阅读说明：本技术 人造大理石用易剥离的保护膜及制备方法 (Easily-stripped protective film for artificial marble and preparation method thereof ) 是由 顾程松 张健 张毅倩 于 2021-09-08 设计创作，主要内容包括：本发明涉及一种人造大理石用易剥离的保护膜及其制备方法,原料的重量份组成如下：聚乙烯80-100份,聚烯烃20-30份,2,5-呋喃二甲酸2-5份,抗氧化剂0.5-1.5份,增塑剂0.5-1.5份,润滑剂0.5-1.0份。本申请的发明人通过实践发现,聚乙烯、聚烯烃和2,5-呋喃二甲酸三者组合使用,互相协同,克服了前述缺陷。且制备的保护膜强度、韧性性能优良,具有较好的耐候性及持粘力稳定性,经数日或久贴剥离力增长不显著,易于揭去,在揭去时人造大理石桌面上没有残胶留存,无留影。(The invention relates to an easily-stripped protective film for artificial marble and a preparation method thereof, wherein the easily-stripped protective film comprises the following raw materials in parts by weight: 80-100 parts of polyethylene, 20-30 parts of polyolefin, 2-5 parts of 2, 5-furandicarboxylic acid, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of plasticizer and 0.5-1.0 part of lubricant. The inventor of the application finds that the combination of polyethylene, polyolefin and 2, 5-furandicarboxylic acid is synergistic, and overcomes the defects. The prepared protective film has excellent strength and toughness, better weather resistance and lasting adhesion stability, insignificant increase of stripping force after being pasted for a plurality of days or a long time, easy uncovering, no residual glue on the artificial marble tabletop when being uncovered and no image.)

1. The utility model provides an artificial marble is with protection film of easy peeling off which characterized in that: the weight portions of the raw materials are as follows: 80-100 parts of polyethylene, 20-30 parts of polyolefin, 2-5 parts of 2, 5-furandicarboxylic acid, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of plasticizer and 0.5-1.0 part of lubricant.

2. The easily peelable protective film for artificial marble according to claim 1, wherein: 90-100 parts of polyethylene, 25-30 parts of polyolefin, 3-5 parts of 2, 5-furandicarboxylic acid, 1-1.2 parts of antioxidant, 1-1.2 parts of plasticizer and 0.5-0.75 part of lubricant.

3. The easily peelable protective film for artificial marble according to claim 2, wherein: 100 parts of polyethylene, 25 parts of polyolefin, 3 parts of 2, 5-furandicarboxylic acid, 1 part of antioxidant, 1 part of plasticizer and 0.5 part of lubricant.

4. The easily peelable protective film for artificial marble according to claim 1, 2 or 3, wherein: the polyethylene is low-density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.06-0.07 KN/M; tensile strength: 600 and 800 MPa; elongation at break: 150-180 percent; temperature resistance: less than or equal to 60 ℃.

5. The easily peelable protective film for artificial marble according to claim 1, 2 or 3, wherein: the polyethylene is medium density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.08-0.11 KN/M; tensile strength: 600-; elongation at break: 180-200 percent; temperature resistance: less than or equal to 60 ℃.

6. The easily peelable protective film for artificial marble according to claim 1 or 2, wherein: the polyethylene is high-density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.22-0.32 KN/M; tensile strength: 600-; elongation at break: 180-220 percent; temperature resistance: less than or equal to 60 ℃.

7. A method for preparing an easily peelable protective film for artificial marble according to any one of claims 1 to 6, wherein: weighing the raw materials according to the weight parts, uniformly mixing and stirring, adding the raw materials into a co-extrusion film blowing machine for blow molding, and rolling after cooling to obtain the transparent ultrahigh-strength PE film.

8. The method for preparing an easily peelable protective film for artificial marble according to claim 7, wherein: the temperature of the blow molding is 150-170 ℃.

Technical Field

The invention relates to an easily-stripped protective film for artificial marble and a preparation method thereof, belonging to the technical field of film material processing.

Background

The artificial marble is made up by using broken stone of natural marble or granite as filling material and cement, gypsum and unsaturated polyester resin as adhesive through the processes of stirring, forming, grinding and polishing. The artificial marble has many characteristics of natural marble. For example, the artificial marble has various colors, good flexibility, unobvious joining treatment, strong sense of unity, colorful, ceramic luster, high appearance hardness, difficult damage, corrosion resistance, high temperature resistance and easy cleaning due to the manual adjustment.

