CN112442323B

CN112442323B - Self-adhesive protective film and preparation method thereof

Info

Publication number: CN112442323B
Application number: CN202011311402.5A
Authority: CN
Inventors: 李忠
Original assignee: Kunshan Jinmeng Plastic Film Co ltd
Current assignee: Kunshan Jinmeng Plastic Film Co ltd
Priority date: 2020-11-20
Filing date: 2020-11-20
Publication date: 2022-08-19
Anticipated expiration: 2040-11-20
Also published as: CN112442323A

Abstract

The invention discloses a self-adhesive protective film and a preparation method thereof. The self-adhesive protective film comprises, by mass, 10-30% of a surface layer, 60-70% of an intermediate layer and 10-20% of an adhesive layer which are sequentially arranged from top to bottom, wherein the surface layer is 100% of polyolefin material; the intermediate layer comprises 85-95% of a polyolefin material and 5-15% of a polyolefin plastomer; the adhesive layer comprises 85-95% of a polyolefin material and 5-15% of a polyolefin plastomer. The self-adhesive protective film prepared by the invention has good temperature resistance, can resist more than 70 ℃, has good compatibility with polyolefin materials, does not have the phenomena of layering and falling, and is particularly suitable for protecting acrylic plates.

Description

Self-adhesive protective film and preparation method thereof

Technical Field

The invention relates to the technical field of self-adhesive protective films, and relates to a self-adhesive protective film and a preparation method thereof.

Background

The protective film is widely applied to the storage and transportation processes of various products to avoid the problems of pollution, scratch and the like of the products. The protective film is covered on the surfaces of a Polycarbonate (PC) plate, a polymethyl methacrylate (PMMA) plate, a Polystyrene (PS) plate and a polypropylene (PP) plate, and can play a role in protection in the processes of storage, transportation and construction.

In the application of the self-adhesive protective film, some use environments require high-temperature (above 70 ℃) resistant use conditions, such as a acrylic plate just produced by attaching a calendering line (after the acrylic plate is produced, the protective film needs to be attached, but the surface temperature of the acrylic plate can reach 70 ℃ generally). The common self-adhesive protective film is usually made of a polyethylene base material, and an adhesive material such as SP1520 of mitsui chemical or 8203 of nordic chemical engineering matched with a polyethylene carrier is used, so that the adhesive material is remained on the surface of an object to be pasted due to high temperature during use.

The self-adhesion protection film of polypropylene substrate has better temperature resistant effect, but the compatibility of the viscous material of polyethylene carrier and polypropylene substrate is not very ideal, though can improve temperature resistant effect, but has the risk that the layering drops.

CN102304329A discloses a self-adhesive protective film and a method for adjusting the initial viscosity of the self-adhesive protective film, wherein a self-adhesive protective film with a low-density polyethylene printing layer, a high-density polyethylene barrier layer and an elastomer self-adhesive layer is processed by a three-layer co-extrusion film blowing method or a three-layer casting method, the elastomer self-adhesive layer is firstly mixed by EVA and PE, then POP or POE is added to adjust the initial viscosity of the self-adhesive protective film, the higher the requirement on the viscosity of the initial viscosity is, the larger the amount of the added POP or POE is, and the mass percentages of the components in the elastomer self-adhesive layer are controlled within the following ranges: EVA: 10 to 50 percent; PE: 10 to 80 percent; POP or POE: 1 to 40 percent. The film has no peculiar smell, good stability, no need of adding various auxiliary agents, easy tearing at high temperature, lower cost than the original film, good transparency, effective prevention of damage to the surface of the plate by sticking the film on the surface of the plate, improvement of the initial viscosity of the self-adhesive protective film, small film sticking difficulty for users, high efficiency and cost reduction. However, the temperature resistance of the self-adhesive protective film prepared by the invention needs to be further improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the self-adhesive protective film and the preparation method thereof, and the prepared self-adhesive protective film has good temperature resistance, can resist more than 70 ℃, has good compatibility with polyolefin materials, does not have the phenomena of layering and falling, and is particularly suitable for protecting acrylic plates.

