KR19990038399A - Plastic composition containing polyvinylbenzyloxycinnamate - Google Patents

Abstract

The present invention relates to a plastic composition containing polyvinyl benzyl oxy cinnamate represented by the following general formula (1), wherein the polyvinyl benzyloxycinnamate, which acts as a light stabilizer, is 0.01 to 5 per gross weight of the plastic composition. It provides a plastic composition which is excellent in light stability by containing no more than% by weight.

Formula 1

(Wherein n is an integer of 2 or more, and R represents an alkyl group containing 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or oxygen).

Description

Plastic composition containing poly vinyl benzyl oxy cinnamate

The present invention relates to a plastic composition containing poly vinyl benzyl oxy cinnamate (hereinafter referred to as PVBOC), in particular containing a certain amount of PVBOC acting as a light stabilizer is not harmful to the human body and excellent in light stability It relates to a plastic composition.

Among the high molecular materials, plastics such as synthetic resins are used not only in daily life but also in the machinery industry and aerospace, and the plastics with new characteristics are not only expanded by adding various additives. Is being developed. Generally, plastics use antioxidants, light stabilizers, thermal stabilizers, plasticizers, pigments, fillers, foaming agents, etc. as additives. Among these additives, polymer degradation occurs in which the polymer material loses its original properties little by little by heat or light. In order to prevent this phenomenon, in particular, oxidation by light, light stabilizers are generally used in plastics. In addition, plastics, which are closely related to daily life, in particular, plastics used for infant toys, food wrapping paper, and medical devices have a lot of direct contact with the human body. Therefore, the material used as an additive of plastics, and among these, the light stabilizer is distributed near the surface of the plastic and is moved from the plastic to the human body in contact with the human body. However, since most of the light stabilizers currently used are low molecular weight substances having a molecular weight of 500 or less, they are absorbed into the human body when they come into contact with the human body, and thus the absorbed light stabilizers have a harmful effect on the human body.

Accordingly, the present invention has been made to solve the above problems, in place of the light stabilizers previously used in plastics, polyvinylbenzyloxycinnamate, that is, PVBOC as a light stabilizer for the plastic composition, safety and light stability to the human body It is an object to provide a plastic composition having excellent effects.

In order to achieve the above object, the plastic composition according to the present invention is characterized in that it contains 0.01 to 5% by weight of PVBOC, based on the total amount of the plastic composition.

In addition, the polyvinylbenzyloxycinnamate according to the present invention for achieving the above object is characterized in that the average molecular weight of 1000 to 1000000.

Hereinafter, the present invention will be described in detail.

Plastic composition according to the present invention, represented by the following formula (1) and contains PVBOC acting as a light stabilizer.

Wherein n is an integer of 2 or more, and R represents an alkyl group containing 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or oxygen. Oxygen here consists of ether bonds.

On the other hand, the PVBOC of the formula (1), that is, a method for producing polyvinylbenzyloxycinnamate is disclosed in detail in the patent application No. 95-44248, the applicant of the present invention.

PVBOC of Formula 1, which acts as a light stabilizer in plastics, is added at 0.01 to 5% by weight, based on the total amount of plastic composition. Preferably from 0.03 to 1.5% by weight, more preferably from 0.1 to 0.6% by weight.

In addition, PVBOC according to the present invention uses an average molecular weight of 1000 to 1000000.

In addition, examples of the plastic used in the present invention are as follows.

1. Mono or diolefin polymers such as polyethylene, polypropylene, polyisobutylene, polybut-1-ene, polymethylpent-1-ene, polyisoprene, polybutadiene and the like; And cycloolefin polymers such as polycyclopentene, polynorbornene and the like

2. Mixtures of the polymers described in 1 above, such as mixtures of polypropylene and polyethylene or polyisobutylene

3. Ethylene / propylene copolymer, propylene / but-1-ene copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene Copolymers of each or each of the above mono or diolefins such as / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylic acid copolymers, and the like.

4. Polystyrene

5. copolymers of styrene or α-styrene including dienes or acrylic derivatives such as styrene / butadiene, styrene / acrylonitrile, styrene / alkylmethacrylate, styrene / acrylonitrile / methylacrylate, and the like; And block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene-butylene / styrene, styrene-ethylene / propylene-styrene, and the like.

