KR100429660B1 - The Harmless Polyolefin Sheet - Google Patents

Abstract

PURPOSE: Provided is a harmless polyolefin sheet, which has durability, chemical resistance, scratch resistance, processability, flexibility and an economical feature that are equal to those of a polyvinyl chloride sheet, and does not generate environmental hormones and thus is not harmful to the human body. CONSTITUTION: The harmless polyolefin sheet is obtained by mixing a polyethylene resin with 1-60 wt% of a cyclic olefin copolymer resin and molding the mixture, wherein the polyolefin sheet has an elongation ratio of 100-1000%, a tensile strength of 4,000-8,000 g/in, a tear strength of 100-400 g/in and a surface tension of 30-44 dyne/cm¬2. More particularly, the polyethylene resin is a mixture of LDPE with HDPE.

Description

Harmless Polyolefin Sheet

The present invention relates to a polyolefin sheet which can be used as various sheets such as marking sheets, interior sheets, decoration sheets, signs, interior and exterior decorative sheets, and in particular, dimensional stability by mixing an appropriate amount of cyclic olefin copolymer resin with polyethylene resin. The present invention relates to a polyolefin sheet which can be guaranteed with weather resistance, chemical resistance, surface gloss, scratch resistance, ease of processing, and low manufacturing cost and is harmless to human body.

Vinyl chloride resin is inexpensive, heat resistant, and can take various forms in ductility and rigidity, so it can be used for flooring, medical equipment, automobile seat cover, wire insulator, marking sheet, interior sheet, decoration sheet, signboard or interior decoration sheet. It is widely used as a raw material for. Since vinyl chloride resins used in many applications are so low in crystallinity that they decompose due to light or heat, they are colored yellow or brown, or their gaseous properties deteriorate. Therefore, stabilizers are always formulated when manufacturing sheets from vinyl chloride resins. . In addition, since vinyl chloride resin alone is relatively rigid and brittle, when used in various sheets and films, phthalic acid (phthalates, dehp, dinp, dbp, etc.) plasticizers and adipic acid (adipates, dhea, etc.) plasticizers are added. Various vinyl chloride sheets prepared by mixing plasticizer and stabilizer with vinyl chloride resin are generally 4,000 to 8,000 g / in tensile strength, 100 to 1000% elongation, and 100 to 400 g. / in tear strength and surface tension of 30 ~ 44dyne / cm2, not only excellent cutting, extensibility, printability and adhesion, but also excellent chemical resistance, scratch resistance, dimensional stability, etc. Today marking sheet, interior sheet, decoration It is widely used as a sheet, signboard or interior decoration sheet.

However, the vinyl chloride sheet used in such many uses releases a large amount of dioxins upon incineration. Such dioxin is a class 1 carcinogen that can be inherited by the World Health Organization (WHO) in 1992, and is classified as a reliable environmental hormone by the World Wildlife Fund (wwf). Produced as chemical contaminants in the process and occurs when burning compounds containing chlorine. These dioxins are chemically stable and do not break down naturally because they are not easily broken down or combined with other substances.They do not dissolve well in water, so they do not escape well in urine or feces. It is a colorless carcinogen that accumulates continuously in the animal's adipose tissue, and even if a small amount is ingested, has a toxic effect of 10,000 times of cyanide and 1,000 times of saccharin.

In addition, the plasticizer contained in the vinyl chloride sheet is not bound to the main body and exists in a floating state, and therefore is easily eluted even with a small impact. Greenpeace warned that phthalic acid-based plasticizers cause liver and kidney disorders and reproductive malformations, and endocrine-disrupting substances. It happened. Furthermore, in developed countries such as Europe and the United States, because plasticizers can cause cancer in the liver and kidneys and may have harmful effects on other organs, safety measures such as banning the sale of vinyl chloride baby toys containing plasticizers or product recalls have been taken. have. Germany, France and Greece prohibit the production and sale of vinyl chloride toys, while Austria, Denmark and Sweden prohibit the use of phthalic plasticizers in toys.

In addition, the stabilizer added to the vinyl chloride sheet also has a deleterious effect on growth, liver, renal uterus and the like during overexposure.

