CN110669450A - Protective film and preparation method thereof - Google Patents

Protective film and preparation method thereof Download PDF

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Publication number
CN110669450A
CN110669450A CN201910971790.0A CN201910971790A CN110669450A CN 110669450 A CN110669450 A CN 110669450A CN 201910971790 A CN201910971790 A CN 201910971790A CN 110669450 A CN110669450 A CN 110669450A
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layer
parts
protective film
polyolefin
agent
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张程
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Shanghai Solid Adhesive Tape Technology Co Ltd
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Shanghai Solid Adhesive Tape Technology Co Ltd
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Priority to CN201910971790.0A priority Critical patent/CN110669450A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to the field of protective films, in particular to a protective film and a preparation method thereof. The protective film comprises a base material film layer and an adhesive layer from top to bottom in sequence; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 10-15 parts of cross-linking agent and 2-5 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 50-100 parts of reactive monomer, 60-80 parts of diluent, 0-10 parts of curing agent and 0-10 parts of stabilizer. The protective film provided by the invention has excellent barrier property, curing formability, light transmittance, expansibility, mechanical property, water resistance, temperature resistance and aging resistance, is environment-friendly, and has no adhesive residue after being stripped.

Description

Protective film and preparation method thereof
Technical Field
The invention relates to the field of protective films, in particular to a protective film and a preparation method thereof.
Background
The protective film is a material with a protective function, is mainly used for protecting the surface of a product or a material in the process of processing and transmission, and prevents the surface of the product or the material from being polluted and damaged, so that the appearance, the grade and the yield of the product are improved. The protective film is generally formed by coating a special pressure-sensitive adhesive on a plastic film or a paper substrate and processing the plastic film or the paper substrate through a special process, has the characteristics of easy sticking, no warping, no surface pollution and the like, and is widely applied to the fields of instruments, furniture, color steel plates, aluminum materials, building profiles, electronics, household appliances, automobiles and the like, so the protective film has an important role.
The invention aims to develop a protective film which has excellent barrier property, curing formability, light transmittance, mechanical property, water resistance, temperature resistance and aging resistance, is environment-friendly and has no adhesive residue after being stripped.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a protective film, which comprises a substrate film layer and a glue layer in sequence from top to bottom; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 10-15 parts of cross-linking agent and 2-5 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 50-100 parts of reactive monomer, 60-80 parts of diluent, 0-10 parts of curing agent and 0-10 parts of stabilizer.
As a preferred technical solution of the present invention, the protective film further includes a silicon oil layer; the silicon oil layer is prepared from the following raw materials in parts by weight: 50-70 parts of organic silicone oil, 6-8 parts of fixing agent, 6-8 parts of stabilizing agent and 50-70 parts of diluent; the silicon oil layer is connected with the upper surface of the substrate film.
As a preferable technical solution of the present invention, the protective film further includes a PET layer; the PET layer is connected with the lower surface of the adhesive layer.
In a preferred embodiment of the present invention, the raw material for preparing the first corona layer and the second corona layer comprises polypropylene.
As a preferred embodiment of the present invention, the polyolefin is a modified polyolefin.
As a preferable technical scheme of the invention, the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite, strontium oxide and a silane coupling agent.
As a preferred embodiment of the present invention, the silane coupling agent is selected from one or more of methyltriethoxysilane, vinyltriethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane, bis [ γ (-triethoxysilyl) propyl ] -tetrasulfide, γ -glycidoxypropyltrimethoxysilane, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine.
In a preferred embodiment of the present invention, the crosslinking agent is t-butylperoxy-3, 5, 5-trimethylhexanoate and/or 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
As a preferable technical scheme of the invention, the weight ratio of the tert-butyl peroxy-3, 5, 5-trimethyl hexanoate to the 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane is (3-6): 1.
the second aspect of the present invention provides a method for preparing the protective film, which can be classified into a direct coating method and a spin coating method.
Has the advantages that: the invention provides a protective film and a preparation method thereof, the protective film is formed by combining a film material and a pressure-sensitive adhesive, and the film obtained by modifying polyolefin and a reactive monomer has excellent barrier property, curing formability, light transmittance, expansibility, mechanical property, water resistance, temperature resistance and aging resistance, is environment-friendly, and has no residual adhesive after being peeled off.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "more preferred", and the like, in the present invention refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the above technical problems, a first aspect of the present invention provides a protective film, which comprises a substrate film layer and a glue layer in sequence from top to bottom; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 10-15 parts of cross-linking agent and 2-5 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 50-100 parts of reactive monomer, 60-80 parts of diluent, 0-10 parts of curing agent and 0-10 parts of stabilizer.
In one embodiment, the protective film further comprises a layer of silicone oil; the silicon oil layer is prepared from the following raw materials in parts by weight: 50-70 parts of organic silicone oil, 6-8 parts of fixing agent, 6-8 parts of stabilizing agent and 50-70 parts of diluent; the silicon oil layer is connected with the upper surface of the substrate film.
In a preferred embodiment, the silicone oil layer is prepared from the following raw materials in parts by weight: 60 parts of organic silicone oil, 7 parts of fixing agent, 7 parts of stabilizing agent and 60 parts of diluting agent.