The PE protective film for the artificial marble tabletop is a macromolecular organic compound with the simplest structure. The PE protective film uses a Polyethylene (PE) plastic film as a base material, and is classified into a high-density polyethylene protective film, a medium-density polyethylene, and a low-density polyethylene according to the difference in density. The PE protective film needs to have the following properties:

1. the protective film is inert to the artificial marble tabletop.

2. The protective film has good adhesion performance to the artificial marble tabletop, and the protective film cannot warp and fall off in the material carrying and processing processes;

3. the protective film has good weather resistance and lasting adhesion stability, the peeling force is not obviously increased after being pasted for a plurality of days or a long time, the protective film is easy to uncover, and no residual glue is left on the artificial marble tabletop when the protective film is uncovered, so that no image is left.

The PE protective film for the artificial marble tabletop in the prior art has good inertia and adhesion performance, but has general weather resistance and lasting adhesion stability, and is easy to remain when peeled off after a long time. The technical problem needs to be solved in practical application.

Disclosure of Invention

The invention aims to solve the defects of the prior art and provides an easily-peeled protective film for artificial marble. The protective film has good weather resistance and lasting adhesion stability, the peeling force is not obviously increased after being pasted for a plurality of days or a long time, the protective film is easy to uncover, no residual glue is left on the artificial marble tabletop when the artificial marble tabletop is uncovered, and no image is left.

The second object of the present invention is to provide a method for preparing an easily peelable protective film for artificial marble.

The technical scheme adopted by the invention for solving the technical problems is as follows:

the utility model provides an artificial marble is with protection film of easy peeling off which characterized in that: the weight portions of the raw materials are as follows: 80-100 parts of polyethylene, 20-30 parts of polyolefin, 2-5 parts of 2, 5-furandicarboxylic acid, 0.5-1.5 parts of antioxidant, 0.5-1.5 parts of plasticizer and 0.5-1.0 part of lubricant.

Cycloolefin polymer (COP) is an amorphous transparent polymer material with a cyclic structure, and is a polymer obtained by ring-opening metathesis polymerization of norbornene monomer by metallocene catalyst and hydrogenation of unsaturated double bonds in the norbornene monomer.

The COP material has the main characteristics that: high transparency and high gloss; high heat resistance and good water vapor air tightness; the glass transition temperature of the transparent resin is 140-170 ℃; high rigidity and high strength; excellent extrusion moldability and thermoformability; good affinity with polyolefin, excellent biocompatibility and chemical inertness, hydrolysis resistance, polar organic solvent resistance, acid resistance and alkali resistance. The inventor of the application applies the protective film which is easy to peel off for processing the artificial marble, fully utilizes the main characteristics of COP materials, and has obvious effect.

The molecular structure of 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic ring, and can effectively improve heat resistance and mechanical property when used for synthesizing high molecular material. Meanwhile, the oxygen barrier property of the furan ring-containing polyester material can be improved by 2-10 times compared with PE used for a packaging material, but the use of 2,5-FDCA also has the defects that the color is darker due to the increase of temperature in the co-agent process, and the tensile modulus and the tensile strength are low due to the low molecular weight of the furan ring-containing polyester material. The inventor of the application finds that the combination of polyethylene, polyolefin and 2, 5-furandicarboxylic acid is synergistic, and overcomes the defects. The prepared protective film has excellent strength and toughness, better weather resistance and lasting adhesion stability, insignificant increase of stripping force after being pasted for a plurality of days or a long time, easy uncovering, no residual glue on the artificial marble tabletop when being uncovered and no image.

Preferably, 90-100 parts of polyethylene, 25-30 parts of polyolefin, 3-5 parts of 2, 5-furandicarboxylic acid, 1-1.2 parts of antioxidant, 1-1.2 parts of plasticizer and 0.5-0.75 part of lubricant.

Preferably, 100 parts of polyethylene, 25 parts of polyolefin, 3 parts of 2, 5-furandicarboxylic acid, 1 part of antioxidant, 1 part of plasticizer and 0.5 part of lubricant.

Preferably, the polyethylene is low density polyethylene, and the protective film thickness: 0.05-0.13 mm; peel strength: 0.06-0.07 KN/M; tensile strength: 600 and 800 MPa; elongation at break: 150-180 percent; temperature resistance: less than or equal to 60 ℃.

Preferably, the polyethylene is medium density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.08-0.11 KN/M; tensile strength: 600-; elongation at break: 180-200 percent; temperature resistance: less than or equal to 60 ℃.

