CN113698891A - Recyclable protective film and preparation method thereof - Google Patents
Recyclable protective film and preparation method thereof Download PDFInfo
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- CN113698891A CN113698891A CN202111102914.5A CN202111102914A CN113698891A CN 113698891 A CN113698891 A CN 113698891A CN 202111102914 A CN202111102914 A CN 202111102914A CN 113698891 A CN113698891 A CN 113698891A
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- protective film
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2231—Oxides; Hydroxides of metals of tin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
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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
- C09J2433/00—Presence of (meth)acrylic polymer
Abstract
The invention relates to a recyclable protective film and a preparation method thereof, and belongs to the technical field of films. The recyclable protective film comprises a base material layer, a release layer arranged on the base material layer and an adhesive layer arranged between the base material layer and the release layer, wherein the adhesive layer comprises the following raw material components in parts by mass: 100 parts of acrylic copolymer, 20-40 parts of ethylene-vinyl acetate copolymer, 10-20 parts of infrared blocking agent, 0.01-2.5 parts of curing agent and 50-100 parts of solvent. The recyclable protective film is environment-friendly, has little smell, can be recycled and granulated after being used, can be recycled and used again, can be manufactured into other low-grade plastic products, and has simple process and easy operation.
Description
Technical Field
The invention relates to the technical field of films, in particular to a recyclable protective film and a preparation method thereof.
Background
High-end smart phones have extremely high requirements on the appearance of glass, metal plates, plastic plates and the like used for display screens or shell materials. These materials are susceptible to contact contamination or scuffing on their surfaces during handling and shipping, and are therefore typically protected from damage and contamination by a protective film covering the surface. The process control equipment in the electronic industry is identified by infrared rays, common protective films can cause infrared rays to overlap to influence identification, and the infrared rays are separated by a barrier film.
Most of common protective films in the market at present take a polyester film as a base material, one side or two sides of the base material are coated with an organic silicon adhesive, an acrylate adhesive, a polyurethane adhesive and a rubber adhesive, and then an isolating film is attached. The used protective film can not be recycled as waste, is difficult to treat, adopts an incineration mode to treat, and causes certain pollution to the environment. Nowadays, the environmental protection awareness is continuously enhanced, and the recyclability of the environmental protection adhesive and the protective film is more and more concerned by people.
Disclosure of Invention
In order to solve the technical problems, the invention provides a recyclable protective film and a preparation method thereof, wherein the ethylene-vinyl acetate copolymer (EVA) and the acrylic acid copolymer have good conformability to materials such as glass and the like, and have no residual glue at high temperature and high humidity; by adding a certain proportion of nano metal oxide into the adhesive, the infrared blocking rate can be adjusted at will according to the application requirements of customers; the EVA adhesive and the base material layer used by the protective film have good thermoplasticity, so the protective film has recyclability and sustainability, and can be recycled to make materials into plastic particles after being used for plastic products, thereby reducing the environmental pollution.
The first purpose of the invention is to provide a recyclable protective film, which comprises a substrate layer, a release layer arranged on the substrate layer and an adhesive layer arranged between the substrate layer and the release layer, wherein the adhesive layer comprises the following raw material components in parts by mass: 100 parts of acrylic copolymer, 20-40 parts of ethylene-vinyl acetate copolymer, 10-20 parts of infrared blocking agent, 0.01-2.5 parts of curing agent and 50-100 parts of solvent.
Further, the infrared blocking agent contains nano metal oxide, and the mass percentage of the nano metal oxide in the infrared blocking agent is 18-35%.
Further, the nano metal oxide is one or more of indium oxide, antimony oxide and tin oxide.
Further, the grade of the infrared blocking agent is GTO-CQ81L-TOL, G-P35-EA or GTO-821-MIBK.
Further, the weight average molecular weight of the acrylic copolymer is 50-80 ten thousand, the solid content is 30-40%, and the glass transition temperature is-45 ℃ to-40 ℃.
Further, the ethylene-vinyl acetate copolymer is a recycled plastic particle, and the vinyl acetate content of the recycled plastic particle is 25-50%.