Organic silicone oil
The organic silicone oil refers to polyorganosiloxane with chain structures with different polymerization degrees. It is prepared through hydrolysis of dimethyldichlorosilane in water to obtain initial condensed ring body, cracking and rectifying to obtain low ring body, mixing the ring body, sealing agent and catalyst together to obtain various mixture with different polymerization degree, and vacuum distillation to eliminate low-boiling point matter to obtain silicone oil.
In the examples, the silicone oil was prepared by: jinan Zhengquan Total chemical Co., Ltd, type: 001.
fixing agent
In one embodiment, the fixative is polyvinylpyrrolidone.
Examples polyvinylpyrrolidone, manufacturer: zhengzhou Jixing chemical products Co., Ltd.
Stabilizer
The stabilizer refers to a chemical capable of increasing the stability of a solution, a colloid, a solid or a mixture. It can slow down reaction, maintain chemical equilibrium, reduce surface tension, and prevent photo, thermal or oxidative decomposition. The source is very wide, and any chemical can be flexibly used according to the design purpose of a formula designer so as to achieve the purpose of stable product quality.
In one embodiment, the stabilizer is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ].
The pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in the examples was prepared by the following manufacturer: hubei cat Er Wao biological medicine, Inc., Cat # goods: 0761.
diluent
The diluent refers to an inert substance added for dilution when the raw material is processed into powder or in order to facilitate spraying.
In one embodiment, the diluent is ethyl acetate.
Examples ethyl acetate, CAS number: 141-78-6.
The preparation method of the silicon oil layer comprises the following steps:
pouring the organic silicon oil into the diluent at a constant speed, stirring simultaneously, adding the curing agent after stirring for 10-15min, stirring at a constant speed for 20-40min, then adding the stabilizer, and stirring at a constant speed for 20-30min to obtain the silicone oil layer.
In a preferred embodiment, the silicone oil layer is prepared by a method comprising the following steps:
pouring the organic silicone oil into the diluent at a constant speed, stirring simultaneously, adding the curing agent after stirring for 12min, stirring at a constant speed for 30min, then adding the stabilizer, and stirring at a constant speed for 25min to obtain the silicone oil layer.
PET
The PET is short for polyethylene terephthalate, and is prepared by exchanging dimethyl terephthalate with ethylene glycol or esterifying terephthalic acid with ethylene glycol to synthesize dihydroxyethyl terephthalate, and then performing polycondensation reaction. Belongs to crystalline saturated polyester, is milk white or light yellow and highly crystalline polymer, and has smooth and glossy surface.
In one embodiment, the protective film further comprises a PET layer; the PET layer is connected with the lower surface of the adhesive layer.
In one embodiment, the PET layer is a PET film.
In the examples, the PET film, manufacturer: shantou Runzhu Xu plastic film Co., Ltd, type: PET-19.
In one embodiment, the raw materials from which the first and second corona layers are made include polypropylene.
In one embodiment, the raw material for making the clear and matte layers comprises erucamide.
Erucamide in the examples, manufacturer: shanghai hua sparkling chemical assistant limited, model: SHHY-A003.
In one embodiment, the antistatic layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 6-10 parts of antistatic agent and 10-15 parts of crosslinking agent.
In a preferred embodiment, the antistatic layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 8 parts of antistatic agent and 12 parts of crosslinking agent.
In a preferred embodiment, the inner layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 12 parts of cross-linking agent and 3 parts of color master batch.
In one embodiment, the anti-oxidation layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 6-12 parts of antioxidant and 10-15 parts of cross-linking agent.
In a preferred embodiment, the anti-oxidation layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 10 parts of antioxidant and 12 parts of crosslinking agent.
Polyolefins
The polyolefin refers to a polymer of ethylene, propylene or higher olefins. English is abbreviated as PO. The polymer material has the advantages of abundant raw materials, low price, easy processing and forming and excellent comprehensive performance, so the polymer material has the largest output and very wide application.
In one embodiment, the polyolefin is selected from one or more of polyethylene, polypropylene, ethylene-propylene copolymers, polybutene-1, poly-4-methylpentene-1, ethylene-vinyl acetate copolymers, ethylene-ethyl (meth) acrylate copolymers, ethylene-methyl (meth) acrylate copolymers, ethylene-acrylic acid copolymers.
In a preferred embodiment, the polyolefin is a modified polyolefin.
In one embodiment, the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite, strontium oxide and a silane coupling agent.
In a preferred embodiment, the weight ratio of the hydroxyapatite to the strontium oxide to the silane coupling agent is 1: (3.5-4.5): (0.6-0.8).
In a preferred embodiment, the weight ratio of the hydroxyapatite to the strontium oxide to the silane coupling agent is 1: 4: 0.7.
hydroxyapatite
The hydroxyapatite refers to natural mineralization of calcium apatite, hydroxyl can be replaced by fluoride, chloride and carbonate ions to generate fluorine-based apatite or chlorine-based apatite, and calcium ions in the hydroxyapatite can be replaced by various metal ions through ion exchange reaction to form M apatite corresponding to the metal ions.
In the examples, hydroxyapatite was prepared by the following manufacturers: west anwanfang biotechnology limited, model: wf-01.
Strontium oxide
The strontium oxide, an oxide, can be prepared by decomposing strontium carbonate or strontium hydroxide, and becomes strontium hydroxide and generates heat when it encounters water.
Strontium oxide in examples, CAS No.: 314-11-0.