Preferably, the polyethylene is high density polyethylene, and the protective film thickness: 0.05-0.13 mm; peel strength: 0.22-0.32 KN/M; tensile strength: 600-; elongation at break: 180-220 percent; temperature resistance: less than or equal to 60 ℃.

The preparation method of the easily-peeled protective film for the artificial marble comprises the steps of weighing the raw materials in parts by weight, uniformly mixing and stirring, adding the raw materials into a co-extrusion film blowing machine for blow molding, cooling and rolling to obtain the transparent ultrahigh-strength PE film. The temperature of the blow molding is 150-170 ℃.

The invention has the beneficial effects that:

cycloolefin polymer (COP) is an amorphous transparent polymer material with a cyclic structure, and is a polymer obtained by ring-opening metathesis polymerization of norbornene monomer by metallocene catalyst and hydrogenation of unsaturated double bonds in the norbornene monomer.

The COP material has the main characteristics that: high transparency and high gloss; high heat resistance and good water vapor air tightness; the glass transition temperature of the transparent resin is 140-170 ℃; high rigidity and high strength; excellent extrusion moldability and thermoformability; good affinity with polyolefin, excellent biocompatibility and chemical inertness, hydrolysis resistance, polar organic solvent resistance, acid resistance and alkali resistance. The inventor of the application applies the protective film which is easy to peel off for processing the artificial marble, fully utilizes the main characteristics of COP materials, and has obvious effect.

The molecular structure of 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic ring, and can effectively improve heat resistance and mechanical property when used for synthesizing high molecular material. Meanwhile, the oxygen barrier property of the furan ring-containing polyester material can be improved by 2-10 times compared with PE used for a packaging material, but the use of 2,5-FDCA also has the defects that the color is darker due to the increase of temperature in the co-agent process, and the tensile modulus and the tensile strength are low due to the low molecular weight of the furan ring-containing polyester material. The inventor of the application finds that the combination of polyethylene, polyolefin and 2, 5-furandicarboxylic acid is synergistic, and overcomes the defects. The prepared protective film has excellent strength and toughness, better weather resistance and lasting adhesion stability, insignificant increase of stripping force after being pasted for a plurality of days or a long time, easy uncovering, no residual glue on the artificial marble tabletop when being uncovered and no image.

Detailed Description

The technical solution of the present invention will be further specifically described below by way of specific examples.

Example 1:

an easily-peeled protective film for artificial marble comprises the following raw materials in parts by weight: 80 parts of polyethylene, 20 parts of polyolefin, 2 parts of 2, 5-furandicarboxylic acid, 0.5 part of antioxidant, 0.5 part of plasticizer and 0.5 part of lubricant. The polyethylene is low-density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.06-0.07 KN/M; tensile strength: 600 and 800 MPa; elongation at break: 150-180 percent; temperature resistance: less than or equal to 60 ℃.

Embodiment 1 a method for preparing an easily peelable protective film for artificial marble, comprising the steps of weighing the raw materials in parts by weight, uniformly mixing and stirring, adding the raw materials into a co-extrusion film blowing machine for blow molding, cooling and rolling to obtain the transparent ultrahigh-strength PE film. The blow molding temperature was 150 ℃.

Example 2

The utility model provides an artificial marble is with protection film of easy peeling off which characterized in that: the weight portions of the raw materials are as follows: 100 parts of polyethylene, 30 parts of polyolefin, 5 parts of 2, 5-furandicarboxylic acid, 1.5 parts of antioxidant, 1.5 parts of plasticizer and 1.0 part of lubricant.

The polyethylene is medium density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.08-0.11 KN/M; tensile strength: 600-; elongation at break: 180-200 percent; temperature resistance: less than or equal to 60 ℃.

Embodiment 2 preparation method of easy-to-peel protective film for artificial marble, weigh each raw materials according to the part by weight, after the even mixing stirring, add in the inflation film manufacturing machine of coextruding blow molding, the rolling after cooling, obtain transparent superhigh intensity PE membrane. The blow molding temperature was 170 ℃.

Example 3

The utility model provides an artificial marble is with protection film of easy peeling off which characterized in that: the weight portions of the raw materials are as follows: 90 parts of polyethylene, 25 parts of polyolefin, 3 parts of 2, 5-furandicarboxylic acid, 1 part of antioxidant, 1 part of plasticizer and 0.5 part of lubricant, wherein the polyethylene is low-density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.06-0.07 KN/M; tensile strength: 600 and 800 MPa; elongation at break: 150-180 percent; temperature resistance: less than or equal to 60 ℃.