One of the purposes of the invention is to provide a self-adhesive protective film, and in order to achieve the purpose, the invention adopts the following technical scheme:

a self-adhesive protective film comprises, by mass, 10-30% of a surface layer, 60-70% of an intermediate layer and 10-20% of an adhesive layer which are arranged in sequence from top to bottom, wherein,

the surface layer is 100% of polyolefin material by mass percentage;

the middle layer comprises 85-95% of polyolefin material and 5-15% of polyolefin plastomer by mass percentage;

the adhesive layer comprises, in mass percent, 85-95% of a polyolefin material and 5-15% of a polyolefin plastomer.

The self-adhesive protective film, the middle layer and the adhesive layer are arranged, so that the content reduction caused by the migration of the polyolefin plastomer can be prevented, the temperature resistance of the material is improved due to the addition of the polyolefin plastomer, the compatibility with the polyolefin material on the surface layer is good, and the phenomena of layering and falling can not occur.

Specifically, the mass percentage of the surface layer is 10 to 30%, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%, etc., the mass percentage of the intermediate layer is 60 to 70%, for example, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, or 70%, etc., and the mass percentage of the pressure-sensitive adhesive layer is 10 to 20%, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%, etc.

Wherein the surface layer is 100% polyolefin material by mass percent.

Wherein the intermediate layer comprises 85-95% by mass of polyolefin material and 5-15% by mass of polyolefin plastomer, for example 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94% or 95% by mass of polyolefin material and the like, and 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15% by mass of polyolefin plastomer and the like.

Wherein, the adhesion layer comprises 85-95% of polyolefin material and 5-15% of polyolefin plastomer by mass percentage, for example, the polyolefin material is 85%, 86%, 87%, 88%, 89% 90%, 91%, 92%, 93%, 94% or 95% by mass percentage, and the polyolefin plastomer is 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15% by mass percentage.

POP (polyolefin plastomer) polyolefin plastomer, most of the base material of the plastomer is ethylene, only the Vercity of DOW, the Vistamaxx of EXXON and the Tafmer of Mitsui are propenyl, all the comonomers are octene, hexene or butene, the comonomer content of POP is less than 20%, and the comonomer content influences the density of POP.

By utilizing the characteristics of low POP seal-opening temperature, hot viscosity, pollution resistance, heat sealing, toughness, tear resistance and transparency, the POP packaging film is applied to the field of food packaging, the fields of fresh food, fresh meat, processed meat, block cheese, milk and the like, the fields of sanitation and medical treatment, the field of elastic films, diapers, elastic waistbands and basement membranes, the field of personal care and the like; POP is suitable for durable applications using its toughness and durability, either as a base polymer or blended with other polymers to improve flow during processing or softness of finished products, including flooring, containers, extruded profiles, and injection and rotomolded products; the POP is suitable for the formula of the hot melt adhesive by utilizing the excellent bonding strength of the POP, has higher bonding force and clean construction, and is used for heat sealing of carton boxes, sanitation and other fields.

The POP VERSIFY 3401 plastomer is a resin with moderate melt flow rate and is widely used in a variety of manufacturing and processing areas, including cast film, extrusion and injection molding processes. The resin is particularly suitable for stretched films and soft films, is also a PP modified material, and has stable performance.

The POP VERSIFY 3401 plastomer has very good mechanical properties. The utility model can resist the breakage caused by falling and squeezing during the use and transportation. Its puncture resistance is three times that of conventional EVA resins and ionomers, and even exceeds that of ultra low density polyethylene which is long-lived in puncture resistance. It also has excellent impact strength. POP VESIFY 3401 is mainly used for: PP modification; packaging the stretched film; the soft fabric film, the fabric and the spraying layer, POP can increase the tensile rate, the puncture resistance, the elasticity and other properties of the material.

POP VESIFY 3401 is generally used as a toughening material of a polypropylene carrier and is used for injection molding industries such as sole materials, wire sleeves and the like. However, the POP VESIFY 3401 can obviously improve the temperature resistance of the polyolefin material and the compatibility with the PP base material.

The polyolefin plastomer is POP VERSIFY 3401.