Further, the curing agent is an epoxy resin and/or an aziridine.
Further, the solvent is one or more of ethyl acetate, toluene and isopropanol.
Further, the substrate layer is a BOPP film, a PE film or a PLA film.
A second object of the present invention is to provide a method for preparing a recyclable protective film, comprising the steps of:
mixing and stirring the acrylic copolymer, the ethylene-vinyl acetate copolymer, the infrared blocking agent, the curing agent and the solvent uniformly, coating the mixture on the corona surface of the substrate layer, drying the mixture, attaching the release layer, and curing to obtain the recyclable protective film.
Further, the temperature of the drying process is 70-75 ℃.
Further, the curing is performed for 3-7d at 30-40 ℃.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the infrared blocking agent is a near-infrared absorbent, namely a substance with absorption capacity on infrared band electromagnetic waves, the size of the infrared absorbent is nano-scale, the absorption capacity on the optical waves can be improved, and the required infrared blocking rate and light transmittance can be adjusted by adjusting the using amount of the infrared blocking agent.
(2) The acrylic copolymer has good cohesion and fluidity, so that the protective film has good conformability and does not have the undesirable phenomena of swelling, wrinkling and the like in the using process. The acrylic copolymer and EVA have good compatibility, the infrared blocking agent is well dispersed in the acrylic copolymer due to excellent dispersibility, and uneven light transmittance and blocking rate can not occur. The recyclable protective film has good thermal stability, and can not generate the phenomena of adhesive residue, micromolecule precipitation and the like under the aging of high temperature and high humidity.
(3) The recyclable protective film adhesive layer is prepared by blending EVA and acrylic acid copolymer, so that the prepared glue is environment-friendly and has small smell, can be recycled and granulated after being used, and can be recycled and used to prepare other low-grade plastic products, and the recyclable protective film adhesive layer is simple in process and easy to operate.
Drawings
In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the present disclosure taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic view of a coating of an embodiment of a recyclable protective film according to the present invention.
The specification reference numbers indicate: 1 is a base material layer; 2 is an adhesive layer; and 3 is a release layer.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
As shown in fig. 1, a recyclable protective film includes a substrate layer 1, a release layer 3 disposed on the substrate layer 1, and an adhesive layer 2 disposed between the substrate layer 1 and the release layer 3.
The recyclable protective film and the preparation method thereof comprise the following steps:
1. 100 parts by weight of acrylic copolymer with the molecular weight of 60-70 ten thousand and the Tg of-40 ℃ to-45 ℃ is weighed.
2. 15 parts by weight of EVA particles having a VA content of 33% are weighed.
3. Weighing 10 parts of GTO-CQ81L-T0L infrared blocking agent.
4. Weighing 1 part by weight of epoxy curing agent.
5. Adding 50 parts by weight of ethyl acetate and 10 parts by weight of isopropanol into the weighed components, uniformly mixing, standing for defoaming, uniformly coating the mixture on a substrate layer to form a glue film, drying the glue film by using a 70 ℃ drying oven, and then attaching a release layer to obtain the recyclable protective film.
Example 2
A recyclable protective film and a preparation method thereof comprise the following steps:
1. 100 parts by weight of acrylic copolymer with the molecular weight of 60-70 ten thousand and the Tg of-40 ℃ to-45 ℃ is weighed.
2. 15 parts by weight of EVA particles with a VA content of 46% are weighed.
3. Weighing 17 parts of GTO-821-MIBK infrared blocking agent.
4. 1 part by weight of aziridine curing agent was weighed.
5. And adding 30 parts by weight of ethyl acetate, 20 parts by weight of toluene and 10 parts by weight of isopropanol into the weighed components, uniformly mixing, standing for defoaming, uniformly coating the mixture on a substrate layer to form a glue film, drying the glue film by using a 70 ℃ oven, and attaching a release layer to obtain the recyclable protective film.
Example 3
A recyclable protective film and a preparation method thereof comprise the following steps:
1. 100 parts by weight of acrylic copolymer with the molecular weight of 70-80 ten thousand and the Tg of-40 ℃ to-45 ℃ is weighed.