6. Polybutadiene to styrene, Polybutadiene to styrene and acrylonitrile, Polybutadiene to styrene and maleic anhydride, Polybutadiene to styrene and alkyl acrylate, Polybutadiene to styrene and alkyl methacrylate, Ethylene to styrene and acrylonitrile Graft copolymers of styrene obtained by grafting an acrylate-butadiene copolymer to propylene and an acrylonitrile and a polyalkyl acrylate to styrene and acrylonitrile; And mixtures with the copolymers described in 5 above, known as ABS, MBS, ASA, AES, etc.

7. Polymers containing halogen, such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene

8. Polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles

9. The monomers described in 8 above, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkylacrylate copolymers, acrylonitrile / vinyl chloride copolymers, acrylonitrile / alkylmethacrylate / butadiene copolymers Copolymers of Each or Each Other

10. Unsaturated alcohols or amines such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinylbenzoate, polyvinyl maleate, polyvinylbutyral, polyallylphthalate, polyallyl melamine or acyl or acetal derivatives thereof Polymer derived from

11. Homopolymers and copolymers of cyclic ethers such as polyethylene glycol, polyethylene oxide, polypropylene oxide or copolymers of these with bis-glycidyl ethers

12. Polyacetals such as polyoxyethylene containing comonomers such as polyoxymethylene and ethylene oxide

13. Polyphenylene Oxides and Sulphides

14. Polyurethane

15. Polyamide 4, Polyamide 6, Polyamide 66, Polyamide 610, Polyamide 11, Polyamide 12, Poly-2, 4, 4-trimethylhexamethylene terephthalamide, Poly-m-phenyleneisophthalamide Polyamides and copolymeramides derived from diamines, dicarboxylic acids, aminocarboxylic acids and the corresponding lactams, such as

16. Polyureas, polyimides, polyamide-imides

17. Polyesters of dicarboxylic acids, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexaneterephthalate, dialcohols, hydroxycarboxylic acids derived from the corresponding lactones

18. Polycarbonate

19. Polysulfones and polyether sulfones

20. Cross-linked polymers derived from aldehydes such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, and phenols, ureas, melamines, etc.

In addition, the following additives may be used in the plastic composition according to the present invention in addition to PVBOC as necessary.

1. Antioxidants

1.1 alkylated monophenols: for example 2, 6-di-tert butyl-4-methylphenol, 2-3-butyl butyl-4, 6-dimethylphenol, 2, 6-di-tert butyl-n-butylphenol , 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-di-cyclopentyl-4-methylphenol, 2, 6-di-octadecyl-4-methylphenol or 2, 4, 6 Tricyclohexylphenol.

1.2 alkylated hydroquinones: 2, 6-di-tert. Butyl-4-methoxyphenol, 2, 5-di-tert. Butyl-hydroquinone or 2, 5-di-tert. Amylhydroquinone.

1.3 hydroxyated thiophenyl ether: 2, 2'-thio-bis- (6-tert-butyl-4-methylphenol), 2, 2'-thio-bis- (4-octylphenol), 4, 4 ' -Thio-bis- (6-tert-butyl-3-methylphenol) or 4, 4'-thio-bis- (6-tert-butyl-2-methylphenol).

1.4 alkylidene-bisphenol: 2, 2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2, 2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2, 2'-methylene-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol], 2, 2'-methylene-bis- (4-methyl-6-cyclohexylphenol), 2, 2'-methylene-bis- (6-nonyl-4-methylphenol), 2, 2'-methylene-bis- (4, 6-di-tert-butylphenol), 2, 2'-ethylidene-bis- (4, 6-di-tert-butylphenol), 2, 2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol), 4, 4'-methylene-bis- (2, 6 -Di-tert-butylphenol), 4,4'-methylene-bis- (6-tert-butyl-2-methylphenol), 1,1'-bis- (5-tert-butyl-4-hydroxy- 2-methylphenylbutane), 2, 6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5-tert-butyl 4-hydroxy-2-methylphenyl) -butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenol) -3-n-dodecylmercaptobutane, ethylene glycol bis -[3.3-bis- (3′-tert butyl-4′-hydroxyfe Yl) -butyrate], di- (tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene or di- [2- (3-tert-butyl-2'-hydroxy-5 ′ -Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate

1.5 benzyl compound: 1,3,5-tris- (3,4-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, di- (3,5-di-3 Tertiary butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert butyl-4-hydroxybenzyl-mercaptoacetate, bis- (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithiol terephthalate, 1,3,5-tris- (3,5-di-tertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4 -Tertiary butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tertiary butyl-4-hydroxyphenyl-phosphonate or monoethyl 3,5 Calcium Salts of Di-butyl-4-hydroxybenzyl-phosphonate