As described above, due to the human hazards of vinyl chloride products, restrictions are imposed on vinyl chloride products in each country, and the place of vinyl chloride products is getting narrower.

This phenomenon is not an exception in various sheet-related fields such as marking sheets, interior sheets, decoration sheets, signboards or interior decorative sheets, and the industry continues to develop products to replace vinyl chloride sheets. The trend is as follows.

(1) Sheets using starch or rubber have better chemical and scratch resistance than vinyl chloride resin, but they have poor dimensional stability, weather resistance, and chemical resistance. In addition, the sheet using acrylic resin, alcohol silane, inorganic polymer, EPS (Expanded Polystyrene) is superior in dimensional stability, chemical resistance, and scratch resistance, but it is not weatherproof compared to vinyl chloride sheet, so it cannot be used outdoors for a long time. In addition, Polyvinyl Butyral resin, Polyvinyl Acetal resin, Glycol-modified PET: Copolyesters (PETG), Poly Butylene Terephthalate (PBT), Acrylonitrile Butadiene Styrene (ABS), Liquid Crystalline Polymer (LCP), Dimethylnaphthalene (DMN), Polyoxymethylene (POM) , PMMA (Polymethylmetacrylate), PPO (Polyphenylene Oxide), PPE (Polyphenylene Ether), PAR (Polyarylate), PEEK (Polyehteretherketone), etc. are also used, but the sheets made of the above resins all have a tensile strength of 9,000 g / in or more and elongation of 100% Subsequently, the above resins are unsuitable as raw materials for the sheet because they do not meet the requirements of the sheet requiring a tensile strength of 4,000 to 8,000 g / in and an elongation of 100 to 1000%.

(2) Recently, biodegradable resins are getting much attention as harmless resins, PLA (Polylactic acid), HA (Hyaluronic acid), PHB (Polyhydroxybutyric acid), PHV (Polyhydroxy valerate), PVA (Polyvinyl alcohol), PHA (Polyhydroxyalkanoate) Sheets made of biodegradable resins such as Polyhydroxyoctanoate, Polyethylene succinate, Polybutylene succinate, Polybutylene adipate, Polybutylene carbonate, Polycaprolactone, Polytetramethylene adipate, Polytetramethylene terephthalate, Polyethylene terephthalate, etc. , Dimensional stability, surface gloss, and workability are remarkably inferior to vinyl chloride sheet. First of all, the elongation rate is 800 to 2000% or more, which does not satisfy the 100 to 1000% elongation rate of the vinyl chloride sheet.

(3) Polyolefin resin, polymethyl methacrylate, ethyl vinyl acetate, or ultra high molecular weight polyethylene is added to the sheet, but it is more expensive than the marketability and the elongation is 800% to 2000% or more. It does not satisfy -1000% elongation rate.

(4) Sheets made of polypropylene (PP) added with thermoplastic elastomers and acrylic polymers such as Styrene-Butadiene rubber, Styrene-Ethylene Block Copolymer, Ethylene-Ethylene Block Copolymer, Styrene-Styrene Block Copolymer, etc. Although it has been, weather resistance and tensile strength is lower than that of vinyl chloride sheet, the cutting properties of the product does not come out, there is a difficulty in processing, there is a problem that the transparency and whitening phenomenon occurs. In addition, the surface tension of 20 to 28 dyne / cm 2 and far less than 32 to 44 dyne / cm 2 of the vinyl chloride resin has a problem of poor printability and adhesion to other resins.

(5) As a substitute for vinyl chloride sheet, recently, sheets made of TPO (Thermoplastic Olefin), TPE (Thermoplastic Elastomer) and TPV (Thermoplastic Vulcanization) have been used, but these sheets are more expensive than vinyl chloride sheet and even if antistatic agents are used, There is still a lot of static electricity, and there are problems such as poor stain resistance, scratch resistance and adhesiveness when coating the surface, and the elongation is more than 700 to 1700% and does not satisfy the 100 to 1000% elongation of the vinyl chloride resin.

