KR100359986B1 - A Resin Composition of Shirinking Film and Sheet for Shutting out UV - Google Patents

Abstract

The present invention relates to a synthetic resin shrink film and sheet composition for outdoor exposure, and more particularly, to a sunscreen shrink film and sheet composition,

0.05 to 0.8% by weight of a benzotriazole-based ultraviolet absorber and 0.01 to 1.0% by weight of a hindered phenol-based UV stabilizer in a resin such as polyethylene, polyalkylene glycol or a derivative thereof as an antistatic agent as an optional component It is prepared by melt-mixing 0.01 to 2.0% by weight and then extruding,

UV-protective resin composition used in food containers or shrink film manufacturing can prevent the deterioration of foods or packaging materials caused by sunlight even when exposed to the outdoors, and can maintain the freshness of foods and extend the shelf life. In addition, the injection molded article requiring ultraviolet sterilization has an advantage of preventing deformation, discoloration, and aging of the resin composition when irradiated with ultraviolet rays. In summary, UV blocking, weather resistance, and permeability to absorb and block harmful ultraviolet rays are prevented. great.

Description

A Resin Composition of Shirinking Film and Sheet for Shutting out UV}

The present invention relates to a resin composition used for the production of food containers for outdoor exposure, packaging films and sheets, and more particularly, 0.05 to 0.8% by weight of a benzotriazole-based ultraviolet absorber and resin in a resin such as polyethylene. Synthetic resin shrink film for outdoor exposure prepared by melt-mixing 0.01 to 1.0% by weight of a phenol-based UV stabilizer and 0.01 to 2.0% by weight of polyalkylene glycol or its derivatives as an antistatic agent as an optional component, followed by extrusion processing And sheets.

In general, all organic matter, including the human body and other living things, are aging and deteriorated by ultraviolet light (UV), and have adverse effects such as carcinogenesis due to the production of thymine dimer, which is harmful to the sun's rays reaching the earth's surface. This is very big. Ultraviolet rays in the sunlight have shorter wavelengths than visible or infrared rays, and are classified into the wavelength ranges of the A region ultraviolet rays (UVA 320 to 400 nm), the B region ultraviolet rays (UVB 280 to 320 nm), and the C region ultraviolet rays (UVC 200 to 280 nm). UV C region is the most energy among ultraviolet rays, but most of them are removed by ozone layer and do not reach the earth's surface. Ultraviolet B region is an area that can cause blistering and burns due to sunlight. Promote skin aging, deterioration and carcinogens act as one cause.

Ultraviolet rays activate various chemicals, altering their structure and altering their properties, degrading their original properties and functions. Especially, organic pigments used in many resin compounds lose their original properties and functions by being activated by ultraviolet rays. . Therefore, by adding a sunscreen and a UV absorber to various resin compositions or by performing a surface treatment, the organic material can be protected by absorbing ultraviolet rays of 400 nm or less that are harmful to organic matter and converting them into harmless thermal energy. Therefore, it does not deteriorate.

The sunscreens generally used so far include organic ultraviolet absorbers such as salicylate, benzotriazole and cyanoacrylate, and inorganic pigments such as titanium oxide, zinc oxide and iron oxide. In addition, UV stabilizers include hindered amines, hindered phenols, and aromatic phosphites.

Accordingly, in order to prepare a resin composition stable to ultraviolet rays, a benzotriazole-based sunscreen agent and a hindered phenol having a substituent on a container, resins, films and sheets, packaging resin compositions, etc. Manufacturing by adding UV-based stabilizer can effectively prevent the aging, destruction and deformation of organic compounds by ultraviolet rays, and can extend the shelf life.

In the past, ultraviolet blocking polyethylene having a weather resistance of 400 nm or less and having weather resistance is known, but they are not only able to block ultraviolet rays sufficiently, but also have a problem in that the blocking ability of ultraviolet rays is also deteriorated with time. This is because the sunscreen and the ultraviolet absorber used were inferior in performance, dispersibility, and compatibility, and the intrinsic color of the resin composition changed over time by adding an excessive amount of the blocking agent and the absorbent to maximize the sunscreen performance. There was a problem of the transition of the additives within.

The present invention is to solve the above-mentioned conventional problems, the object of the present invention is that the physical properties of the resin does not change due to photochemical deformation, discoloration, aging, etc. of the resin composition even when irradiated with ultraviolet rays, excessive exposure to ultraviolet rays It is to provide a resin composition of the polyethylene shrink film and sheet for UV protection to maximize the UV protection effect and the shielding effect of ultraviolet rays to general food or organic matter.

1 is a graph showing ultraviolet absorbing ability of 2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5-chloro benzotriazole as an ultraviolet absorber.

