3D曲面屏自修复TPU保护膜。Coat the optical-grade hard TPU glue on the PET release film C with a thickness of 50μm, dry and cure at 90-120℃ to form an optical-grade hard TPU resin film with a thickness of 200μm; Adhesive acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 ℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 40μm. In the optical-grade high-viscosity acrylic The pressure-sensitive adhesive layer is covered with a release film B with a thickness of 50μm; the release film C is removed, and the optical-grade self-healing paint is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110°C, an optical self-healing coating with a thickness of 30μm is formed, and then a release film A with a thickness of 50μm is covered on the surface of the self-healing coating, rewinding, and curing at 60°C after rewinding 48h, get 3D curved screen self-repairing TPU protective film.
实施例4Example 4
光学级自修复涂料组成包括:100重量份的多羟基聚氨酯丙烯 酸酯、150重量份的乙酸正丁酯、10重量份的含硅流平剂、100重量份的六亚甲基二异氰酸酯的二聚体;Optical grade self-healing coating composition includes: 100 parts by weight of polyhydroxy urethane acrylate, 150 parts by weight of n-butyl acetate, 10 parts by weight of silicon-containing leveling agent, 100 parts by weight of dimerization of hexamethylene diisocyanate body;
光学级硬质TPU胶水由异佛尔酮二异氰酸酯、聚己内酯多元醇及1,4-丁二醇按摩尔比1:0.92:0.08混合并通过二月桂酸二丁基锡的催化作用在N,N-二甲基甲酰胺中聚合而成;Optical grade hard TPU glue is mixed with isophorone diisocyanate, polycaprolactone polyol and 1,4-butanediol at a molar ratio of 1:0.92:0.08 and is catalyzed by dibutyltin dilaurate in N, Polymerized from N-dimethylformamide;
光学级高粘性丙烯酸压敏胶水由由100重量份丙烯酸乙酯、30重量份甲基丙烯酸、10质量份丙烯酸羟丙酯通过偶氮二异庚腈的催化作用在环己烷中聚合而成;还加入2重量份的六亚甲基二异氰酸酯的三聚体。Optical grade high-viscosity acrylic pressure-sensitive adhesive is made by polymerizing 100 parts by weight of ethyl acrylate, 30 parts by weight of methacrylic acid, and 10 parts by weight of hydroxypropyl acrylate in cyclohexane through the catalytic action of azobisisoheptonitrile; 2 parts by weight of trimer of hexamethylene diisocyanate was also added.
该3D曲面屏自修复TPU保护膜的制备方法如下:The preparation method of the 3D curved screen self-repairing TPU protective film is as follows:
将光学级硬质TPU胶水涂布在厚度为38μm的PET离型膜C上,在90-120℃温度下烘干固化后形成厚度为200μm的光学级硬质TPU树脂膜层;将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成厚度为35μm的光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层厚度为38μm的离型膜B;撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成厚度为30μm的光学级自修复涂层,再在自修复涂层表面覆盖厚度为38μm的离型膜A,收卷,收卷后放置于60℃条件下熟化48h,得到3D曲面屏自修复TPU保护膜。Coat the optical-grade hard TPU glue on the PET release film C with a thickness of 38μm, dry and cure at 90-120℃ to form an optical-grade hard TPU resin film with a thickness of 200μm; The viscous acrylic pressure-sensitive adhesive is coated on the optical-grade hard TPU resin film layer, dried and cured at a temperature of 80-120 ℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer with a thickness of 35μm. In the optical-grade high-viscosity acrylic The pressure-sensitive adhesive layer is covered with a release film B with a thickness of 38μm; the release film C is removed, and the optical-grade self-healing paint is coated on the other side of the optical-grade hard TPU resin film layer, at 80- After drying and curing at 110℃, an optical-grade self-repairing coating with a thickness of 30μm is formed, and then a release film A with a thickness of 38μm is covered on the surface of the self-repairing coating, rewinding, and curing at 60℃ after rewinding 48h, get 3D curved screen self-repairing TPU protective film.