2. 20 parts by weight of EVA particles having a VA content of 33% are weighed.
3. Weighing 20 parts of infrared blocking agent with the brand number of G-P35-EA.
4. Weighing 1 part by weight of epoxy curing agent.
5. Adding 50 parts by weight of ethyl acetate, 10 parts by weight of toluene and 10 parts by weight of isopropanol into the weighed components, uniformly mixing, standing for defoaming, uniformly coating the mixture on a substrate layer to form a glue film, drying the glue film by using a 70 ℃ oven, and attaching a release layer to obtain the recyclable protective film.
Example 4
A recyclable protective film and a preparation method thereof comprise the following steps:
1. 100 parts by weight of acrylic copolymer with the molecular weight of 70-80 ten thousand and the Tg of-40 ℃ to-45 ℃ is weighed.
2. 20 parts by weight of EVA particles with a VA content of 46% are weighed.
3. Weighing 10 parts of GTO-CQ81L-T0L infrared blocking agent.
4. 1 part by weight of the epoxy curing agent and 0.2 part by weight of the aziridine curing agent were weighed out.
5. Adding 60 parts by weight of ethyl acetate and 10 parts by weight of isopropanol into the weighed components, uniformly mixing, standing for defoaming, uniformly coating the mixture on a substrate layer to form a glue film, drying the glue film by using a 70 ℃ drying oven, and attaching a release layer to obtain the recyclable protective film.
Comparative example
1. 100 parts by weight of acrylic copolymer with the molecular weight of 60-70 ten thousand and the Tg of-40 ℃ to-45 ℃ is weighed.
2. 20 parts by weight of EVA particles having a VA content of 33% are weighed.
3. Weighing 1 part by weight of epoxy curing agent.
4. Adding 60 parts by weight of ethyl acetate and 10 parts by weight of isopropanol into the weighed components, uniformly mixing, standing for defoaming, uniformly coating the mixture on a substrate layer to form a glue film, drying the glue film by using a 70 ℃ drying oven, and attaching a release layer to obtain the protective film.
Test method
To better illustrate the technical effects of the present invention, the protective films prepared in the above examples 1 to 4 and comparative examples were tested for their performance, wherein the test criteria are as follows:
thickness test method reference: astm d 3652;
adhesion test methods reference: ASTM D3330;
the high-temperature and high-humidity test method comprises the following steps: placing the sample in an RH environment of 60 ℃ and 90 percent for 72 hours, taking out, standing for 1 hour at normal temperature, and observing the appearance, wherein no residual glue is qualified.
Samples of inventive examples 1-4 and comparative examples were tested according to the above test standards, and table 1 shows the relevant parameters of the finally measured samples:
TABLE 1
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
| Thickness of the layer used (μm) | 60 | 60 | 60 | 60 | 60 |
| Peeling force (gf/inch) | 31 | 29 | 25 | 29 | 30 |
| High temperature high humidity ring test 60 ℃ 90% RH | OK | OK | OK | OK | OK |
| Infrared rejection (%) | 85 | 90 | 97 | 82 | 8.5 |
| Light transmittance (%) | 55 | 52 | 45 | 57 | 90.5 |
According to experimental data, the high-temperature high-humidity environment-friendly rubber coating has excellent infrared blocking performance, and the phenomena of rubber residue and degumming can not occur after high-temperature high-humidity environment measurement. The barrier rate is increased, the transmittance is reduced, and the conventional product requires that a certain barrier rate and transmittance are ensured, generally the barrier rate is controlled to be 85-97%, and the transmittance is controlled to be 45-60%.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The utility model provides a recoverable protection film, includes the substrate layer, sets up from the type layer on the substrate layer with set up in the substrate layer with from the gluing agent layer between the type layer, its characterized in that, the raw materials component and the part by mass of gluing agent layer are: 100 parts of acrylic copolymer, 20-40 parts of ethylene-vinyl acetate copolymer, 10-20 parts of infrared blocking agent, 0.01-2.5 parts of curing agent and 50-100 parts of solvent.