Silane coupling agent
The molecular structural formula of the silane coupling agent is generally as follows: Y-R-Si (OR)3(wherein Y-organic functional group, SiOR-siloxy). The siloxy group is reactive with inorganic species and the organofunctional group is reactive or compatible with organic species. Thus, when a silane coupling agent intervenes between the inorganic and organic interfaces, a bonding layer of organic matrix-silane coupling agent-inorganic matrix may be formed.
In one embodiment, the silane coupling agent is selected from one or more of methyltriethoxysilane, vinyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane, bis [ γ (-triethoxysilyl) propyl ] -tetrasulfide, γ -glycidoxypropyltrimethoxysilane, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine.
In a preferred embodiment, the silane coupling agents are gamma-glycidoxypropyltrimethoxysilane and N, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine.
In a preferred embodiment, the weight ratio of gamma-glycidoxypropyltrimethoxysilane to N, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine is 1: (2-3).
In a preferred embodiment, the weight ratio of gamma-glycidoxypropyltrimethoxysilane to N, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine is 1: 2.
examples gamma-glycidoxypropyltrimethoxysilane, manufacturer: shenzhen ai Tuo chemical Co.
Examples N, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine, manufacturer: shenzhen ai Tuo chemical Co.
In a preferred embodiment, the modified polyolefin is a modified polypropylene.
The modified polypropylene comprises the following steps:
(1) preheating polypropylene in an oven at 100-120 deg.C for 8-12 min;
(2) uniformly mixing the preheated polypropylene, hydroxyapatite, strontium oxide and a silane coupling agent, and then mixing for 10-12 minutes at the temperature of 160-180 ℃ to obtain a mixed material;
(3) and transferring the mixed material into a flat press, carrying out hot pressing at the temperature of 190 ℃ and 200 ℃ and at the pressure of 180 ℃ and 200MPa for 9-11 minutes to obtain a hot pressing material, and carrying out cold pressing for 8-12 minutes to obtain the modified polypropylene.
In a preferred embodiment, the modified polypropylene comprises the following steps:
(1) preheating polypropylene in an oven at 120 deg.C for 10 min;
(2) uniformly mixing the preheated polypropylene, hydroxyapatite, strontium oxide and a silane coupling agent, and then mixing for 12 minutes at the temperature of 180 ℃ to obtain a mixed material;
(3) and transferring the mixed material into a flat press, carrying out hot pressing at the temperature of 200 ℃ and the pressure of 180MPa for 10 minutes to obtain hot pressing material, and carrying out cold pressing for 10 minutes to obtain the modified polypropylene.
Examples polypropylene, manufacturer: industrial company, linadebo, trade mark: HL 451J.
The inventor finds that the barrier property, curing formability, aging resistance and water resistance of the film can be improved by adding hydroxyapatite, strontium oxide and a silane coupling agent as a polyolefin modifier, and the probable reason is that the hydroxyapatite can form a compact hydroxyapatite layer on the surface of polyolefin and has a barrier effect on the polyolefin film, each unit cell of the hydroxyapatite contains 10 calcium ions, 6 phosphate ions and 2 hydroxyl groups, and the strontium oxide can react with the calcium ions to form a layer of strontium calcium hydroxyphosphate on the surface of the hydroxyapatite to adsorb the calcium ions, reduce the surface charge of the hydroxyapatite, prevent the growth of hydroxyapatite crystals, prevent the agglomeration of the hydroxyapatite and improve the dispersibility; in addition, silicon hydroxyl formed after hydrolysis of the gamma-glycidyl ether oxypropyl trimethoxysilane can be subjected to dehydration condensation with hydroxyl to form a covalent bond, so that the influence of hydroxyl hydrophilicity on polyolefin on hydroxyapatite is compensated, the coupling agent can also generate a-P-O-Si-bond with the hydroxyapatite, and a stable chelate can be generated with metal, so that the corrosion of the metal is slowed down; the amino group carried by the N, N-diethyl-N' - [ tri (1-methylethoxy) silicon-based ] -1, 4-phenylenediamine can be adsorbed by the hydrogen bond reaction with the phosphate radical on the surface of the hydroxyapatite, thereby further preventing the hydroxyapatite from generating intermolecular aggregation and improving the dispersibility of the hydroxyapatite on a film substrate; meanwhile, after the silicon oxygen groups are hydrolyzed by N, N-diethyl-N' - [ tri (1-methylethoxy) silicon-based ] -1, 4-phenylenediamine, the exposed amino groups can be cooperated with the amino groups in the trimethylhexamethylenediamine curing agent to improve the curing speed. In addition, after the coupling agent is cured to form a film, better waterproof and corrosion-resistant capabilities can be provided. The inventor unexpectedly finds that the aniline group in the N, N-diethyl-N' - [ tri (1-methylethoxy) silicon-based ] -1, 4-phenylenediamine can directly react with VOC possibly existing in hot-melt peelable glue, so that the protective film is more environment-friendly and pollution-free.
Elastic body
The elastic body is a high polymer material which has obvious deformation under weak stress and can be quickly recovered to be close to the original state and size after the stress is relaxed.
In one embodiment, the elastomer is an ethylene-based elastomer or a propylene-based elastomer.
The elastomer in the examples is a propylene-based elastomer, manufacturer: hong Gu sea plastics Co., Ltd, Dongguan city, model number: 6202 FL.