下面对实施例1~4制得的3D曲面屏自修复TPU保护膜进行性能测试,实施例1~4的光学性能测试结果如表1所示:The performance test of the 3D curved screen self-repairing TPU protective film prepared in Examples 1 to 4 is performed below. The optical performance test results of Examples 1 to 4 are shown in Table 1:
表1Table 1
Figure PCTCN2021082268-appb-000001
Figure PCTCN2021082268-appb-000001
结合实施例1~4中的光学性能测试结果,由表1可知,实施例1~4所得3D曲面屏自修复TPU保护膜透光率大于90%,雾度小于1%,水接触角达到105°以上,动摩擦系数<0.2,增加滑动操作触感。Combined with the optical performance test results in Examples 1 to 4, it can be seen from Table 1 that the self-repairing TPU protective film for 3D curved screens obtained in Examples 1 to 4 has a light transmittance of more than 90%, a haze of less than 1%, and a water contact angle of 105 Above °, the coefficient of dynamic friction is less than 0.2, which increases the touch of sliding operation.
以上显示和描述了本申请的基本原理和主要特征和本申请的优点。本行业的技术人员应该了解,本申请不受上述实施例的限制,上述实施例和说明书中描述的只是说明本申请的原理,在不脱离本申请精神和范围的前提下,本申请还会有各种变化和改进,这些变化和改进都落入要求保护的本申请范围内。本申请要求保护范围由所附的权利要求书及其等效物界定。The above shows and describes the basic principles and main features of the application and the advantages of the application. Those skilled in the industry should understand that this application is not limited by the above-mentioned embodiments. The above-mentioned embodiments and descriptions only illustrate the principles of this application. Without departing from the spirit and scope of this application, this application will also have Various changes and improvements, these changes and improvements all fall within the scope of the claimed application. The scope of protection claimed by this application is defined by the appended claims and their equivalents.

Claims (10)

  1. 一种3D曲面屏自修复TPU保护膜,其特征在于,包括自上而下贴合的离型膜A、光学级自修复涂层、光学级硬质TPU树脂膜层、光学级高粘性丙烯酸压敏胶层、离型膜B;A self-repairing TPU protective film for 3D curved screens, which is characterized in that it includes a top-down laminated release film A, an optical-grade self-repairing coating, an optical-grade hard TPU resin film layer, and an optical-grade high-viscosity acrylic pressure Sensitive adhesive layer, release film B;
    所述光学级自动修复涂层由光学级自修复涂料涂布而成,所述光学级自修复涂料组成包括:The optical-grade self-healing coating is coated by optical-grade self-healing paint, and the composition of the optical-grade self-healing paint includes:
    100重量份的自修复树脂、60~150重量份的第一溶剂、1~10重量份的爽滑助剂、30~100重量份的第一固化剂。100 parts by weight of the self-healing resin, 60-150 parts by weight of the first solvent, 1-10 parts by weight of the slip aid, and 30-100 parts by weight of the first curing agent.
  2. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,所述自修复树脂为多羟基丙烯酸酯、多羟基聚氨酯丙烯酸酯、多羟基硅改性丙烯酸酯、多羟基氟改性丙烯酸酯中的一种或几种;所述第一溶剂为乙酸乙酯、乙酸正丁酯、甲苯、丙二醇甲醚醋酸酯、丁酮中的一种或几种;所述爽滑助剂为含氟流平剂、含硅流平剂、氟硅流平剂中的一种或几种;所述第一固化剂为六亚甲基二异氰酸酯的二聚体或三聚体。The 3D curved screen self-healing TPU protective film according to claim 1, wherein the self-healing resin is polyhydroxy acrylate, polyhydroxy urethane acrylate, polyhydroxy silicon modified acrylate, polyhydroxy fluorine modified One or more of acrylate; the first solvent is one or more of ethyl acetate, n-butyl acetate, toluene, propylene glycol methyl ether acetate, and methyl ethyl ketone; the slip aid is One or more of a fluorine-containing leveling agent, a silicon-containing leveling agent, and a fluorosilicone leveling agent; the first curing agent is a dimer or trimer of hexamethylene diisocyanate.