1.6 Acylaminophenols: 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide or 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydride Roxianiline) -S-triazine

1.7 esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols

2. UV absorbers and light stabilizers

2.1 Derivatives of benzotriazoles: for example 2- (2′-hydroxyphenyl) -benzotriazole, 5′-methylbenzotriazole, 5′-tertiary butylbenzotriazole, 5-chloro-3 ′, 5'-di-tert butylbenzotriazole

2.2 Benzophenone derivatives: for example 2-hydroxybenzophenone, 4-hydroxybenzophenone, 4-methoxybenzophenone, 4-octoxybenzophenone

2.3 Esters of Substituted or Unsubstituted Benzoic Acids: for example 4-tert-Butyl-phenylsalicylate, Phenylsalicylate, Octylphenyl Salicylate, Dibenzoylezolcinol, Bis- (4-tert-Butylbenzoyl ) -Resorcinol, Benzoylesolecinol

2.4 acrylates: for example α-cyano-β, β-diphenylacrylate, methyl-α-carbomethoxy-cinnamate, methyl-α-cyano-β-methyl-p-methoxy cinnamate, Butyl-α-cyano-β-methyl-p-methoxy cinnamate

2.5 Nickel compounds: for example nickel complexes of 2,2′-thio-bis [4- (1,1,3,3-tetramethylbutyl) -phenol)]

2.6 Steric hindrance amines: for example bis- (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) seva Kate, bis- (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert butyl-4-hydroxybenzylmalonate

2.7 oxalic acid diamides: for example 4,4'-dioctyloxy-oxananilide, 2,2'-dioctyloxy-5,5'-di-tert-butyl oxananilide, 2,2'-didodecyl Ci-5,5′-di-tert-butyl oxananilide, 2-ethoxy-2′-ethyloxananilide, N, N′-bis- (3-dimethylaminopropyl) oxalamide, 2-ethoxy- 5-tert-butyl-2'-ethyloxananilide

3. Metal deactivators: for example N, N'-diphenyloxalamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis-salicyloylhydrazine, N, N'-bis -(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicylylamino-1,2,4-triazole, bisbenzylidene oxalic acid dihydrazide

4. Phosphites and phosphonites: for example triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, tris -(2,4-di-tert-butyl phenyl) phosphite, diisodecylpentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis- (2,4-di-tert-butyl phenyl)- 4,4′-biphenylene diphosphonite

5. Compounds that decompose peroxides: esters of β-thiodipropionic acid such as lauryl, stearyl, myristyl, tridecyl ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole , Zinc dibutyldithiocarbamate, dioctadecyl disulfite, pentaerythritol, tetrakis- (β-dodecyl mercapto) propionate

6. Stabilizers for polyamides, for example iodine or phosphorus compounds and divalent manganese salts mixed with copper salts

7. Basic Stabilizer

8. Crystal generators: for example 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid

9. Fillers and reinforcing agents: eg calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulphate, metal oxides, metal hydroxides, carbon black, graphite.

In addition to the above additives, plasticizers, lubricants, emulsifiers, pigments, antistatic agents, foaming agents, flame retardants, fluorescent brighteners and the like can be added.

Hereinafter, the present invention will be described through Examples and Comparative Examples, but is not limited thereto.

Example 1

After the LDPE composition containing PVBOC represented by the formula (2) having the substituent of R in the formula (1) having 2-ethylhexyl and an average molecular weight of 5000 was made into a film having a thickness of 200 μm, the film was subjected to light conditions of 45 ° South Florida. It was left to. After standing, the light stability of the composition was measured by measuring the time (kLy) at which the degree of elongation of the film became 50% of the initial state.

Comparative Example 1

Comparative Example 1 was used in place of PVBOC, except for using LDPE composition of 2- (2-hydroxy-3,5-di-tertiary-amylphenyl) -2H-benzotriazole represented by the following formula (3): Photostability was measured in the same manner as in Example 1.

