CN112048253B - Self-adhesion type protection film - Google Patents

Self-adhesion type protection film Download PDF

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Publication number
CN112048253B
CN112048253B CN202010920351.XA CN202010920351A CN112048253B CN 112048253 B CN112048253 B CN 112048253B CN 202010920351 A CN202010920351 A CN 202010920351A CN 112048253 B CN112048253 B CN 112048253B
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styrene
protective film
block copolymer
self
adhesive
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CN112048253A (en
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王东庆
方隽云
龚太敏
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Zhejiang Jiemei Electronic and Technology Co Ltd
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Zhejiang Jiemei Electronic and Technology Co Ltd
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L53/02—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 of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • 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

Abstract

The invention relates to a technology in the field of films or sheets, in particular to a self-adhesive protective film, which comprises a surface layer, a core layer and a bonding layer; wherein, the surface layer comprises a mixture of styrene-butadiene block copolymer and/or styrene-isoprene block copolymer, olefin elastomer and parting agent. The invention introduces styrene-butadiene block copolymer and/or styrene-isoprene block copolymer into the surface layer, and takes olefin elastomer as a support body; the olefin elastomer or the carbamate polymer is introduced into the core layer, so that the cold and hot alternating following performance of the protective film is improved, the restorability after deformation is good, the plastic thin neck phenomenon after deformation is eliminated, the adhesion force of the self-adhesion protective film is stable, and the protective film cannot be peeled off due to the fact that the protective film cannot be enlarged in the using process.

