CN109651969B - Protective film and preparation method thereof - Google Patents

Protective film and preparation method thereof Download PDF

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CN109651969B
CN109651969B CN201811475035.5A CN201811475035A CN109651969B CN 109651969 B CN109651969 B CN 109651969B CN 201811475035 A CN201811475035 A CN 201811475035A CN 109651969 B CN109651969 B CN 109651969B
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protective film
ethylene
adhesive layer
density
layer
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CN109651969A (en
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张彦
陈强
胡金福
李刚
唐海江
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Ningbo Exciton Technology Co Ltd
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Ningbo Exciton Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/32—Making multilayered or multicoloured articles
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • 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
    • C09J2453/00—Presence of block copolymer
    • C09J2453/006—Presence of block copolymer in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention relates to the field of protective film materials, in particular to a protective film on the back of a brightness enhancement film and a preparation method thereof. The invention provides a protective film and a preparation method thereof, aiming at solving the problem that the existing protective film is not easy to peel. The protective film comprises a surface layer and an adhesive layer, wherein the surface layer comprises polypropylene resin and polyethylene resin, and the adhesive layer comprises metallocene polypropylene and polyolefin resin. The protective film provided by the invention is easy to peel and good in adhesive force stability, and is suitable for being used as a back protective film of a bright enhancement film. Moreover, the protective film provided by the invention is prepared in a two-layer co-extrusion casting mode, the process operation is convenient, and the production cost is low.