2. The recyclable protective film of claim 1, wherein: the infrared blocking agent contains nano metal oxide, and the nano metal oxide accounts for 18-35% of the infrared blocking agent by mass; the nano metal oxide is one or more of indium oxide, antimony oxide and tin oxide.
3. The recyclable protective film of claim 1, wherein: the weight average molecular weight of the acrylic copolymer is 50-80 ten thousand, the solid content is 30-40%, and the glass transition temperature is-45 ℃ to-40 ℃.
4. The recyclable protective film of claim 1, wherein: the ethylene-vinyl acetate copolymer is a recycled plastic particle, and the vinyl acetate content of the ethylene-vinyl acetate copolymer is 25-50%.
5. The recyclable protective film of claim 1, wherein: the curing agent is epoxy resin and/or aziridine.
6. The recyclable protective film of claim 1, wherein: the solvent is one or more of ethyl acetate, toluene and isopropanol.
7. The recyclable protective film of claim 1, wherein: the substrate layer is BOPP membrane, PE membrane or PLA membrane.
8. A method for preparing a recyclable protective film according to any of claims 1 to 7, comprising the steps of:
mixing and stirring the acrylic copolymer, the ethylene-vinyl acetate copolymer, the infrared blocking agent, the curing agent and the solvent uniformly, coating the mixture on the corona surface of the substrate layer, drying the mixture, attaching the release layer, and curing to obtain the recyclable protective film.
9. The method for preparing a recyclable protective film according to claim 8, comprising: the temperature of the drying process is 70-75 ℃.
10. The method for preparing a recyclable protective film according to claim 8, comprising: the curing is performed for 3-7 days at 30-40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111102914.5A CN113698891A (en) | 2021-09-17 | 2021-09-17 | Recyclable protective film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111102914.5A CN113698891A (en) | 2021-09-17 | 2021-09-17 | Recyclable protective film and preparation method thereof |
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| CN113698891A true CN113698891A (en) | 2021-11-26 |
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| CN202111102914.5A Pending CN113698891A (en) | 2021-09-17 | 2021-09-17 | Recyclable protective film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574120A (en) * | 2022-04-02 | 2022-06-03 | 极天羽技术股份有限公司 | Recyclable infrared blocking protective film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449437A (en) * | 2013-09-17 | 2015-03-25 | 浙江天源能源科技有限公司 | Preparation method for transparent heat-insulation pressure-sensitive type functional membrane |
| CN106010343A (en) * | 2016-07-12 | 2016-10-12 | 斯迪克新型材料（江苏）有限公司 | Protective film easy to recycle |
| CN106661410A (en) * | 2014-08-20 | 2017-05-10 | 株式会社可乐丽 | Acrylic adhesive composition and adhesive product |
| CN111394006A (en) * | 2020-03-27 | 2020-07-10 | 深圳市高仁电子新材料有限公司 | Preparation method of infrared-blocking EVA (ethylene-vinyl acetate copolymer) film |
-
2021
- 2021-09-17 CN CN202111102914.5A patent/CN113698891A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449437A (en) * | 2013-09-17 | 2015-03-25 | 浙江天源能源科技有限公司 | Preparation method for transparent heat-insulation pressure-sensitive type functional membrane |
| CN106661410A (en) * | 2014-08-20 | 2017-05-10 | 株式会社可乐丽 | Acrylic adhesive composition and adhesive product |
| CN106010343A (en) * | 2016-07-12 | 2016-10-12 | 斯迪克新型材料（江苏）有限公司 | Protective film easy to recycle |
| CN111394006A (en) * | 2020-03-27 | 2020-07-10 | 深圳市高仁电子新材料有限公司 | Preparation method of infrared-blocking EVA (ethylene-vinyl acetate copolymer) film |
Non-Patent Citations (1)
| Title |
|---|
| 李广宇等: "《胶黏剂原材料手册》", 31 August 2004, 国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114574120A (en) * | 2022-04-02 | 2022-06-03 | 极天羽技术股份有限公司 | Recyclable infrared blocking protective film and preparation method thereof |
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