Antistatic agent
The antistatic agent refers to an additive which is added into plastic or coated on the surface of a molded article for the purpose of reducing static electricity accumulation. Antistatic agents can be classified into internal type antistatic agents and external type antistatic agents, mainly internal type antistatic agents, and temporary type antistatic agents and permanent type antistatic agents, depending on the method of use.
In one embodiment, the antistatic agent is an ethylene-sodium acrylate copolymer.
Examples ethylene-sodium acrylate copolymer, manufacturer: guangzhou Dongxin International trade company, brand: the dow is.
Antioxidant agent
Antioxidants are chemical substances which, when present in only small amounts in polymer systems, retard or inhibit the progress of the oxidation process of the polymer, thereby preventing the aging of the polymer and extending its useful life, also known as "age resistors". Antioxidants help protect the above-mentioned polymers and the overall binder system from the effects of thermal and oxidative degradation that often occur during the manufacture and application of film compositions and in the ambient environment to which the final product is normally exposed, primarily as a result of deterioration in the appearance, physical properties, etc. of the composition.
In one embodiment, the antioxidant is octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate.
Examples octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate, manufacturer: shengmei plastication science and technology limited, Dongguan city, CAS number: 2082-79-3.
Crosslinking agent
The cross-linking agent is also called bridging agent, and reacts with the hydrocarbon resin to form bridge bonds between polymer molecular chains, so that the polymer becomes insoluble substances with a three-dimensional structure. Crosslinking agents are mainly used in high molecular materials (rubbers and thermosetting resins). Because the molecular structure of the high molecular material is like a long line, the high molecular material has low strength when not crosslinked, is easy to break and has no elasticity, the crosslinking agent has the function of generating chemical bonds among linear molecules, so that the linear molecules are mutually connected to form a net structure.
In one embodiment, the crosslinking agent is t-butylperoxy-3, 5, 5-trimethylhexanoate and/or 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
In a preferred embodiment, the weight ratio of tert-butylperoxy-3, 5, 5-trimethylhexanoate to 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane is (3-6): 1.
in a preferred embodiment, the weight ratio of tert-butylperoxy-3, 5, 5-trimethylhexanoate to 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane is 5: 1.
examples tert-butyl peroxy-3, 5, 5-trimethylhexanoate, manufacturer: guangdong Zhongqi New Material science and technology Co., Ltd, Cat #: 52070.
example 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, manufacturer: guangdong Zhongqi New Material science and technology Co., Ltd, Cat #: 2156.
the inventor finds that the water resistance, light transmittance, peeling strength and aging resistance of the film can be improved by adding the cross-linking agent, and probably because the tert-butyl peroxy-3, 5, 5-trimethyl hexanoate contains ester groups, alkyl groups and the like, has large steric hindrance and hydrophobicity, so that the water resistance of the film is improved, and the hydrophobic tert-butyl peroxy-3, 5, 5-trimethyl hexanoate can make up the problem of water resistance reduction caused by hydroxyapatite; but the peroxide (2-ethylhexyl) tert-amyl carbonate is decomposed in advance and unstable during casting film making, and the 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane is compounded with the peroxide (tert-butyl peroxide) ethyl carbonate to make up for the problem of high peroxidation activity of a cross-linking agent, ensure complete cross-linking, form a net structure and improve the peel strength and the aging resistance; simultaneously inhibits the crystallinity of polyolefin and improves the light transmittance.
Color master batch
The color master batch refers to a novel special coloring agent for high polymer materials, and is also called a pigment preparation. Color concentrates are composed of three basic elements, a pigment or dye, a carrier and additives, and are aggregates prepared by uniformly supporting an excessive amount of pigment in a resin, and can be referred to as pigment concentrates, so that they have a higher tinctorial strength than the pigment itself. During processing, a small amount of color master batch is mixed with uncolored resin, and colored resin or products with designed pigment concentration can be obtained.
In one embodiment, the color masterbatch is a PP color masterbatch.
In the examples, the PP masterbatch was manufactured by: kraien chemical (china) limited, cat #: 10001.
the substrate film layer comprises the following preparation steps:
and simultaneously feeding the first corona layer, the bright layer, the antistatic layer, the inner layer, the antioxidation layer, the matte layer and the second corona layer into a machine head of a co-extruder, fusing and extruding to form a film bubble, and cooling and molding the film bubble under cooling air at 15-25 ℃.
In one embodiment, the substrate film layer has a thickness of 30 to 300 μm.
In a preferred embodiment, the thickness of the substrate film layer is 200 μm.
In one embodiment, the reactive monomer is selected from one or more of methyl acrylate, epoxy resin, epoxy acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, isobutyl acrylate, acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl methacrylate, polyfluoro-containing acrylates, ethoxyethoxyethyl acrylate, isobornyl acrylate, dodecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, 2-phenoxyethyl acrylate, tetrahydrofuran acrylate, tripropylene glycol diacrylate, 1,6 hexanediol diacrylate.
In a preferred embodiment, the reactive monomer is acrylic acid.
In a preferred embodiment, the acrylic acid is a modified acrylic acid.
In a preferred embodiment, the modified acrylic acid is a polyfluoro acrylic acid derivative obtained by modifying acrylic acid with a modified silane coupling agent.