  3. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,所述离型膜A和离型膜B均为PET基材的硅油离型膜,所述离型膜A和离型膜B的厚度范围均为20~60μm。The 3D curved screen self-healing TPU protective film according to claim 1, wherein the release film A and the release film B are both silicone oil release films of PET substrate, and the release film A and the release film The thickness of the film B is in the range of 20 to 60 μm.
  4. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,所述光学级硬质TPU树脂膜层是由光学级硬质TPU胶水涂布而成,所述光学级硬质TPU胶水由多异氰酸酯、聚酯多元醇和扩链剂通过催化剂的作用在第二溶剂中聚合而成;所述光学级硬质TPU树脂膜层的厚度范围为50~200μm。The 3D curved screen self-repairing TPU protective film according to claim 1, wherein the optical-grade hard TPU resin film layer is coated with optical-grade hard TPU glue, and the optical-grade hard TPU The glue is formed by polymerizing polyisocyanate, polyester polyol and chain extender in a second solvent through the action of a catalyst; the thickness of the optical-grade hard TPU resin film layer ranges from 50 to 200 μm.
  5. 根据权利要求4所述的3D曲面屏自修复TPU保护膜,其特征在于,所述多异氰酸酯为六亚甲基二异氰酸酯或其多聚体、异佛尔酮二异氰酸酯或其多聚体中的一种或几种;所述聚酯多元醇为常规聚酯多元醇、聚己内酯多元醇和聚碳酸酯二醇中的一种或几种;所述扩链剂为乙二醇、1,4-丁二醇、1,6-己二醇、甘油、三羟甲基丙烷中的一种或几种;所述催化剂为二月桂酸二丁基锡;所述第二溶剂为乙酸乙酯、甲苯、丁酮、N,N-二甲基甲酰胺中的一种或几种。The 3D curved screen self-healing TPU protective film according to claim 4, wherein the polyisocyanate is hexamethylene diisocyanate or its polymer, isophorone diisocyanate or its polymer One or more; the polyester polyol is one or more of conventional polyester polyol, polycaprolactone polyol and polycarbonate diol; the chain extender is ethylene glycol, 1, One or more of 4-butanediol, 1,6-hexanediol, glycerin, and trimethylolpropane; the catalyst is dibutyltin dilaurate; the second solvent is ethyl acetate, toluene One or more of, butanone, N,N-dimethylformamide.
  6. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,所述光学级高粘性丙烯酸压敏胶层是由光学级高粘性丙烯酸压敏胶水涂布而成,所述光学级高粘性丙烯酸压敏胶水由100重量份丙烯酸软单体、10~30重量份丙烯酸硬单体、3~10份羟基丙烯酸单体通过引发剂的作用在第三溶剂中聚合而成;所述光学级高粘性丙烯酸压敏胶层的厚度范围为15~40μm。The 3D curved screen self-healing TPU protective film according to claim 1, wherein the optical-grade high-viscosity acrylic pressure-sensitive adhesive layer is coated with optical-grade high-viscosity acrylic pressure-sensitive adhesive. The high-viscosity acrylic pressure-sensitive adhesive is polymerized by 100 parts by weight of soft acrylic monomer, 10-30 parts by weight of hard acrylic monomer, and 3-10 parts of hydroxy acrylic monomer in a third solvent through the action of an initiator; The thickness of the high-viscosity acrylic pressure-sensitive adhesive layer ranges from 15 to 40 μm.