The polyolefin material is polyethylene or polypropylene.

The adhesive comprises, by mass, 20% of a surface layer, 65% of a middle layer and 15% of an adhesive layer which are arranged in sequence from top to bottom.

The polyolefin material of the surface layer is polypropylene BD212 CF.

Preferably, the polyolefin material of the middle layer and the adhesion layer is polypropylene RD208 CF.

The polyolefin material of the surface layer is polyethylene LDPE 2420K or LDPE 2420H.

Preferably, the polyolefin material of the middle layer and the adhesion layer is polyethylene LDPE 2420K, polyethylene LDPE2420H or polyethylene HDPE HF 560.

As a preferable scheme of the invention, the adhesive comprises 20% of a surface layer, 65% of a middle layer and 15% of an adhesion layer which are arranged in sequence from top to bottom in percentage by mass, wherein,

the surface layer is 100% of polypropylene BD212CF by mass percentage;

the middle layer comprises 85-95% of polypropylene RD208CF and 5-15% of POP VERSIFY 3401 by mass percentage;

the adhesive layer comprises 85-95% of polypropylene RD208CF and 5-15% of POP VERSIFY 3401 by mass percentage.

Comprises 20 percent of surface layer, 65 percent of middle layer and 15 percent of adhesion layer which are arranged from top to bottom in sequence according to mass percentage, wherein,

the surface layer is 100% of polyethylene LDPE 2420K by mass percentage;

the middle layer comprises 85-95% of polyethylene LDPE 2420K and 5-15% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer comprises 85-95% of polyethylene LDPE 2420K and 5-15% of POP VERSIFY 3401 in percentage by mass.

The second purpose of the present invention is to provide a method for preparing the self-adhesive protective film according to the first purpose, comprising the following steps: the material is prepared by a three-layer coextrusion casting method.

Wherein the temperature of the three-layer co-extrusion extruder is 190-210 ℃, such as 190 ℃, 195 ℃, 200 ℃, 205 ℃ or 210 ℃ and the like; the temperature of the die is 200 ℃ to 220 ℃, for example, 200 ℃, 205 ℃, 210 ℃, 215 ℃ or 220 ℃.

Compared with the prior art, the invention has the beneficial effects that:

the self-adhesive protective film has good temperature resistance, can resist more than 70 ℃, has good compatibility with polyolefin materials, does not generate the phenomena of layering and falling, and is particularly suitable for protecting acrylic plates.

Detailed Description

The technical solution of the present invention is further described below by way of specific embodiments.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

Example 1

The self-adhesive protective film of the embodiment adopts a polypropylene base material, and comprises, by mass percent, a surface layer of 20%, a middle layer of 65%, and an adhesive layer of 15%, wherein,

the surface layer is 100% of PP BD212CF in percentage by mass;

the middle layer comprises 90% of PP RD208CF and 10% of POP VERSIFY 3401 in mass percentage;

the adhesive layer comprises 90% by mass of PP RD208CF and 10% by mass of POP VERSIFY 3401.

The manufacturers of PP BD212CF and PP RD208CF of the surface layer and the intermediate layer are Borealis , POP VERSIFY 3401 of the intermediate layer and the adhesive layer are dow chemical, and PP RD208CF of the adhesive layer is singapore sumitomo chemical.

The preparation method of the self-adhesive protective film of the embodiment is as follows: the composite material is prepared by a three-layer coextrusion casting method, wherein the temperature of an extruder is 200 ℃, and the temperature of a die head is 210 ℃.

Example 2

The self-adhesive protective film of the embodiment adopts a polyethylene base material, and comprises, by mass percent, a surface layer of 20%, a middle layer of 65%, and an adhesive layer of 15%, wherein,

the surface layer is 100 percent of LDPE 2420K by mass percentage;

the middle layer comprises 90% of LDPE 2420K and 10% of POP VERSIFY 3401 in mass percentage;

the adhesive layer comprises 90% LDPE 2420K and 10% POP VERSIFY 3401 by mass.

Wherein the LDPE 2420K manufacturer of the surface layer, the middle layer and the adhesive layer is Zhonghai shell, and the POP VERSIFY 3401 manufacturer of the middle layer and the adhesive layer is American Dow chemical.