In a preferred embodiment, the weight ratio of the acrylic acid, the polyfluoroacrylic acid derivative and the modified silane coupling agent is 1: (0.7-0.9): (0.4-0.6).
In a preferred embodiment, the weight ratio of the acrylic acid, the polyfluoroacrylic acid derivative and the modified silane coupling agent is 1: 0.8: 0.5.
in a preferred embodiment, the polyfluoroacrylic acid derivative is dodecafluoroheptyl methacrylate.
In a preferred embodiment, the modified silane coupling agent is obtained by modifying a silane coupling agent with an epoxy group-containing compound.
In a preferred embodiment, the epoxy group-containing compound is epichlorohydrin.
In a preferred embodiment, the silane coupling agent is bis (3- (methylamino) propyl) trimethoxysilane.
Examples acrylic acid, manufacturer: dupont Dow company, trade designation: 1430.
examples dodecafluoroheptyl methacrylate, manufacturer: shanghai-sourced leaf Biotechnology, Inc., Cat number: s63482-5 g.
Epichlorohydrin in the examples, the manufacturer: shandong Xu Chen chemical technology Co., Ltd.
Examples bis (3- (methylamino) propyl) trimethoxysilane, manufacturer: shanghai Jinjinle industry Co., Ltd, product number: JJL573 90202020202.
Examples azobisisobutyronitrile, manufacturer: changzhou city enlightening chemical Co., Ltd, product number: qd 78671.
In the examples, xylene, manufacturer: zibo Xuyin chemical Co., Ltd.
The modified silane coupling agent comprises the following steps:
120-125g of bis (3- (methylamino) propyl) trimethoxysilane is dissolved in 120-125g of toluene, stirred for 2-2.5h at room temperature, added with 0.5-0.6mol of epichlorohydrin and reacted for 4-5h at 50-60 ℃.
In a preferred embodiment, the modified silane coupling agent comprises the steps of:
120g of bis (3- (methylamino) propyl) trimethoxysilane was dissolved in 120g of toluene, stirred at room temperature for 2 hours, and 0.5mol of epichlorohydrin was added thereto to react at 60 ℃ for 5 hours.
The modified acrylic acid comprises the following steps:
(1) adding acrylic acid, polyfluoroacrylic acid derivatives and modified silane coupling agents into a four-neck reaction flask provided with an electric stirring paddle, a condensation pipe, a nitrogen inlet pipe and a thermometer, adding an initiator of azobisisobutyronitrile, wherein the weight of the azobisisobutyronitrile is 60-65% of the total weight of the acrylic acid, the polyfluoroacrylic acid derivatives and the modified silane coupling agents, and finally adding a xylene solvent;
(2) introducing nitrogen for 30-40 min at normal temperature to eliminate oxygen in the system;
(3) and continuously introducing nitrogen, heating the oil bath to 80-85 ℃, stirring, refluxing and reacting for 2-2.5h, and cooling to room temperature to obtain the modified acrylic acid.
In a preferred embodiment, the modified acrylic acid comprises the steps of:
(1) adding acrylic acid, polyfluoroacrylic acid derivatives and modified silane coupling agents into a four-neck reaction flask provided with an electric stirring paddle, a condensation pipe, a nitrogen inlet pipe and a thermometer, adding an initiator of azobisisobutyronitrile, wherein the weight of the azobisisobutyronitrile is 60 percent of the total weight of the acrylic acid, the polyfluoroacrylic acid derivatives and the modified silane coupling agents, and finally adding a xylene solvent;
(2) introducing nitrogen for 30 minutes at normal temperature, and removing oxygen in the system;
(3) and continuously introducing nitrogen, heating the oil bath to 85 ℃, stirring and refluxing for reaction for 2 hours, and cooling to room temperature to obtain the modified acrylic acid.
The inventor finds that the water resistance, the stretchability and the mechanical property of the adhesive can be improved by modifying the acrylic resin, and no adhesive residue exists, and the probable reason is that multiple fluorine atoms carried by the polyfluoroacrylic acid derivative have hydrophobicity and can improve the water resistance of the film, and the modified silane coupling agent can improve the hydrophobicity of the film, and simultaneously, epoxy groups react with hydroxyl groups in a base material, so that the cohesiveness is enhanced, and the stretchability and the mechanical property of the adhesive are improved; in addition, the weight ratio of the acrylic acid to the polyfluoroacrylic acid derivative to the modified silane coupling agent is 1: (0.7-0.9): (0.4-0.6), the adhesive force between the glue and the film formed by taking the modified acrylic resin as the base material is greater than the cohesive force of the glue, and no residual glue is left after the cold tearing after the high-temperature baking at 180 ℃.
The adhesive layer comprises the following steps:
and uniformly mixing the reactive monomer, the diluent, the curing agent and the stabilizer according to the proportion to obtain the high-performance polyurethane adhesive.
In one embodiment, the thickness of the glue layer is 5-300 μm.
In a preferred embodiment, the thickness of the glue layer is 200 μm.
The second aspect of the present invention provides a method for producing the protective film as described above, which can be classified into a direct coating method and a spin coating method.
The direct coating method comprises the following steps:
(1) compounding the base material film with the silicon oil layer after corona treatment, and placing the base material film in an oven for 1 to 2 days;
(2) after corona is carried out on the upper surface of the base material film, the base material film and the glue layer are compounded into a drying oven, and the mixture is placed for 7 days to be stable.