The present invention has been made in order to solve the problems of the conventional vinyl chloride sheet, the object of the present invention by mixing a predetermined amount of a cyclic olefin copolymer in a polyethylene resin, the physical properties of the conventional vinyl chloride sheet, 100 to 1000% elongation, By providing tensile strength of 4,000 ~ 8,000g / in, 100 ~ 400g / in tear strength and surface tension of 30 ~ 44dyne / cm2, the durability, chemical resistance, scratch resistance, processability, flexibility and economicality of vinyl chloride sheet are secured. Furthermore, by solving the hazard problem of vinyl chloride sheet, it is to provide a polyolefin sheet which is free of environmental hormones and harmless to human body.

The present invention is implemented by the embodiment having the following configuration in order to achieve the above object.

According to one embodiment of the present invention, the polyolefin sheet of the present invention is characterized in that the polyethylene resin is molded by mixing a predetermined amount of cyclic olefin copolymer resin.

According to another embodiment of the present invention, the polyolefin sheet of the present invention is molded by mixing a predetermined amount of a cyclic olefin copolymer resin in polyethylene resin, 100 to 1000% elongation, 4,000 to 8,000 g / in tensile strength, 100 to 400 g / in tear strength and surface tension of 30 to 44 dyne / cm < 2 >.

According to another embodiment of the present invention, the polyolefin sheet of the present invention is characterized in that it is molded by mixing a predetermined amount of polyethylene resin 1 ~ 60wt% cyclic olefin copolymer resin.

According to another embodiment of the present invention, the polyol peffin sheet of the present invention is characterized by being molded by mixing a predetermined amount of cyclic olefin copolymer resin in a polyethylene resin in which LDPE and HDPE are mixed in a predetermined ratio.

According to another embodiment of the present invention, the polyolefin sheet of the present invention, a predetermined amount of cyclic olefin copolymer resin mixed with polyethylene resin, PP, PBT, m-PPE, Polyethersulfone (PES), PAR, PSF and UHMW- It is characterized by molding by mixing at least one resin selected from the group consisting of 1 ~ 50wt% PE.

Applicants describe the embodiments described above in detail below.

Experimental condition

Tensile strength, elongation rate and tensile strength of the tables and test examples shown here are all measured by pulling at both sides at a speed of 500 mm / min with a 180 ° peeling test on a 10 mm x 10 mm specimen. The force at the time of breaking a specimen by pulling it at both sides with the speed tester at 500mm / min divided by the unit area.The tearing strength is the force at the time of breaking the specimen by pulling both sides at the speed of 500mm / min with the 180 ° peeling tester. It is the force divided by the film or sheet thickness, and the elongation is the elongation until the specimen breaks by pulling at both sides at a speed of 500mm / min with a 180 ° peeling test. Here, the polyethylene resins used are products of LG Petrochemical, Hanwha Chemical, Daelim Chemical, Honam Petrochemical, Hyundai Petrochemical, and Samsung General Chemical Co., Ltd., and the cyclic olefin copolymer resin is Ilwoong Platech and Hanil Hi-Tech. The product was used by TICONA. In addition, the surface tension of each sheet was a bottle type surface tension measurement product of the United States Diversified Enterprises. In the following, TD stands for TransverseDirection and MD stands for Mechanical Direction.

Applicant shows the physical properties of the vinyl chloride sheet currently widely used prior to the description of the present invention in order to aid the understanding of the present invention in Comparative Example 1 below.

Comparative Example 1

Physical Properties of PVC Sheet The tensile strength MD 4,000 ~ 8,000g / in TD 4,000 ~ 8,000g / in Elongation MD 100-1000% TD 100-1000% Tear strength MD 100-300 g / in TD 200-400 g / in thickness 100 μm

These physical properties make vinyl chloride sheet have excellent durability, chemical resistance, scratch resistance, processability, flexibility and economy. Applicant was able to obtain a sheet that is harmless to the human body while having the physical properties of the vinyl chloride sheet by molding the sheet by mixing the cyclic olefin copolymer resin with polyethylene based on this fact.

Comparative Example 2

Polyethylene resins are harmless to the human body, and are classified into HDPE (High Density Polyethylene), MDPE (Medium Density Polyethylene), LDPE (Low Density Polyethylene), and LLDPE (Linear Low Density Polyethylene). Physical properties of the 'polyethylene sheet') are as shown in Tables 2 to 3.