  7. 根据权利要求6所述的3D曲面屏自修复TPU保护膜,其特征在于,所述丙烯酸软单体为丙烯酸正丁酯、丙烯酸乙酯、丙烯酸异辛酯、丙烯酸月桂酯、甲基丙烯酸月桂酯中的两种或几种;所述丙烯酸硬单体为丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、醋酸乙烯酯、丙烯酰胺、丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯中的两种或几种;所述羟基丙烯酸单体为丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯中的一种或几种;所述引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化二苯甲酰、过氧化月桂酰中的一种或几种;所述第三溶剂 为乙酸乙酯、甲苯、丙酮、环己烷中的一种或几种。The 3D curved screen self-healing TPU protective film according to claim 6, wherein the acrylic soft monomer is n-butyl acrylate, ethyl acrylate, isooctyl acrylate, lauryl acrylate, lauryl methacrylate Two or more of the acrylic acid hard monomers are acrylic acid, methacrylic acid, methyl methacrylate, vinyl acetate, acrylamide, isobornyl acrylate, and glycidyl methacrylate. Several; the hydroxy acrylic monomer is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate; the initiator It is one or more of azobisisobutyronitrile, azobisisoheptonitrile, dibenzoyl peroxide, and lauroyl peroxide; the third solvent is ethyl acetate, toluene, acetone, and cyclohexane One or more of alkanes.
  8. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,在涂布过程中,所述光学级高粘性丙烯酸压敏胶水中添加0.1~2%的第二固化剂,所述第二固化剂为六亚甲基二异氰酸酯的二聚体或三聚体。The 3D curved screen self-healing TPU protective film according to claim 1, characterized in that, in the coating process, 0.1-2% of the second curing agent is added to the optical-grade high-viscosity acrylic pressure-sensitive adhesive water, and the The second curing agent is a dimer or trimer of hexamethylene diisocyanate.
  9. 根据权利要求1所述的3D曲面屏自修复TPU保护膜,其特征在于,所述3D曲面屏自修复TPU保护膜的透光率大于90%,雾度小于1%,水接触角达到105°以上,动摩擦系数<0.2。The 3D curved screen self-healing TPU protective film according to claim 1, wherein the light transmittance of the 3D curved screen self-healing TPU protective film is greater than 90%, the haze is less than 1%, and the water contact angle reaches 105° Above, the dynamic friction coefficient is less than 0.2.
  10. 一种3D曲面屏自修复TPU保护膜的制备方法,其特征在于,包括如下步骤:A method for preparing a self-repairing TPU protective film for a 3D curved screen, which is characterized in that it comprises the following steps:
    (1)将光学级硬质TPU胶水涂布在PET离型膜C上,在90-120℃温度下烘干固化后形成光学级硬质TPU树脂膜层;(1) Coat the optical grade hard TPU glue on the PET release film C, dry and cure at 90-120℃ to form an optical grade hard TPU resin film layer;
    (2)将光学级高粘性丙烯酸压敏胶水涂布到光学级硬质TPU树脂膜层上,在80-120℃温度下烘干固化后形成光学级高粘性丙烯酸压敏胶层,在光学级高粘性丙烯酸压敏胶层上覆盖一层离型膜B;(2) Coat optical-grade high-viscosity acrylic pressure-sensitive adhesive on the optical-grade hard TPU resin film layer, and dry and cure at 80-120℃ to form an optical-grade high-viscosity acrylic pressure-sensitive adhesive layer. A layer of release film B is covered on the high-viscosity acrylic pressure-sensitive adhesive layer;
    (3)撕掉离型膜C,将光学级自修复涂料涂布在所述光学级硬质TPU树脂膜层的另一面,在80-110℃温度下烘干固化后形成光学级自修复涂层,再在自修复涂层表面覆盖离型膜A,收卷,收卷后放置于50~60℃条件下熟化48~72h,得到3D曲面屏自修复TPU保护膜。(3) Tear off the release film C, apply an optical-grade self-healing coating on the other side of the optical-grade hard TPU resin film layer, and dry and cure at a temperature of 80-110°C to form an optical-grade self-healing coating Then cover the release film A on the surface of the self-healing coating, rewind, and place it at 50-60°C after rewinding and curing for 48-72h to obtain a 3D curved screen self-repairing TPU protective film.
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