The transfer coating method comprises the following steps:
(1) compounding the PET film serving as a substrate with the adhesive layer, and then feeding the PET film and the adhesive layer into a drying oven to obtain a glued PET film;
(2) the corona and the glued PET film on the upper surface of the substrate film are compounded and are stable after being placed for 15 days.
In one embodiment, the thickness of the protective film is 5 to 500 μm.
In a preferred embodiment, the thickness of the protective film is 400 μm.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
The protective film comprises a base material film layer and an adhesive layer from top to bottom in sequence; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 12 parts of cross-linking agent and 3 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 75 parts of reactive monomer, 70 parts of diluent, 5 parts of curing agent and 5 parts of stabilizing agent;
the protective film also comprises a silicon oil layer; the silicon oil layer is prepared from the following raw materials in parts by weight: 60 parts of organic silicone oil, 7 parts of fixing agent, 7 parts of stabilizing agent and 60 parts of diluting agent; the silicon oil layer is connected with the upper surface of the base material film;
the fixing agent is polyvinylpyrrolidone, and the manufacturer comprises: zhengzhou jixing chemical products limited, CAS No.: 9003-39-8;
the stabilizer is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, CAS number: 6683-19-8;
the diluent is ethyl acetate, CAS No.: 141-78-6;
the preparation method of the silicon oil layer comprises the following steps:
pouring the organic silicone oil into the diluent at a constant speed, stirring simultaneously, adding the curing agent after stirring for 12min, stirring at a constant speed for 30min, then adding the stabilizer, and stirring at a constant speed for 25min to obtain the silicone oil layer.
The organic silicon oil is prepared from the following raw materials: jinan Zhengquan Total chemical Co., Ltd, type: 001;
the preparation raw materials of first corona layer and second corona layer are polypropylene, and the producer: industrial company, linadebo, trade mark: HL 451J;
the bright layer and the matte layer are prepared from erucamide as a raw material, and the manufacturer comprises the following components: shanghai hua sparkling chemical assistant limited, model: SHHY-A003;
the antistatic layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 8 parts of antistatic agent and 12 parts of crosslinking agent;
the inner layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 12 parts of cross-linking agent and 3 parts of color master batch;
the anti-oxidation layer is prepared from the following raw materials in parts by weight: 75 parts of polyolefin, 65 parts of elastomer, 10 parts of antioxidant and 12 parts of crosslinking agent;
the polyolefin is modified polyolefin;
the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite, strontium oxide and a silane coupling agent;
the weight ratio of the hydroxyapatite to the strontium oxide to the silane coupling agent is 1: 4: 0.7;
the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane and N, N-diethyl-N' - [ tri (1-methylethoxy) silicon-based ] -1, 4-phenylenediamine;
the weight ratio of the gamma-glycidoxypropyltrimethoxysilane to the N, N-diethyl-N' - [ tri (1-methylethoxy) silyl ] -1, 4-phenylenediamine is 1: 2;
the hydroxyapatite is prepared by the following raw materials: west anwanfang biotechnology limited, model: wf-01; the strontium oxide, CAS No.: 314-11-0; the gamma-glycidoxypropyltrimethoxysilane, CAS no: 2530-83-8; the N, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine, manufacturer: shenzhen ai Tuo chemical Co., Ltd;
the modified polyolefin comprises the following steps:
(1) preheating polyolefin in an oven at 120 ℃ for 10 min;
(2) uniformly mixing the preheated polyolefin with hydroxyapatite, strontium oxide and a silane coupling agent, and then mixing for 12 minutes at the temperature of 180 ℃ to obtain a mixed material;
(3) and transferring the mixed material into a flat press, carrying out hot pressing at the temperature of 200 ℃ and the pressure of 180MPa for 10 minutes to obtain hot pressing material, and carrying out cold pressing for 10 minutes to obtain the modified polyolefin.
The elastomer is a propylene-based elastomer, and the type is as follows: 6202 FL;
the antistatic agent is an ethylene-sodium acrylate copolymer, and the manufacturer comprises: guangzhou Dongxin International trade company, brand: the Dow;
the antioxidant is octadecanol-3- [3, 5-di-tert-butyl-4- (2-hydroxy-propoxy) -phenyl ] propionate, CAS number: 2082-79-3;
the cross-linking agent is tert-butyl peroxy-3, 5, 5-trimethyl hexanoate and/or 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane;
the weight ratio of the tert-butyl peroxy-3, 5, 5-trimethyl hexanoate to the 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane is 5: 1;
the tert-butyl peroxy-3, 5, 5-trimethylhexanoate, CAS No.: 13122-18-4; the 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, CAS number: 78-63-7;
the color master batch is a PP color master batch, and is prepared by the following steps: kraien chemical (china) limited, cat #: 10001;
the substrate film layer comprises the following preparation steps:
and simultaneously feeding the first corona layer, the bright layer, the antistatic layer, the inner layer, the antioxidation layer, the matte layer and the second corona layer into a machine head of a co-extruder, fusing and extruding to form a film bubble, and cooling and molding the film bubble under cooling air at 15-25 ℃.