The preparation method of the self-adhesive protective film of this example is the same as that of example 1.

Example 3

This example is different from example 1 in the amount of POP VERSIFY 3401 used in the intermediate layer and the adhesive layer, and is otherwise the same as example 1.

Specifically, the middle layer comprises 95% of PP RD208CF and 5% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer comprises 95% of PP RD208CF and 5% of POP VERSIFY 3401 by mass percent.

Example 4

This example is different from example 1 in the amount of POP VERSIFY 3401 used in the intermediate layer and the adhesive layer.

Specifically, the middle layer comprises 85% of PP RD208CF and 15% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer comprises 85% of PP RD208CF and 15% of POP VERSIFY 3401 by mass percent.

Example 5

This example is different from example 1 in the mass percentages of the surface layer, the intermediate layer and the adhesive layer, and is otherwise the same as example 1.

Specifically, the adhesive comprises, by mass, 10% of a surface layer, 70% of an intermediate layer and 20% of an adhesive layer which are sequentially arranged from top to bottom.

Example 6

This example is different from example 1 in the mass percentages of the surface layer, the intermediate layer, and the adhesive layer, and is otherwise the same as example 1.

Specifically, the adhesive comprises, by mass, 20% of a surface layer, 60% of a middle layer and 20% of an adhesive layer which are sequentially arranged from top to bottom.

Comparative example 1

The self-adhesive protective film of the embodiment adopts a polyethylene base material, and comprises 20% of a surface layer, 65% of a middle layer and 15% of an adhesive layer which are sequentially arranged from top to bottom in percentage by mass, wherein,

the surface layer is 100 percent of LDPE2420H in percentage by mass;

the middle layer comprises 40% HDPE HF560 and 60% LDPE2420H by mass percentage;

the adhesive layer comprises 90% LDPE2420H and 10% POP VERSIFY 3401 by mass.

Wherein the LDPE2420H of the surface layer, the intermediate layer and the adhesive layer was made from kakkiso, the HDPE HF560 of the intermediate layer was made from japan JPE, and the POP VERSIFY 3401 of the adhesive layer was made from american dow chemical.

The self-adhesive protective film of this comparative example was prepared in the same manner as in example 1.

Comparative example 2

This comparative example differs from example 1 in that it does not contain an intermediate layer, only the surface layer and the adhesive layer, and is otherwise the same as example 1.

Comparative example 3

This comparative example differs from example 1 in that the polyolefin plastomer POP VERSIFY 3401 of the interlayer and the adhesive layer was replaced with SP1520 of mitsui chemistry, otherwise identical to example 1.

Comparative example 4

This comparative example differs from example 1 in that the amount of POP VERSIFY 3401 used was different for the interlayer and the adhesive, and was otherwise the same as example 1.

Specifically, the middle layer comprises 99% of PP RD208CF and 1% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer comprises 99% of PP RD208CF and 1% of POP VERSIFY 3401 by mass percent.

Comparative example 5

This comparative example is different from example 1 in the amount of POP VERSIFY 3401 used in the intermediate layer and the adhesive layer, and is otherwise the same as example 1.

Specifically, the middle layer comprises 80% of PP RD208CF and 20% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer comprises 80% of PP RD208CF and 20% of POP VERSIFY 3401 by mass percent.

The self-adhesive protective films obtained in examples 1 to 6 and comparative examples 1 to 5 were subjected to performance tests, and the test results are shown in table 1.

The test method of the temperature resistance comprises the following steps: the prepared self-adhesive protective film is attached to an acrylic plate and then placed for 12 hours at the temperature of 60 ℃ and 1 hour at the temperature of 70 ℃.

Wherein, the testing standard of the viscosity is carried out according to GB/T2792-1981, and the specific testing conditions are that the temperature is 25 ℃, the humidity is 60 percent, and the stripping force of the material is tested under the testing conditions.

TABLE 1

As can be seen from Table 1, the polypropylene substrate is adopted in the example 1 of the invention, the film has better hardness, can resist high temperature of more than 70 ℃, has good compatibility with polyolefin materials, and does not have the phenomena of layering and falling off.