The plastic compositions according to Example 1 and Comparative Example 1 are shown in Table 1, and the results of the light stability measurements are shown in Table 2.

ingredient weight % Control group 1 Example 1 Comparative Example 2 LDPE Resin 99.35 99.05 99.05 2,6-di-tert-butyl-4-methylphenol 0.05 0.05 0.05 PVBOC 0.3 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole 0.3 CaCO ₃ 0.3 0.3 0.3 Erucamide (C ₂₁ CONH ₂ ) 0.1 0.1 0.1 Bis- (1, 2, 2, 6, 6-pentamethylpiperidyl) sebacate 0.2 0.2 0.2

Control group 1 Example 1 Comparative Example 1 Optical stability (kLy) 25 245 150

As can be seen in Table 2, the LDPE compositions of Example 1 and Comparative Example 1 were 6 times better in Comparative Example 1, 9.8 times better in Example 1 than in Comparative Example 1 containing no light stabilizer. In addition, Example 1 containing a photo stabilizer of PVBOC according to the present invention, which contains 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole which is a conventional light stabilizer Photostability was 1.6 times better than Comparative Example 1.

Example 2

The degree of absorption of PVBOC having an average molecular weight of 5000 represented by Formula 2 into the transdermal was tested by the following method.

Percutaneous absorption testing was performed using a Franz type diffusion cell, an autosampler, and a cell drive system with adjustable rpm, with an effective diffusion area of 1.77 cm2 and a receiver volume of 7.0 ml. It was. First, the dorsal skin of the female hairless mice of 8 to 9 weeks was peeled off so that the dermis side of the skin faced the receptor and the epidermis faced the donor compartment.

The PVBOC of Formula 2 was dissolved in 33% by weight of caprylic acid / capric acid triglyceride and 180 mg was applied to the dorsal skin of hairless mice mounted in a French type diffusion cell. The receptor compartment was filled with a solution made up to 2% by adding Volpo 20 (polyoxyethylene oleic ether) to a pH 7.4 solution buffered with 50 mM phosphate solution. The solution of the receptor was stirred continuously with a magnetic stirrer during the experiment. The solution in the receptor was also changed to a fresh solution every six hours. After the experiment was finished (24 hours after the start of the experiment), the solution of the receptor was collected and the skin of the hairless mouse which was used as a membrane was recovered, and the surface thereof was washed twice with 1 ml of acetone. The washed skin was ground finely and the PVBOC penetrated into the skin was extracted with CH ₂ Cl ₂ . In addition, PVBOC penetrated into the receptor solution through the skin was extracted with CH ₂ Cl ₂ . A precipitate of CH ₂ Cl ₂ solution was filtered and PVBOC was quantified by HPLC.

Comparative Example 2

The same method as in Example 2 was used except that 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole having a molecular weight of 351 represented by Chemical Formula 3 was used instead of PVBOC. Percutaneous absorption of 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole was tested accordingly.

HPLC quantification by HPLC in the tests of Example 2 and Comparative Example 2 resulted in penetration into the skin and through the skin PVBOC and 2- (2-hydroxy-3,5-di-tert-amylphenyl) found in the receptor solution The weight percent of -2H-benzotriazole is shown in Table 3.

In skin (% by weight) Skin pain (% by weight) PVBOC 0. 12 0 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole 0. 53 0. 002

As can be seen in Table 3, PVBOC is absorbed to the skin compared to conventional light stabilizer 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole It can be seen that is significantly small.

As described above, the polyvinylbenzyloxycinnamate according to the present invention, that is, the plastic composition containing PVBOC is harmless to the human body and is excellent in light stability.

Claims (3)

A plastic composition comprising polyvinylbenzyloxycinnamate (PVBOC) represented by the following Chemical Formula 1 by 0.01 to 5% by weight, based on the total weight of the plastic composition. Formula 1 (Wherein n is an integer of 2 or more, and R represents an alkyl group containing 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or oxygen). The plastic composition of claim 1, wherein the polyvinylbenzyloxycinnamate (PVBOC) has an average molecular weight of 1000 to 1000000. The said plastic composition is a monoolefin polymer, a diolefin polymer, a cycloolefin polymer, a monoolefin copolymer, a diolefin copolymer, a monoolefin / diolefin copolymer, a polystyrene, and a styrene copolymer. , α-styrene copolymers, styrene block copolymers, styrene graft copolymers, polymers containing halogen elements, polymers of α, β-unsaturated acids, copolymers of α, β-unsaturated acids, unsaturated alcohols or amines or these Polymers derived from acyl or acetal derivatives of cyclic ether homopolymers, cyclic ether copolymers, polyacetals, polyurethanes, copolymer amides of diamines and polyamides, copolymer amides of dicarboxylic acids and polyamides, aminocarboxylic acids and polyamides Of copolymerized amide, polyester, polycarbonate, polysulfone, polyether sulfone, aldehyde and A plastic composition, comprising at least one plastic selected from the group consisting of phenolic polymers, aldehyde and urea polymers, aldehyde and melamine polymers.