The reaction type monomer is acrylic acid, and the manufacturer comprises: dupont Dow company, trade designation: 1430;
the acrylic acid is modified acrylic acid;
the modified acrylic acid is obtained by modifying acrylic acid through polyfluoro acrylic acid derivatives and modified silane coupling agents;
the weight ratio of the acrylic acid to the polyfluoro acrylic acid derivative to the modified silane coupling agent is 1: 0.8: 0.5;
the polyfluoro acrylic acid derivative is methacrylic acid dodecafluoroheptyl ester, and the product number is as follows: CAS number: 2261-99-6;
the modified silane coupling agent is obtained by modifying a silane coupling agent by an epoxy group-containing compound;
the epoxy group-containing compound is epichlorohydrin, CAS number: 106-89-8;
the silane coupling agent is bis (3- (methylamino) propyl) trimethoxysilane, CAS number: 31024-70-1;
the modified silane coupling agent comprises the following steps:
120g of bis (3- (methylamino) propyl) trimethoxysilane was dissolved in 120g of toluene, stirred at room temperature for 2 hours, and 0.5mol of epichlorohydrin was added thereto to react at 60 ℃ for 5 hours.
The modified acrylic acid comprises the following steps:
(1) adding acrylic acid, polyfluoro acrylic acid derivatives and modified silane coupling agents into a four-mouth reaction flask provided with an electric stirring paddle, a condensation pipe, a nitrogen inlet pipe and a thermometer, adding an initiator of azobisisobutyronitrile (CAS number: 78-67-1), wherein the weight of the azobisisobutyronitrile is 60 percent of the total weight of the acrylic acid, the polyfluoro acrylic acid derivatives and the modified silane coupling agents, and finally adding a xylene solvent (CAS number: 1330-20-7);
(2) introducing nitrogen for 30 minutes at normal temperature, and removing oxygen in the system;
(3) and continuously introducing nitrogen, heating the oil bath to 85 ℃, stirring and refluxing for reaction for 2 hours, and cooling to room temperature to obtain the modified acrylic acid.
The adhesive layer comprises the following steps:
and uniformly mixing the reactive monomer, the diluent, the curing agent and the stabilizer according to the proportion to obtain the high-performance polyurethane adhesive.
The preparation method of the protective film can be divided into a direct coating method and a rotary coating method;
the direct coating method comprises the following steps:
(1) compounding the base material film with the silicon oil layer after corona treatment, and placing the base material film in an oven for 2 days;
(2) after corona is carried out on the upper surface of the base material film, the base material film and the glue layer are compounded into a drying oven, and the mixture is placed for 7 days to be stable.
Example 2
The protective film comprises a base material film layer and an adhesive layer from top to bottom in sequence; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 70 parts of polyolefin, 60 parts of elastomer, 10 parts of cross-linking agent and 2 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 75 parts of reactive monomer, 70 parts of diluent, 5 parts of curing agent and 5 parts of stabilizing agent;
the other operations were the same as in example 1.
Example 3
The protective film comprises a base material film layer and an adhesive layer from top to bottom in sequence; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 80 parts of polyolefin, 70 parts of elastomer, 15 parts of cross-linking agent and 5 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 100 parts of reactive monomer, 80 parts of diluent, 10 parts of curing agent and 10 parts of stabilizer;
the other operations were the same as in example 1.
Example 4
Example 4 differs from example 1 in that:
the isolation layer is a PET layer, and the PET layer is connected with the upper surface of the adhesive layer;
the PET layer is a PET film, and the manufacturer comprises: shantou Runzhu Xu plastic film Co., Ltd, type: PET-19;
the preparation method of the protective film comprises the following steps:
(1) compounding the PET film serving as a substrate with the adhesive layer, and then feeding the PET film and the adhesive layer into a drying oven to obtain a glued PET film;
(2) the corona and the glued PET film on the upper surface of the substrate film are compounded and are stable after being placed for about 15 days.
Comparative example 1
Comparative example 1 differs from example 1 in that: the polyolefin is unmodified.
Comparative example 2
Comparative example 2 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite.
Comparative example 3
Comparative example 3 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with strontium oxide.
Comparative example 4
Comparative example 4 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with silane coupling agent.
Comparative example 5
Comparative example 5 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite and strontium oxide.
Comparative example 6
Comparative example 6 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite and silane coupling agent.
Comparative example 7
Comparative example 7 differs from example 1 in that: the modified polyolefin is obtained by modifying polyolefin with strontium oxide and a silane coupling agent.
Comparative example 8
Comparative example 8 differs from example 1 in that: the weight ratio of the hydroxyapatite to the strontium oxide to the silane coupling agent is 1: 1: 0.7.
comparative example 9
Comparative example 9 differs from example 1 in that: the weight ratio of the hydroxyapatite to the strontium oxide to the silane coupling agent is 1: 7: 0.7.
comparative example 10
Comparative example 10 differs from example 1 in that: the inner layer is free of a crosslinking agent.
Comparative example 11
Comparative example 11 differs from example 1 in that: the cross-linking agent is tert-butyl peroxy-3, 5, 5-trimethyl hexanoate.
