KR100187313B1 - Highly antioxidant olefinic resin composition - Google Patents

Abstract

A resin composition having high antioxidant and improved heat stability and weather resistance, comprising a resin, a solution of a hypophosphite compound in an organic solvent, a heat stabilizer and a weathering stabilizer based on a blocking amine.

Description

High Antioxidant Resin Composition

The present invention relates to a resin composition having high antioxidant properties. More specifically, the present invention relates to a highly antioxidant resin composition containing a resin, a heat stabilizer and a weathering stabilizer based on blocking amines, which are excellent in thermal stability and weather resistance.

The amount of resin used in exterior materials is increasing year by year. Such exterior resins require weather resistance depending on the application. Various weathering stabilizers have been developed for this purpose. Recently, mainly used are blocking amine based stabilizers called so-called blocking amine light stabilizers (HALS), and when they are used outdoors, the reduction of mechanical properties or color tone change of the resin composition is better than the conventional weathering stabilizers. The reason for this is that it is possible to prevent the occurrence of the defect (see Japanese Patent Laid-Open No. 86645/1984).

Since weathering stabilizers cannot impart process stability or thermal stability to the resin, generally the resin composition includes a heat stabilizer (e.g., a blocking phenol based heat stabilizer, a sulfur based heat stabilizer and a phosphite ester based heat stabilizer). Add.

However, under certain conditions, a resin composition containing both a heat stabilizer and a blocking amine based weathering stabilizer may be degraded due to lack of thermal stability such as gelation or seizure during processing or decolorization after processing. . In addition, when exposed to the outside atmosphere, the quality of the resin composition may be degraded due to lack of weather resistance, such as a decrease in mechanical properties or a change in gloss or color tone. Therefore, conventional resin compositions are not satisfactory in both thermal stability and weather resistance. Although the thermal stability and weather resistance to some extent can be improved by adding higher amounts of heat stabilizer and blocking amine based weathering stabilizer to the resin, the resin composition may be yellowed, or the heat stabilizer and / or blocking amine based weathering stabilizer. It may bleed on the surface and damage the appearance of the molded part.

In particular, when the blocking phenol based heat stabilizer and the blocking amine based weathering stabilizer are used in combination, the blocking phenol based heat stabilizer causes yellowing of the resin, and the blocking amine based weathering stabilizer is a heat resistant blocking phenol based heat stabilizer. It is known to interfere with the antioxidant activity of a topic.

An object of the present invention is to improve the thermal stability and weather resistance of a highly antioxidant resin composition containing a resin, a heat stabilizer and a blocking amine based weathering stabilizer.

According to the present invention, there is provided a highly antioxidant resin composition containing a resin, a solution of a hypophosphite compound in an organic solvent, a heat stabilizer, and a weathering stabilizer based on a blocking amine.

As the heat stabilizer used in the present invention, a blocking phenol compound such as a 2, 6-dialkylphenol derivative and a 2-alkylphenol derivative, a sulfur-containing compound having a thiol or thioether bond containing a divalent sulfur atom, or The compound which has a phosphite ester bond containing a trivalent phosphorus atom can be illustrated.

Examples of the blocking phenol-based heat stabilizer include the following compounds (1) to (8).

Examples of the sulfur-containing heat stabilizer include the compounds of the following (9) to (16).

(Wherein R is an alkyl group having 12, 13 or 14 carbon atoms)

Examples of the phosphite ester based heat stabilizer include the compounds of the following (17) to (33).

(Wherein R is an alkyl group having 12 to 15 carbon atoms)

The above heat stabilizers can be used independently or as a mixture.

The blocking amine based weathering stabilizer is preferably a 2, 2, 6, 6-tetraalkylpiperadine derivative having a substituent at the 4-position and a molecular weight of 250 or more. As a substituent of 4-position, a carboxylic acid residue, an alkoxy group alkylamino group, etc. can be illustrated. The N-position may be substituted with an alkyl group, for example. Specific examples of the blocking amine based weathering stabilizer include the following compounds (34) to (41).