Physical Properties of LDPE Sheet The tensile strength MD 500-2500 g / in TD 500-2500 g / in Elongation MD 600-2000% TD 600-2000% Tear strength MD 350 ~ 500g / in TD 400-600 g / in Melt index 0.5 ~ 8g / 10min importance 0.86-0.95 g / Surface tension 20 ~ 28dyne / thickness 100 μm

Physical Properties of HDPE Sheets The tensile strength MD 1,500-4,000 g / in TD 1.500-4,000 g / in Elongation MD 550-2000% TD 550-2000% Tear strength MD 200-400 g / in TD 250-450 g / in Melt index 0.02 ~ 0.3g / 10min importance 0.93-1.05 g / Surface tension 20 ~ 28dyne / thickness 100 μm

Polyethylene sheet is harmless and does not release environmental hormones, but it is lower than vinyl chloride sheet in tensile strength as shown in Tables 2 and 3, and is higher in elongation and tear strength, so it is not cut properly during processing. It has a problem in that the durability is poor when exposed to ultraviolet rays over a long period of time, the elongation rate is higher than necessary, and the surface tension is low, resulting in poor printability and poor adhesion with other papers.

Comparative Example 3

On the other hand, the physical properties of the sheet of the cyclic olefin copolymer resin (hereinafter referred to as `` cyclic olefin copolymer sheet '') are as follows.

Physical Properties of Cycloolefin Copolymer Sheet The tensile strength 5,000-8,000 g / in Elongation 30-100% Tear strength Melt index 10 ~ 30g / 10min importance 1.00-1.20g / thickness 100 μm

The cyclic olefin copolymer sheet has the advantages of excellent transparency, low water absorption, and excellent chemical resistance than vinyl chloride sheet, but it has disadvantages such as high flexibility and low tensile strength due to its low elongation and high tensile strength. have.

As described above, the cyclic olefin copolymer or polyethylene alone cannot obtain the physical properties such as the vinyl chloride sheet, but it is noted that the polyethylene sheet and the cyclic olefin copolymer sheet exhibit opposite physical properties. The olefin copolymer resin was mixed to prepare a polyolefin sheet.

The polyolefin sheet is first mixed with a cyclic olefin copolymer resin into a polyethylene resin made of HDPE only, second is a method of molding by mixing a cyclic olefin copolymer resin into a polyethylene resin made of only LDPE, third HDPE and LDPE is mixed in a predetermined ratio It can be produced by a method of molding by mixing the cyclic olefin copolymer resin to the polyethylene resin. The first method has a problem that the extrusion of the sheet is difficult because the melt index of the HDPE is lower than the melt index of the cyclic olefin copolymer, and the second method is a cyclic olefin although the melt index of the LDPE is close to the melt index of the cyclic olefin copolymer. Since the amount of the copolymer resin should be excessively high, the manufacturing cost is high and the cost control is difficult. Therefore, Applicant prepared the polyolefin sheet by the third method and it will be described below.

Experimental Example 1

Applicant mixes 74% by weight of polyethylene resin with LDPE and HDPE at 7: 3, 13% by weight of cyclic olefin copolymer, 4% by weight of antioxidant, 6% by weight of anti-blocking agent, and 3% by weight of UV absorber. The polyolefin sheet having a thickness of 100 μm was extruded by the blow method, and the tensile strength, the elongation rate, the tear strength and the surface tension were measured by the method described above for the sheet, and the measured values are shown in Table 5 below.

Physical Properties of Polyolefin Sheets The tensile strength MD 4,200-7,600 g / in TD 4,500 ~ 8,200g / in Elongation MD 180-720% TD 220-840% Tear strength MD 120 ~ 260g / in TD 230 ~ 420g / in Surface tension 30-42 dyne /

As described above, in the polyolefin sheet, tensile strength, elongation rate, and tear strength were close to those of the vinyl chloride sheet, thereby obtaining flexibility, processability, durability, and chemical resistance of the vinyl chloride sheet.