Description

Protective film and preparation method thereof
Technical Field
The invention relates to the field of protective film materials, in particular to a protective film on the back of a brightness enhancement film and a preparation method thereof.
Background
In recent years, with the rapid development of the electronics industry, there has been an increasing demand for ultra-thin displays such as liquid crystal displays. The liquid crystal display is mainly formed by combining various optical films. To protect the optical film from dirt or scratches during handling and assembly, the surface needs to be protected. As the protective film on the back surface of the bright enhancement film, the protective film is required to have an appropriate adhesive force. And after the protective film is attached to the bright enhancement film and wound and tightened, the situations of difficult peeling and the like can not be generated. And also, it is required that the adherend surface is not contaminated after the protective film is peeled off.
Disclosure of Invention
The invention provides a protective film and a preparation method thereof, aiming at solving the problem that the existing protective film is not easy to peel. The protective film provided by the invention is easy to peel and good in adhesive force stability, and is suitable for being used as a back protective film of a bright enhancement film. Moreover, the protective film provided by the invention is prepared in a two-layer co-extrusion casting mode, the process operation is convenient, the production cost is low, the physical property is good, the adhesive force stability is good, the influence of the adhesive force along with the change of temperature and time is small, and the protective film is very suitable for being used as a back protective film of a bright enhancement film.
In order to solve the technical problems, the invention adopts the following technical scheme to realize:
the invention provides a protective film which comprises a surface layer and an adhesive layer, wherein the surface layer comprises polypropylene resin and polyethylene resin, and the adhesive layer comprises metallocene polypropylene and polyolefin resin.
The adhesive layer is adhered to the surface layer.
Further, the protective film consists of a surface layer and an adhesive layer, wherein the surface layer consists of polypropylene resin and polyethylene resin, and the adhesive layer consists of metallocene polypropylene and polyolefin resin.
The protective film can be used as a protective film on the back surface of the bright enhancement film.
Further, the polypropylene resin of the surface layer is an ethylene-propylene block copolymer, and the polyethylene resin is low-density polyethylene or high-density polyethylene.
Further, the density of the ethylene-propylene block copolymer of the skin layer is in the range of 0.90 to 0.91g/cm3In the meantime. The ethylene-propylene block copolymer of the skin layer has a melt index of 4.0 to 9.0g/10 min.
Further, the density of the low-density polyethylene is 0.905-0.933g/cm3And the melt index is between 4.0 and 6.0g/10 min. Preferably, the low density polyethylene has a density of from 0.922 to 0.931g/cm3In the meantime.
Of said high density polyethyleneThe density is 0.945 to 0.965g/cm3And the melt index is between 5.0 and 9.0g/10 min. Preferably, the high density polyethylene has a density of from 0.952 to 0.961g/cm3And the melt index is between 5.0 and 7.0g/10 min.
Furthermore, the content of the ethylene-propylene block copolymer in the surface layer is 70-90%, and the content of the low-density polyethylene or the high-density polyethylene is 10-30%. The percentage is weight percentage.
Further, in the protective film, the adhesive layer is one or more of metallocene polypropylene and polyolefin resin.
Furthermore, the metallocene polypropylene of the adhesive layer is metallocene ethylene-octene copolymer elastomer.
Further, the density of the metallocene ethylene-octene copolymer elastomer of the adhesive layer is 0.87-0.90g/cm3And the melt index is between 4.0 and 10.0g/10 min. Preferably, the metallocene ethylene-octene copolymer elastomer has a density of 0.87-0.88g/cm3And the melt index is between 6.0 and 8.0g/10 min. This type of polypropylene has a nanocrystalline structure, is lower in density and softer, and has better physical and heat resistance properties than conventional polyolefin elastomers.
Further, the polyolefin resin of the adhesive layer is an ethylene-propylene random copolymer with the density of 0.86-0.905g/cm3And the melt index is between 3.0 and 8.0g/10 min. Preferably, the ethylene-propylene random copolymer of the adhesive layer has a density of 0.86 to 0.88g/cm3In the meantime.
Furthermore, the content of the metallocene ethylene-octene copolymer elastomer in the adhesive layer is 70-100%, and the content of the ethylene-propylene random copolymer is 0-30%. The percentage is weight percentage.
Further, the content of the ethylene-propylene block copolymer in the surface layer is 75-90%, and the content of the low-density polyethylene or the high-density polyethylene is 10-25%; the content of the metallocene ethylene-octene copolymer elastomer in the adhesive layer is 90-100%, and the content of the ethylene-propylene random copolymer is 0-10%; the percentage is weight percentage. The foregoing technical solutions include examples 1-3 and examples 6-8.
Further, the content of the ethylene-propylene block copolymer in the surface layer is 75-90%, and the content of the low-density polyethylene is 10-25%; the content of the metallocene ethylene-octene copolymer elastomer in the adhesive layer is 90-100%, and the content of the ethylene-propylene random copolymer is 0-10%; the percentage is weight percentage. The foregoing technical solutions include examples 1 to 3.
The protective film is characterized in that the total thickness of the protective film is 38-42 mu m, the proportion of the thickness of the surface layer to the thickness of the whole film is 80-85%, and the proportion of the thickness of the adhesive layer to the thickness of the whole film is 15-20%.
The protective film provided by the invention is prepared in a two-layer co-extrusion casting mode.
By adopting the formula of the protective film provided by the invention, the protective film produced in a two-layer co-extrusion mode can have the performance close to that of the protective film produced in a three-layer co-extrusion mode.
The preparation method of the protective film saves the processes of material mixing and granulation.
Compared with the prior art, the protective film provided by the invention has the beneficial effects that the protective film is easy to peel off and has good adhesion stability, and is suitable for being used as the protective film on the back surface of the bright enhancement film. The protective film provided by the invention is prepared by adopting a two-layer co-extrusion casting mode, and compared with the conventional three-layer co-extrusion casting mode, the protective film can simplify the feeding process, shorten the manual operation time and effectively reduce the production cost. Meanwhile, the protective film can realize physical properties and adhesive force properties similar to those of a three-layer co-extrusion mode by adjusting the content of low-density or high-density polyethylene on the surface layer. In addition, the metallocene polypropylene with a nano-crystalline structure adopted by the protective film adhesive layer is softer and has better physical property compared with the conventional polyolefin, and the adhesive force required by the back surface of the bright enhancement film can be met only by a single raw material, so that the material mixing and granulating processes are omitted, and the production cost is further reduced while the adhesive force stability is realized.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to these examples.
The performance test method for the protective film is as follows:
(1) tensile Strength and elongation at Break test
An American Instron universal tester is used, the reference standard being GB/T1040.3.