The hypophosphite compound used for this invention is represented by the following general formula (A).

Xa (H ₂ PO ₂ ) b (A)

[Wherein X is a metal ion, ammonium ion or quaternary phosphonium ion, a and b are positive, provided that axc = b is satisfied (c is the valence of X)]

Specific examples of compound (A) include lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, magnesium hypophosphite, calcium hypophosphite, hypophosphite zinc, hypophosphite titanium, vanadium hypophosphite, molybdenum hypophosphite, manganese hypophosphite, Hypophosphite cobalt, ammonium hypophosphite, ammonium hypophosphite, diethylammonium hypophosphite, triethylammonium hypophosphite, tetraethylammonium hypophosphite, tetrabutyl phosphonium hypophosphite, tetraphenylphosphonium hypophosphite, etc. are mentioned.

As the organic solvent in which the hypophosphite compound is dissolved, a hypophosphite can be dissolved and a solvent having a boiling point higher than the processing temperature of the resin is preferably used. Examples of organic solvents are protic polar solvents, such as polyhydric alcohols and polyamines, preferably having a molecular weight of 50,000 or less, and aprotic polar solvents such as alkylsulfones. Specific examples of protic solvents include ethylene glycol, diethylene glycol, polyethylene glycol (molecular weight: 150-50,000), polypropylene glycol (molecular weight: 134-50,000), glycerin, diglycerin, hexaglycerin, trimethylolpropane, hexamethylenediamine Etc. Specific examples of aprotic solvents include dimethyl sulfoxide and the like.

Examples of resins used in the present invention include olefin homopolymers (e.g. polyethylene, polypropylene, poly-1 -butene, poly-4-methyl-1-pentene, etc.), olefin copolymers (e.g. ethylene-propylene block copolymers). , Ethylene-propylene random copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1- pentene copolymer, ethylene-1-octene copolymer, propylene-1-butene air Copolymers of olefins and polar vinyl compounds (e.g., ethylene-vinyl acetate, ethylene-methyl methacrylate copolymers, etc.) and olefin polymers such as ionomer resins, acrylic resins such as polymethyl methacrylate, and poly Ester resins, polyamide resins, polycarbonate resins, phenol resins, polyvinyl chloride resins, polyurethane resins, and the like.

The quantity of the component contained in the resin composition of this invention is as follows.

The heat stabilizer is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the resin. If it is less than 0.01 part by weight, thermal stability is not effectively improved. If it exceeds 10 parts by weight, the thermal stability is not significantly improved and such a large amount is not economical. In addition, undesirably the heat stabilizer bleeds or discolors.

The blocking amine based weathering stabilizer is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the resin. If it is less than 0.01 weight part, weather resistance will not improve effectively. If it exceeds 10 parts by weight, the weather resistance no longer improves and such a large amount is not economical. Also, undesirably weathering stabilizers bleed or discolor.

The amount of the hypophosphite compound added is generally 0.001 to 100 parts by weight based on 1 part by weight of the blocking amine base weathering stabilizer. If it is less than 0.001 weight part, thermal stability and weather resistance will not improve effectively. If it exceeds 100 parts by weight, the thermal stability and weather resistance are not significantly improved, and such a large amount is not economical, and the amount of the solution added to the resin tends to bleed the hypophosphite compound solution.

The amount of the organic solvent is selected such that 0.01-30 parts by weight of the solution containing the hypophosphite compound is used in an amount less than the saturation amount relative to 100 parts by weight of the resin. If the amount of the solution is less than 0.01 part by weight, the amount of the hypophosphite compound added to the resin is not sufficient, and thermal stability and weather resistance do not satisfactorily improve. If the amount of solution exceeds 30 parts by weight, the solution tends to bleed.

The resin composition of the present invention may contain a UV light absorber, an anti fog agent, an antistatic agent, a lubricant, a filler, a flame retardant, a pigment, and the like in an amount that does not impair the effects of the present invention.

The method of blending the components is not critical and the components are formulated in a general manner such as a half-blow mixer, mixing roll, extruder and the like.