In addition, through the above experimental example, the Applicant has a surface tension of 20 ~ 28 dyne / Compared to the polyethylene sheet, which is only about the degree, by mixing the amorphous cyclic olefin copolymer resin, the surface of the polyolefin sheet is changed from nonpolar to polar and the surface tension is 30 to 42 dyne / As the degree of improvement is improved, the printability and adhesion to other papers were superior to the polyethylene sheet.

In addition, the polyolefin sheet of the present invention can be melted by high temperature heat and formed into a rolling or compression method such as the T-DIE method or the BLOW method, so that the yield per unit time is reduced by the T-DIE method or the BLOW method. Convenience and quality stability did not come out, mainly produced by the calendering method or cast method is significantly higher than the conventional vinyl chloride sheet, it was also confirmed that high productivity can be secured.

Experimental Example 2

Applicant sets the weight ratio of polyethylene and cyclic olefin copolymer resin to 87wt%, antioxidant 4wt%, antibroking agent 6wt%, UV absorber 3wt%, and then changed the weight ratio of cyclic olefin copolymer resin from 1wt% to 60wt%. After fabricating the sheet, the tensile strength, the elongation rate, and the tear strength were measured for each of the above test conditions.

[Graph 1] Tensile Strength

[Graph 2] Elongation

[Graph 3] Tear Strength

According to the above graph 1-3, as the weight ratio of the olefin copolymer resin increased from 1wt% to 60wt%, the tensile strength, elongation rate and tear strength of the polyolefin resin showed a tendency to drop gradually, but 1 of the cyclic olefin copolymer Tensile strength, elongation and tear strength of the polyolefin resin were all similar to those of the vinyl chloride sheet over the entire range of ˜60 wt%, thereby obtaining the flexibility, processability, durability, and chemical resistance of the vinyl chloride sheet.

In addition, the above experimental example shows that by controlling the weight ratio of the cyclic olefin copolymer resin, the physical properties of the vinyl chloride sheet can be obtained and the cost can be controlled.

According to another embodiment of the present invention, the polyolefin sheet of the present invention, PP (Polypropylene), PBT (Polybutylene Terephthalate), m-PPE (Modified Polyphenylene Ether), PES (Polyethersulfone), PAR (Polyarylate) PSF (Polysulfone), The strength or elongation can be adjusted by adding 1 to 50 parts by weight by selecting one or more from a group consisting of harmless resins such as UHMW-PE (Ultra-High-Molecular-Weight Polyethylen).

Applicant has described the embodiments of the present invention above, it is obvious that various changes and modifications that implement the technical idea of the present invention also fall within the scope of the present invention.

Since the polyolefin sheet of the present invention does not use plasticizers or stabilizers as the vinyl chloride resin or additives, it does not discharge dioxins or harmful substances to humans, and therefore, it is harmless to the human body and can realize the physical properties of vinyl chloride sheet. Processability, flexibility, chemical resistance, durability, and scratch resistance can be secured. Furthermore, it has excellent printability and adhesion to other papers, so it can be applied to various applications such as marking sheet, interior sheet, signboard, interior decoration sheet, etc. It can have an effect that can replace the existing vinyl chloride sheet.

In addition, the polyolefin sheet of the present invention, unlike the T-DIE method or the rolling or compression method such as the BLOW method, the T-DIE method that can easily heat up, unlike the vinyl chloride sheet does not come out of the convenience or quality stability of the work or Since it can be manufactured by the rolling or compression method like the blow method, it has the effect of improving the productivity and lowering the manufacturing cost.

Claims (5)

A harmless polyolefin sheet formed by mixing 1 to 60 wt% of a cyclic olefin copolymer resin in a polyethylene resin, wherein the polyolefin sheet has a stretch ratio of 100 to 1000%, a tensile strength of 4,000 to 8,000 g / in, and a 100 to 400 g / in A harmless polyolefin sheet having a tear strength and a surface tension of 30 to 44 dyne / cm 2. delete delete The harmless polyolefin sheet according to claim 1, wherein the polyethylene resin is a mixture of LDPE and HDPE. According to claim 1, PP, PBT, m-PPE, PES (Polyethersulfone), PAR, PSF and a harmless polyolefin sheet prepared by mixing 1 to 50wt% of at least one resin selected from the group consisting of UHMW-PE.