The sunscreen shrink film and sheet resin composition according to the present invention,

0.05 to 0.8 wt% of a benzotriazole-based ultraviolet absorber as a primary antioxidant represented by the following formula (1);

(Wherein X is hydrogen or a halogen compound, and R ₁ and R ₂ are straight or branched chain alkyl groups having 1 to 8 carbon atoms)

0.01 to 1.00% by weight of a hindered phenol ultraviolet stabilizer as a secondary antioxidant represented by the following formula (2);

(Wherein R ₃ and R ₄ are straight or branched chain alkyl groups having 1 to 8 carbon atoms, and R ₅ is an ester having a straight or branched chain alkyl groups having 10 to 30 carbon atoms)

The balance is low density polyethylene (LDPE) resin, high density polyethylene (HDPE) resin, polypropylene (PP) resin, ethylene-propylene copolymer resin, ethylene-1-butene copolymer resin, ethylene vinyl acetate resin (EVA) and polyvinyl chloride (PVC) And at least one resin selected from the group consisting of resins:

As an optional component, 0.01 to 2.0% by weight of an antistatic agent polyalkylene glycol or a derivative thereof may be included.

The UV blocking shrink film and the sheet resin composition according to the present invention are manufactured by melt-mixing the above composition components and then extruding.

There are no particular restrictions on the type of resin usable in the present invention, but low density polyethylene (LDPE) resin, high density polyethylene (HDPE) resin, polypropylene (PP) resin, ethylene-propylene copolymer resin, ethylene-1-butene copolymer resin, ethylene Any one or combination of vinyl acetate resin (EVA) or polyvinyl chloride (PVC) resin can be used, preferably polyethylene resin, more preferably low density polyethylene resin.

The benzotriazole system as a sunscreen and absorber shows excellent ultraviolet absorption effect in the ultraviolet range of 280-390 nm, and the benzoate-based ultraviolet absorber shows excellent ultraviolet absorption effect in the ultraviolet range of 250-300 nm. .

Therefore, the ultraviolet A region, which is harmful to the human body and adversely affects the organic compound and modifies the components of the compound, can sufficiently exhibit the harmful ultraviolet blocking effect and the absorption effect only by the use of a benzotriazole system. An organic sunscreen agent capable of blocking the UV region of ˜390 nm is used.

The benzotriazole-based compound of the organic blocker that can be used in the present invention is not particularly limited as long as it is stable and does not change its structure during compression kneading at 200 ° C. or higher. Examples thereof include 2- (3 ′, 5-di-). t-butyl-2'-hydroxyphenyl) -5-chloro benzotriazole, 2- (3 ', 5-di-isobutyl-2'-hydroxyphenyl) -5-chloro benzotriazole, 2- ( 2'-hydroxy-3'-isopropyl-5'-octylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl -5'-octylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-isooctylphenyl) -5-chlorobenzotriazole, 2- (2 Single or any combination thereof, such as' -hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole The.

In the present invention, in addition to the sunscreen as described above, 0.01 to 1.0% by weight of a hindered phenol-based UV stabilizer is added, wherein the hindered phenol-based UV stabilizer serves to enhance weather resistance. As a hindered phenol-based UV stabilizer that serves as a secondary antioxidant, octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate , Hexamethylene-bis-3- (3'.5'-di-t-butyl-4'-hydroxycinamide), or 2-2'-methylenebis- (4-methyl-6-t-butylphenone) Or any combination thereof, and the like, but the present invention is not limited thereto.

In the present invention, in addition to the above-described ultraviolet absorber and ultraviolet stabilizer, an antistatic agent may be added as an optional component in order to remove the chargeability, preferably 0.01 to 2.00% by weight of polyalkylene glycol or derivatives thereof. You may.

Polyalkylene and its derivatives include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoglycidyl ether and the like.

Polyethylene resin that can be preferably used in the present invention, the density is 0.910 ~ 0.935g / ㎠, preferably 0.910 ~ 0.925g / ㎠, the melt index is used 1 to 20g / 10 minutes, An ultraviolet absorber and an ultraviolet stabilizer as described above, and optionally an antistatic agent, are melt-extruded to prepare an expanded film.

The film according to the present invention is subjected to an extrusion extrusion process under the conditions of the extrusion molding temperature of the extruder is 150 ~ 195 ℃, preferably about 160 ℃ to 190 ℃, most preferably 165 ℃, the expansion ratio in the die It is 1.5-3.0, and the favorable range of drawability which is a measure of how much the film was stretched at the time of extrusion, and a measure of how fast the winding speed can be carried out is 3-7. In addition, the freezing line, which is the point at which solidification starts when the melted resin is solidified into a bubble film, is related to the cooling rate and the cooling temperature. The height of the freezing line is 40 to 60 cm to produce a film having a thickness of 70 to 120 μm. . In the ultraviolet ray screening test of the present invention, a wavelength range of 280 to 400 nm is measured by using an ultraviolet-visible spectrometer (UV / VIS SPECTROMETER), which is a DU 650 model of Beckman, USA, to measure the average transmittance of each wavelength. Calculate the blocking rate by substituting the following equation:

Blocking Rate = 100-Transmittance

In the ultraviolet exposure test of the present invention, the AT65 Ci65 / XWA tester model was used to measure the tensile strength after irradiating ultraviolet light for 720 hours (30 days) using a xenon lamp, and the tensile strength test was performed by INSTRON. The 4204 model was used under the conditions of ASTM D-882.