(2) Peel force test
The Kejian tensile tester is adopted, and the reference standard is GB/T2792.
(3) Measurement of light transmittance and haze
A DNH7000 haze meter manufactured by NDK corporation of Japan was used, and the reference standard was GB/T2410.
(4) Adhesion stability test
And sticking the prepared film on the back surface of the brightness enhancement film, compacting by using a film laminating machine, placing in a 50 ℃ oven for 72 hours, and cooling to room temperature for carrying out a peeling force test.
Example 1
The protective film provided by the invention sequentially comprises a surface layer and an adhesive layer. The surface layer is formed by compounding ethylene-propylene block copolymer and low-density polyethylene according to the weight ratio of 90: 10. Wherein the ethylene-propylene block copolymer has a density of 0.90g/cm3The melt index was 9.0g/10 min. The density of the low density polyethylene is 0.922g/cm3The melt index was 4.0g/10 min.
The adhesive layer adopts metallocene ethylene-octene copolymer elastomer. The copolymer elastomer had a density of 0.87g/cm3The melt index was 6.0g/10 min.
The surface layer had a thickness of 34 μm and the adhesive layer had a thickness of 6 μm.
Example 2
The protective film provided in example 1, except that:
the surface layer is formed by compounding ethylene-propylene block copolymer and low-density polyethylene according to the weight ratio of 75: 25.
Example 3
The protective film provided in example 1, except that:
the adhesive layer adopts metallocene ethylene-octeneThe copolymer elastomer and the ethylene-propylene random copolymer are prepared according to the mass ratio of 90: 10. Wherein the density of the ethylene-propylene random copolymer is 0.88g/cm3The melt index was 8.0g/10 min.
Example 4
The protective film provided in example 1, except that:
the surface layer is prepared from ethylene-propylene block copolymer and low-density polyethylene according to the weight ratio of 80: 20.
The adhesive layer is prepared from metallocene ethylene-octene copolymer elastomer and ethylene-propylene random copolymer according to the mass ratio of 85: 15.
Example 5
The protective film provided in example 1, except that:
the surface layer is prepared by compounding ethylene-propylene block copolymer and low-density polyethylene according to the weight ratio of 70: 30. Wherein the ethylene-propylene block copolymer has a density of 0.91g/cm3The melt index was 4.0g/10 min. The density of the low density polyethylene was 0.931g/cm3The melt index was 6.0g/10 min.
The adhesive layer is prepared from metallocene ethylene-octene copolymer elastomer and ethylene-propylene random copolymer according to the mass ratio of 70: 30.
Example 6
The protective film provided in example 1, except that:
the surface layer is prepared from ethylene-propylene block copolymer and high-density polyethylene according to the weight ratio of 75: 25. Wherein the ethylene-propylene block copolymer has a density of 0.91g/cm3The melt index was 4.0g/10 min. The density of the high density polyethylene is 0.952g/cm3The melt index was 5.0g/10 min.
Example 7
The protective film provided in example 1, except that:
the surface layer is formed by compounding ethylene-propylene block copolymer and high-density polyethylene according to the weight ratio of 90: 10. Wherein the ethylene-propylene block copolymer has a density of 0.91g/cm3A melt index of4.0g/10 min. The density of the high density polyethylene is 0.952g/cm3The melt index was 5.0g/10 min.
The adhesive layer adopts metallocene ethylene-octene copolymer elastomer. The density of the copolymer elastomer was 0.88g/cm3The melt index was 8.0g/10 min.
Example 8
The protective film provided in example 1, except that:
the surface layer is prepared by compounding ethylene-propylene block copolymer and high-density polyethylene according to the weight ratio of 80: 20. Wherein the high density polyethylene has a density of 0.961g/cm3The melt index was 7.0g/10 min.
The adhesive layer is prepared from metallocene ethylene-octene copolymer elastomer and ethylene-propylene random copolymer according to the mass ratio of 90: 10. Wherein the copolymer elastomer has a density of 0.88g/cm3The melt index was 8.0g/10 min. The density of the ethylene-propylene random copolymer was 0.86g/cm3The melt index was 3.0g/10 min.
Comparative example 1
A protective film comprises a surface layer and an adhesive layer. The surface layer is prepared by adopting ethylene-propylene block copolymer. The density of the ethylene-propylene block copolymer was 0.90g/cm3The melt index was 9.0g/10 min.
The adhesive layer adopts metallocene ethylene-octene copolymer elastomer. The copolymer elastomer had a density of 0.87g/cm3The melt index was 6.0g/10 min.
Table 1 formulations of protective films provided in examples 1 to 8 of the present invention and comparative example 1
Figure BDA0001891972600000061
Table 2 main property test results of the protective films provided in examples 1 to 8 of the present invention and comparative example 1
Figure BDA0001891972600000062
Figure BDA0001891972600000071
The protective films obtained in the embodiments and the comparative examples are attached to the back surface of the bright enhancement film through a film laminating machine, the stripping performance of the protective film is tested by a manual method, and meanwhile, after the protective film is torn off, whether residual glue or other pollution exists on the back surface of the bright enhancement film is observed under light. The specific test results are shown in table 3.
Table 3 main property test results of the protective films provided in examples 1 to 8 of the present invention and comparative example 1
Figure BDA0001891972600000072
The test results of the comparative example and the embodiment are compared to obtain that the protective film provided by the embodiment of the invention has the advantages of good bonding effect with the back surface of the bright enhancement film, good physical property, easy peeling and good adhesion stability. The experimental scheme of comparative example 1 is easy to peel off and the like because the surface layer is smooth and is tightly adhered to the adhesive layer. Further, the protective films provided in examples 1 to 3 and examples 6 to 8 according to the present invention have a good adhesion effect to the back surface of the bright enhancement film, and are easy to peel off. However, when the peel force is less than 2.37gf/25mm, slight edge lifting, edge lifting or bulging is liable to occur, and when the peel force for bonding is more than 3.5gf/25mm, the peelability is impaired. Therefore, in view of the overall performance of the protective film, and the releasability and the test performance over time for the back surface of the bright enhancement film, examples 1 to 3 are preferably used as the protective film for the back surface of the bright enhancement film.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (2)

1. A protective film, characterized in that it is composed of a skin layer composed of an ethylene-propylene block copolymer and a low-density polyethylene, and an adhesive layer composed of a metallocene ethylene-octene copolymer elastomer and an ethylene-propylene random copolymer; the content of the ethylene-propylene block copolymer in the surface layer is 75-90%, and the content of the low-density polyethylene is 10-25%; the content of the metallocene ethylene-octene copolymer elastomer in the adhesive layer is 90-100%, and the content of the ethylene-propylene random copolymer is 0-10%; the percentage is weight percentage.
2. A method for preparing a protective film according to claim 1, wherein the protective film is prepared by two-layer co-extrusion casting.
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CN114507486B (en) * 2020-11-16 2024-02-20 象山激智新材料有限公司 High-temperature-resistant protective film and preparation method thereof
CN114774008B (en) * 2022-06-17 2022-09-13 宁波长阳科技股份有限公司 High-low-density POE (polyolefin elastomer) co-extrusion packaging adhesive film and preparation method thereof

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