Description

Self-adhesion type protection film
Technical Field
The invention relates to the technology in the field of films or sheets, in particular to a self-adhesive protective film.
Background
In the processing and transportation processes in the fields of synthetic resin boards, metal plates, coated steel plates, LEDs, wafer dicing, and the like, a surface protective film is often coated to protect the surfaces of these products from stains.
The surface protection film comprises a base material layer based on thermoplastic resin and an adhesive layer fixed on one side of the base material layer, and the surface protection film is bonded on the surface of an adherend through the adhesive layer for protection in the processing and transportation of the adherend and can be peeled off when the adherend is used. Therefore, the pressure-sensitive adhesive layer of the surface protective film is required to have an appropriate adhesive force, to be capable of being attached to the surface of an adherend to prevent stains from adhering to or scratching the surface, and to be easily peeled by hand.
The self-adhesive protective film sold in the market at present is a high-temperature-resistant clean self-adhesive protective film which is prepared by using polypropylene or polyethylene as a base material, for example, the high-temperature-resistant clean self-adhesive protective film disclosed in 2015, 02, 18 and the preparation method thereof, wherein the protective film comprising a self-adhesive layer, an intermediate layer and a back material layer is obtained by co-extruding and blowing the film, the self-adhesive layer is prepared by compounding a metallocene polypropylene low-density elastomer, SEBS and low-density polyethylene, and the combination performance shown by the co-polymerization of the three components is utilized, so that the whole double-sided adhesive film has better adhesive strength and high-temperature resistance, and the effective combination and processing stability in the co-extruding and blowing process are ensured.
In some cases, for example, when the film is required to be deformed by cold or heat together with an object to be attached, the following property of the base material is poor, and bubbles are generated and even the film is curled. Protective films used in the LED industry require a certain amount of deformation and then recover, however, the above substrates exhibit a "neck-in" phenomenon of plastics, which makes them unsatisfactory for use.
Also, for example, in the chinese patent invention entitled "CN 105602478B" on the granted bulletin date of 2016, 05, and 25, a self-adhesive polyethylene protective film and a method for preparing a self-adhesive layer thereof are disclosed, which improve a self-adhesive layer, wherein the self-adhesive layer is formed by mixing a polyolefin elastomer (POP/POE) or a styrene block copolymer (SEBS) with polyethylene and then adding Polyisobutylene (PIB), and although the obtained self-adhesive polyethylene protective film has good initial adhesion, strong adhesion and high stability, the obtained self-adhesive polyethylene protective film still has the defects of poor followability and poor resilience.
Disclosure of Invention
In order to solve the technical problems, the invention reduces the isotacticity of the surface layer and the core layer of the protective film so as to reduce the crystallinity of the protective film and improve the following property and the rebound resilience of the protective film, thereby obtaining the self-adhesive protective film which has an amorphous structure.
The invention adopts the following technical scheme:
a self-adhesive protective film comprises a surface layer, a core layer and a bonding layer; wherein, the surface layer comprises a mixture of styrene-butadiene block copolymer and/or styrene-isoprene block copolymer, olefin elastomer and parting agent.
According to the technical scheme, the styrene-butadiene block copolymer and/or the styrene-isoprene block copolymer are introduced into the surface layer as a framework, and the isotacticity of the surface layer is reduced, so that the crystallinity of the protective film is reduced, the surface layer is endowed with sufficient elasticity, and the protective film can recover the original shape after being stretched.
Preferably, the specific contents of the components in the surface layer are as follows:
styrene-butadiene block copolymer and/or styrene-isoprene block copolymer: 29-80 wt%;
olefin elastomer: 19-70 wt%;
a release agent: 1-10 wt%.
If the weight of the styrene-butadiene block copolymer and/or the styrene-isoprene block copolymer is less than 29wt%, the surface layer is too hard and loses the following property; if the amount is more than 80wt%, the surface layer is too soft, the tear strength is low, and the film tends to be broken during stretching in use.
Since the styrene-isoprene block copolymer has a carbon chain length longer than that of the styrene-butadiene block copolymer, and is more flexible, the skin layer may preferably include a mixture of the styrene-isoprene block copolymer, the olefin elastomer and the release agent.
The olefin elastomer serves to increase the support of the skin. The amount of the olefin elastomer added is 19 to 70 wt%, and if it is too small, the material has a high softness and is liable to break after stretching. If too much, the resiliency and conformability of the material will be poor and the neck-thinning phenomenon will occur upon stretching.
Preferably, the olefinic elastomer is an amorphous random copolymer, optionally a random copolymer of ethylene, butene or octene, or a polymer synthesized for the purpose of reducing the isotacticity of polypropylene (propylene polymers are generally crystalline and have a high isotacticity).
Preferably, the core layer comprises a styrene-butadiene block copolymer and/or a styrene-isoprene block copolymer and an olefin elastomer. Through the improvement to the sandwich layer is constituteed, reduces the isotacticity of sandwich layer, and the further degree of crystallinity that cooperates the top layer to reduce the protection film promotes the followability and the resilience of protection film.
Preferably, the core layer comprises a styrene-butadiene block copolymer and/or a styrene-isoprene block copolymer and a urethane polymer. The carbamate polymer has certain polarity, can be better fused with a styrene-butadiene block copolymer and a styrene-isoprene block copolymer, and has better self resilience, so that the following property and the resilience of the film are better.
Preferably, the tie layer comprises 40 to 80 weight percent of a styrene-butadiene block copolymer and 20 to 60 weight percent of a tackifying resin.
If the styrene-butadiene block copolymer is less than 40 wt%, the adhesive force is lowered and it is difficult to obtain a necessary adhesive force, and if it exceeds 80wt%, the adhesive force is too high and the subsequent unwinding ability is impaired. The styrene content in the block copolymer is 10-30 wt%, and if the styrene content is less than 10wt%, the cohesive strength is too low, and residual glue is easily caused during tearing; if it exceeds 30wt%, the elasticity is too high, and the required adhesiveness is difficult to obtain, and the conformability is poor.
Preferably, the tackifier resin is at least one of a hydrogenated petroleum resin, a terpene resin, and a phenol-modified terpene resin, and the viscosity of the adhesive layer can be adjusted.
More preferably, the tie layer comprises 50 to 60wt% of a styrene-butadiene block copolymer, 20 to 35wt% of a tackifying resin, and 5 to 30wt% of an acrylic elastomer. The acrylic elastomer is an acrylic-based block copolymer, and can increase the softness of the adhesive layer, so that the adhesive layer has better fitting property when being attached to the coated body.
Preferably, the total thickness of the self-adhesive film is 30-80 μm, and the thickness of the adhesive layer is not more than 20%.
The self-adhesive protective film adopts a three-layer co-extrusion molding mode, 3 layers of casting formed by the bonding layer, the middle layer and the surface layer are subjected to composite molding through melting extrusion in a T-shaped die, the adhesive force of the prepared protective film is 45-150Gf/25mm, and the uncoiling force is not more than 100 Gf/25 mm; the 100% stress at definite elongation is not more than 4MPa, and the 100% stress at definite elongation is recovered between 40-100%.
Through the implementation of the technical scheme, the protective film has the following advantages:
the invention introduces styrene-butadiene block copolymer and/or styrene-isoprene block copolymer into the surface layer, and takes olefin elastomer as a support body; the olefin elastomer or the carbamate polymer is introduced into the core layer, so that the cold and hot alternating following performance of the protective film is improved, the restorability after deformation is good, the plastic thin neck phenomenon after deformation is eliminated, the adhesion force of the self-adhesion protective film is stable, and the protective film cannot be peeled off due to the fact that the protective film cannot be enlarged in the using process.
Detailed Description
The following is a description of the preferred embodiments of the present invention and a further description of the technical solutions of the present invention, but the following embodiments are only preferred embodiments of the present invention and do not limit the present invention.
The self-adhesive protective film with an amorphous structure comprises a surface layer, a core layer and an adhesive layer, and is prepared by co-extruding a surface layer composition, a core layer composition and an adhesive layer composition in a molten state into a film in a T-shaped die.
Evaluation criteria for rebound resilience and followability:
the 100% stress at definite elongation is not more than 4MPa, and the 100% stress at definite elongation is recovered between 40% and 100%, which shows that the following property and the rebound resilience are good.
100% stress recovery at elongation: the film between the clamps is relaxed after stretching for 100%, and the difference between the length of the film and the original length between the clamps accounts for the percentage of the original length.
The composition of the layers of the examples and comparative examples is shown in table 1 below:
and the performance of the protective films obtained in the examples and the comparative examples is tested, and the results are shown in Table 2:
Figure DEST_PATH_IMAGE002
Figure DEST_PATH_IMAGE004
remarking:
*1: the stuck object is PET, and the stretching speed is 500 mm/min;
*2: the bonding layer is adhered to the surface layer.