Embodiment 3 preparation method of easy-to-peel protective film for artificial marble, weigh each raw materials according to the part by weight, after the even mixing stirring, add in the inflation film manufacturing machine of coextruding blow molding, the rolling after cooling, obtain transparent superhigh intensity PE membrane. The blow molding temperature was 160 ℃.

Example 4

The utility model provides an artificial marble is with protection film of easy peeling off which characterized in that: the weight portions of the raw materials are as follows: 100 parts of polyethylene, 30 parts of polyolefin, 5 parts of 2, 5-furandicarboxylic acid, 1.2 parts of antioxidant, 1.2 parts of plasticizer and 0.75 part of lubricant. The polyethylene is medium density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.08-0.11 KN/M; tensile strength: 600-; elongation at break: 180-200 percent; temperature resistance: less than or equal to 60 ℃.

Embodiment 4 preparation method of easy-to-peel protective film for artificial marble, weigh each raw material according to the part by weight, after the even mixing stirring, add in the inflation film manufacturing machine of coextruding blow molding, the rolling after cooling, obtain transparent superhigh intensity PE membrane. The blow molding temperature was 170 ℃.

Example 5

An easily-peeled protective film for artificial marble comprises the following raw materials in parts by weight: 100 parts of polyethylene, 25 parts of polyolefin, 3 parts of 2, 5-furandicarboxylic acid, 1 part of antioxidant, 1 part of plasticizer and 0.5 part of lubricant. The polyethylene is high-density polyethylene, and the thickness of the protective film is as follows: 0.05-0.13 mm; peel strength: 0.22-0.32 KN/M; tensile strength: 600-; elongation at break: 180-220 percent; temperature resistance: less than or equal to 60 ℃.

Embodiment 5 preparation method of easily peeled protective film for artificial marble, weigh each raw material according to the part by weight, after the homogeneous mixing stirring, add in the inflation film manufacturing machine and blow molding, roll after cooling, obtain the transparent ultrahigh strength PE film. The temperature of the blow molding is 150-170 ℃.

The invention has the beneficial effects that:

cycloolefin polymer (COP) is an amorphous transparent polymer material with a cyclic structure, and is a polymer obtained by ring-opening metathesis polymerization of norbornene monomer by metallocene catalyst and hydrogenation of unsaturated double bonds in the norbornene monomer.

The COP material has the main characteristics that: high transparency and high gloss; high heat resistance and good water vapor air tightness; the glass transition temperature of the transparent resin is 140-170 ℃; high rigidity and high strength; excellent extrusion moldability and thermoformability; good affinity with polyolefin, excellent biocompatibility and chemical inertness, hydrolysis resistance, polar organic solvent resistance, acid resistance and alkali resistance. The inventor of the application applies the protective film which is easy to peel off for processing the artificial marble, fully utilizes the main characteristics of COP materials, and has obvious effect.

The molecular structure of 2, 5-furandicarboxylic acid (2,5-FDCA) contains aromatic ring, and can effectively improve heat resistance and mechanical property when used for synthesizing high molecular material. Meanwhile, the oxygen barrier property of the furan ring-containing polyester material can be improved by 2-10 times compared with PE used for a packaging material, but the use of 2,5-FDCA also has the defects that the color is darker due to the increase of temperature in the co-agent process, and the tensile modulus and the tensile strength are low due to the low molecular weight of the furan ring-containing polyester material. The inventor of the application finds that the combination of polyethylene, polyolefin and 2, 5-furandicarboxylic acid is synergistic, and overcomes the defects. The prepared protective film has excellent strength and toughness, the protective films of examples 1-5 have good weather resistance and lasting adhesion stability, the peeling force does not increase remarkably after being pasted for a plurality of days or a long time, the protective films are easy to remove, and no residual glue is left on the artificial marble tabletop when the artificial marble tabletop is removed, so that no shadow is left.

1. And (3) viscosity testing: the protective films of examples 1-5 adhered readily to the material of the surface, leaving no residual glue. Can be bent by 90 degrees without cracks.

2. And (3) load testing: bonding the load for 360 hours at an ambient temperature of 25-50 ℃. The protective film is peeled off, and no adhesive residue is left on the surface.

3. Ultraviolet aging test: the protective film was free of cracks and residues after peeling when exposed to a 300W UV lamp at an ambient temperature of 50 ℃ for 60 hours.

4. Moisture and heat aging test: the environmental temperature is 60 ℃, the humidity is 80%, and after the protective film is stripped, the residual glue can not be left and the surface of the artificial marble can not be corroded after 240 hours.

The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.