Hereinafter, the present invention will be described in more detail with reference to examples, which should be understood to illustrate the present invention but not to limit the scope of the present invention.

(Example)

Example 1

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5-chloro, a sunscreen, for 100% by weight of a low density polyethylene resin having a melt index of 3 g / 10 min and a density of 0.923 g / cm 3 0.05 wt% of benzotriazole and 0.5 wt% of octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate, an ultraviolet stabilizer, were added and the average molecular weight 1.0 wt% of the polyethylene glycol of 25,000 or more was added and expanded-extruded at 190 ° C. to form a 100 μm thick film. The test results are shown in Table 1 below.

Example 2

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.2 wt% chlorobenzotriazole and 0.5 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as UV stabilizers were added and averaged as antistatic agent. 1.0 wt% of polyethyleneglycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 1 below.

Comparative Example 1

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.4 wt% chlorobenzotriazole and 0.5 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as UV stabilizers were added and averaged as antistatic agent 1.0 wt% of polyethyleneglycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 1 below.

Example 3

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.6 wt% chlorobenzotriazole and 0.5 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as UV stabilizers were added and averaged as antistatic agent 1.0 wt% of polyethyleneglycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 1 below.

Example 4

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.8 wt% chlorobenzotriazole and 0.5 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as UV stabilizers were added and averaged as an antistatic agent 1.0 wt% of polyethyleneglycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 1 below.

Example 5

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.4% by weight of chloro benzotriazole and 0.01% by weight of ultraviolet stabilizer octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate were added and averaged as an antistatic agent. 1.0 wt% of polyethylene glycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 2 below.

Example 6

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.4 wt% chlorobenzotriazole and 0.2 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as UV stabilizers were added and averaged as antistatic agent 1.0 wt% of polyethylene glycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 2 below.

Example 7

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.4 wt% chlorobenzotriazole and 0.8 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate, an ultraviolet stabilizer, were added and averaged as an antistatic agent. 1.0 wt% of polyethylene glycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 2 below.

Example 8

2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5- as a sunscreen against 100% by weight of a low density polyethylene resin having a melt index of 3.0 g / 10 min and a density of 0.923 g / cm 3 0.4 wt% chlorobenzotriazole and 1.1 wt% octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate, an ultraviolet stabilizer, were added and averaged as an antistatic agent. 1.0 wt% of polyethylene glycol having a molecular weight of 25,000 or more was added and expanded extrusion was carried out at a temperature of 190 ° C. to form a 100 μm thick film. The test results are shown in Table 2 below.

As described above, the use of the film made of the UV-protective resin composition of the present invention not only improves the durability and light transmittance of the film when used as a film for a vinyl house, but also is harmful when used for food packaging such as food and beverages. Ultraviolet rays can be effectively blocked to maintain the freshness of food and the like and to extend the shelf life. In addition, in the case of injection molded articles requiring ultraviolet sterilization such as disposable syringes, useful effects such as preventing deformation, discoloration and aging of the resin by ultraviolet irradiation can be obtained.

Claims (7)

Shrinkage film and sheet resin composition for UV protection consisting of (correction): 0.05 to 0.8% by weight of 2- (3 ', 5-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole as a primary antioxidant represented by the following formula (1); (Formula 1) 0.01 to 1.00% by weight of octadecyl-3- (3'.5'-di-t-butyl-4'-hydroxyphenyl) -propionate as a secondary antioxidant represented by the following formula (2); And (Formula 2) The balance is low density polyethylene (LDPE) resin, high density polyethylene (HDPE) resin, polypropylene (PP) resin, ethylene-propylene copolymer resin, ethylene-1-butene copolymer resin, ethylene vinyl acetate resin (EVA) and polyvinyl chloride (PVC) ) At least one resin selected from the group consisting of resins. The shrink-proofing film and sheet resin composition for UV blocking as claimed in claim 1, further comprising 0.01 to 2.0% by weight of polyalkylene glycol or a derivative thereof as an antistatic agent. (delete) (delete) (delete) (delete) The shrink film and sheet resin for blocking ultraviolet rays according to claim 1, wherein the resin is low density polyethylene, has a density of 0.910 to 0.935 g / cm 2, and a melt index of 1 to 20 g / 10 minutes.