Claims (6)

1. A self-adhesive protective film comprises a surface layer, a core layer and a bonding layer; the surface layer comprises 29-80wt% of styrene-butadiene block copolymer and/or styrene-isoprene block copolymer, 19-70 wt% of olefin elastomer and 0.1-10 wt% of release agent;
the core layer comprises an olefin elastomer and one or two of a styrene-butadiene block copolymer and a styrene-isoprene block copolymer; or
The core layer comprises a urethane polymer and one or two of a styrene-butadiene block copolymer and a styrene-isoprene block copolymer;
the uncoiling force of the protective film is not more than 100 Gf/25mm, the 100% stress at definite elongation is not more than 4MPa, and the 100% stress at definite elongation is recovered between 40 and 100%.
2. The self-adhesive protective film according to claim 1, wherein the adhesive layer comprises 40 to 80wt% of styrene-butadiene block copolymer and 20 to 60wt% of tackifying resin.
3. The self-adhesive protective film according to claim 1, wherein the adhesive layer comprises 50 to 60wt% of styrene-butadiene block copolymer, 20 to 35wt% of tackifying resin and 5 to 30wt% of acrylic elastomer.
4. The self-adhesive protective film according to claim 2 or 3, wherein the styrene content in the styrene-butadiene block copolymer is 10 to 30 wt%.
5. The self-adhesive protective film according to claim 2 or 3, wherein the tackifying resin is at least one of a hydrogenated petroleum resin, a terpene resin and a phenolic-modified terpene resin.
6. The self-adhesive protective film according to claim 1, wherein the total thickness of the protective film is 30 to 80 μm, and the thickness of the adhesive layer is not more than 20% of the total thickness of the protective film.
CN202010920351.XA 2020-09-04 2020-09-04 Self-adhesion type protection film Active CN112048253B (en)

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