Example 2 a polyethylene substrate was used and the film was softer and had better adhesion.

Example 3 reduction in the amount of POP VERSIFY 3401 used for the interlayer and adhesive layer reduced the viscosity.

Example 4 increasing the amount of POP VERSIFY 3401 in the interlayer and adhesive layers increased the viscosity.

The mass percentages of the surface, intermediate and adhesive layers of examples 5 and 6 increase the percentage of adhesive layers, which increases the production cost because the adhesive material is expensive.

The intermediate layer of comparative example 1, with the addition of HDPE, provides a film with good temperature resistance and good adhesion.

Comparative example 2, which contained no intermediate layer and only surface layer and adhesive layer, POP VERSIFY 3401 migrated with a reduced amount, and made the viscosity unstable, sometimes resulting in no viscosity on the surface.

Comparative example 3 replacement of the polyolefin plastomer POP VERSIFY 3401 of the middle and adhesive layers with SP1520 of three well chemistry would risk residue and peel.

Too little POP VERSIFY 3401 in the middle layer and adhesive layer of comparative example 4 reduced the viscosity with little tack.

Comparative example 5 the amount of POP VERSIFY 3401 in the intermediate and adhesive layers was too large, so that the viscosity was too high to affect the unwinding properties of the film roll.

The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.

Claims

1. A self-adhesive protective film resistant to high temperature of 70 ℃ is characterized by comprising, by mass percentage, 10-30% of a surface layer, 60-70% of an intermediate layer and 10-20% of an adhesive layer which are sequentially arranged from top to bottom, wherein,

the surface layer is 100% of polyolefin material by mass percentage;

the middle layer consists of 85-95% of polyolefin material and 5-15% of polyolefin plastomer by mass percentage;

the adhesion layer consists of 85-95% of polyolefin material and 5-15% of polyolefin plastomer by mass percentage;

the polyolefin plastomer is POP VERSIFY 3401;

the polyolefin material is polyethylene or polypropylene.

2. The self-adhesive protective film according to claim 1, comprising 20% of the surface layer, 65% of the intermediate layer and 15% of the adhesive layer in this order from top to bottom in percentage by mass.

3. The self-adhesive protective film according to claim 1, wherein the polyolefin material of the surface layer is polypropylene BD212 CF.

4. The self-adhesive protective film according to claim 1, wherein the polyolefin material of the middle layer and the adhesive layer is polypropylene RD208 CF.

5. The self-adhesive protective film according to claim 1, wherein the polyolefin material of the surface layer is polyethylene LDPE 2420K or LDPE 2420H.

6. The self-adhesive protective film according to claim 1, wherein the polyolefin material of the middle layer and the adhesive layer is polyethylene LDPE 2420K, polyethylene LDPE2420H or polyethylene HDPE HF 560.

7. The self-adhesive protective film according to claim 1, comprising 20% of the surface layer, 65% of the intermediate layer and 15% of the adhesive layer, which are arranged in this order from top to bottom,

the surface layer is 100% of polypropylene BD212 CF;

the middle layer consists of 85-95% of polypropylene RD208CF and 5-15% of POP VERSIFY 3401 in percentage by mass;

the adhesive layer consists of 85-95% by mass of polypropylene RD208CF and 5-15% by mass of POP VERSIFY 3401.

8. The self-adhesive protective film according to claim 1, comprising 20% of the surface layer, 65% of the intermediate layer and 15% of the adhesive layer, which are arranged in this order from top to bottom,

the surface layer is 100% of polyethylene LDPE 2420K by mass percentage;

the middle layer consists of 85-95% of polyethylene LDPE 2420K and 5-15% of POP VERSIFY 3401 in percentage by mass;

9. A process for the preparation of a self-adhesive protective film according to any one of claims 1 to 8, characterized in that it comprises the following steps: the material is prepared by a three-layer coextrusion casting method.

10. The preparation method as claimed in claim 9, wherein the temperature of the extruder for the three-layer co-extrusion is 190-210 ℃ and the temperature of the die head is 200-220 ℃.