Comparative example 12
Comparative example 12 differs from example 1 in that: the cross-linking agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
Comparative example 13
Comparative example 13 differs from example 1 in that: the weight ratio of the tert-butyl peroxy-3, 5, 5-trimethyl hexanoate to the 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane is 1: 1.
comparative example 14
Comparative example 14 differs from example 1 in that: the weight ratio of the tert-butyl peroxy-3, 5, 5-trimethyl hexanoate to the 2, 5-dimethyl-2, 5-bis (tert-butyl peroxy) hexane is 9: 1.
comparative example 15
Comparative example 15 differs from example 1 in that: the acrylic acid is unmodified.
Comparative example 16
Comparative example 16 differs from example 1 in that: the modified acrylic acid is acrylic acid modified by polyfluoro acrylic acid derivatives.
Comparative example 17
Comparative example 17 differs from example 1 in that: the modified acrylic acid is obtained by modifying acrylic acid by using a modified silane coupling agent.
Comparative example 18
Comparative example 18 differs from example 1 in that: the modified acrylic acid is obtained by modifying acrylic acid with polyfluoro acrylic acid derivatives and silane coupling agents.
Comparative example 19
Comparative example 19 differs from example 1 in that: the weight ratio of the acrylic acid to the polyfluoro acrylic acid derivative to the modified silane coupling agent is 1: 0.4: 0.1.
comparative example 20
Comparative example 20 differs from example 1 in that: the weight ratio of the acrylic acid to the polyfluoro acrylic acid derivative to the modified silane coupling agent is 1: 1.2: 1.
comparative example 21
Comparative example 21 differs from example 1 in that:
the polyolefin is unmodified;
the inner layer is free of a cross-linking agent;
the acrylic acid is unmodified.
Evaluation of Performance
1. Protective film gas permeability:
o is measured with reference to the gas permeability of Plastic films and sheets of Standard GB/T1038-20002The amount of permeate.
2. Protective film 180 ° peel strength:
the measurement was carried out by an electronic universal tester (the adherend was a standard test steel plate, and the peel rate was 300mm/min) in accordance with GB/T2792-1995 "180 ℃ peel strength test method for pressure-sensitive adhesive tapes".
3. High humidity and high temperature resistance of the protective film:
the pressure-sensitive adhesive is uniformly coated on glass, the glass is placed in an environment with the temperature of 85 ℃ and the relative humidity of 85% for storage for 48 hours, and then the glass is peeled off to observe the condition of residual adhesive.
4. And (3) testing the light transmittance of the protective film:
the light transmittance was measured with reference to the standard GB/T2410-2008 using a haze meter (model: U3000).
TABLE 1 Performance test
Figure BDA0002232336790000191
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims (10)

1. The protective film is characterized by comprising a base material film layer and a glue layer from top to bottom in sequence; the base material film layer sequentially comprises a first corona layer, a bright layer, an antistatic layer, an inner layer, an anti-oxidation layer, a matte layer and a second corona layer; the inner layer is prepared from the following raw materials in parts by weight: 70-80 parts of polyolefin, 60-70 parts of elastomer, 10-15 parts of cross-linking agent and 2-5 parts of color master batch; the adhesive layer is prepared from the following raw materials in parts by weight: 50-100 parts of reactive monomer, 60-80 parts of diluent, 0-10 parts of curing agent and 0-10 parts of stabilizer.
2. The protective film of claim 1, further comprising a layer of silicone oil; the silicon oil layer is prepared from the following raw materials in parts by weight: 50-70 parts of organic silicone oil, 6-8 parts of fixing agent, 6-8 parts of stabilizing agent and 50-70 parts of diluent; the silicon oil layer is connected with the upper surface of the substrate film.
3. The protective film of claim 1, further comprising a PET layer; the PET layer is connected with the lower surface of the adhesive layer.
4. The protective film of claim 1, wherein a raw material for preparing the first corona layer and the second corona layer comprises polypropylene.
5. The protective film of claim 1, wherein the polyolefin is a modified polyolefin.
6. The protective film according to claim 5, wherein the modified polyolefin is obtained by modifying polyolefin with hydroxyapatite, strontium oxide, and a silane coupling agent.
7. The protective film according to claim 6, wherein the silane coupling agent is selected from one or more of methyltriethoxysilane, vinyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ - (methacryloyloxy) propyltrimethoxysilane, bis [ γ (-triethoxysilyl) propyl ] -tetrasulfide, γ -glycidoxypropyltrimethoxysilane, N-diethyl-N' - [ tris (1-methylethoxy) silyl ] -1, 4-phenylenediamine.
8. Protective film according to claim 1, characterized in that the cross-linking agent is tert-butyl peroxy-3, 5, 5-trimethylhexanoate and/or 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
9. The protective film according to claim 8, wherein the weight ratio of tert-butylperoxy-3, 5, 5-trimethylhexanoate to 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane is (3-6): 1.
10. a method for producing the protective film according to any one of claims 1 to 9, wherein the production method is classified into a direct coating method and a transfer coating method.
CN201910971790.0A 2019-10-14 2019-10-14 Protective film and preparation method thereof Withdrawn CN110669450A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116515429A (en) * 2023-07-05 2023-08-01 山东泰宝信息科技集团有限公司 Acrylic pressure-sensitive adhesive for screen printing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116515429A (en) * 2023-07-05 2023-08-01 山东泰宝信息科技集团有限公司 Acrylic pressure-sensitive adhesive for screen printing
CN116515429B (en) * 2023-07-05 2023-08-22 山东泰宝信息科技集团有限公司 Acrylic pressure-sensitive adhesive for screen printing

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