According to the present invention, by adding a hypophosphite compound solution to a resin composition containing a heat stabilizer and a blocking amine based weathering stabilizer, the thermal stability and weather resistance of the resin composition are significantly improved.

The resin composition of the present invention is molded in the form of films, sheets, fibers, and molded articles, or used in various fields such as agricultural films, automobile parts materials and the like. In particular, films made from the resin compositions of the invention containing polyethylene, such as polyethylene or ethylene-1-butene copolymers, or ethylene vinyl acetate copolymers, are useful as packaging films or cover materials for agricultural greenhouses or tunnels. . The resin composition of the present invention is useful as an exterior material that requires high weather resistance, such as an automobile part such as a bumper, and a building material such as a roof of a garage, for example.

The invention will be illustrated by the following examples, which do not limit the scope of the invention.

In the Examples the test method is as follows.

[Thermal stability test]

Using a test sample (1 g) having a thickness of 1 mm, the oxygen absorption induction period is measured by a polymer deterioration measuring apparatus (manufactured by Shibayama Scientific Co., Ltd.) in an amount of 40 ml oxygen in a dark place at a predetermined container internal temperature. The oxygen absorption induction period is represented by the time until the amount of oxygen decreases to 0.9 ml, or the time until the internal oxygen volume shows the minimum volume when decomposition gas is generated after the vessel temperature stabilizes. The longer the oxygen absorption induction period, the better the resistance to oxidative degradation, i.e., the better the thermal stability.

Weathering test

Test samples in the form of JIS No. 3 dumbbell bells were subjected to Eye Super UV Tester (SUV) at 100mw / cm ² light energy, 24cm distance from the light source, 600 ℃ hot air temperature and 33% relative humidity. Aging is performed using W11 (manufactured by Eye Graphics Co., Ltd.). The aging sample was subjected to elongation test using Autograph (trade name) DSS 100 (manufactured by Shimadzu Co., Ltd.) to measure elongation rate (%). Half-life). The half life is large and the weather resistance is excellent.

Various solutions of hypophosphite compounds are listed in Table 1.

TABLE 1

Note: 1) Nakaraitesk Co., Ltd. Manufacture molecular weight 190-210.

2) Nakaraitesk Co., Ltd. Manufacture molecular weight 380-420.

EXAMPLES 1-4

The resins, heat stabilizers, blocking amine based weathering stabilizers and hypophosphite compound solutions shown in Table 2 are combined and kneaded at 150 ° C. for 5 minutes using a half-blow mixer. The mixture is then granulated using an extruder and the wetlet is prepared. The pellets are molded into a sheet of 1 mm thickness by pressure molding or a 50 μm thick film by inflation molding, and subjected to thermal stability test (container internal temperature 210 ° C.) and weather resistance test, respectively.

The results are shown in Table 2. Each resin composition has excellent antioxidant properties.

[Comparative Examples 1 to 4]

Except not using the hypophosphite compound solution, the sheet | seat and a film are shape | molded in the same manner as Examples 1-4, and a thermal stability test and a weather resistance test are performed.

The results are shown in Table 2. None of the resin compositions have excellent antioxidant properties.

TABLE 2

LDPE: Low Density Polyethylene (Sumikasen F 208-0, manufactured by Sumitomo Chemical Co., Ltd.)

BHT: Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.)

1010 Irganox 1010 (manufactured by Ciba Geigy)

HALS 944: Chimassorb 944 LD (manufactured by Ciba Geigy)

HALS 500: Cyasorb UV 3346 (manufactured by American Cyanamide Company)

[Examples 5 to 13]

The resin, heat stabilizer, blocking amine-based weather stabilizer and hypophosphite compound solution shown in Table 3 were mixed and kneaded with a Labolast mill (manufactured by Toyo Seiki Seisakusho) at 160 ° C. and 60 rpm for 5 minutes, and then pressurized. Molding forms a sheet 1 mm thick. The sheet is subjected to a thermal stability test (vessel internal temperature: 210 ° C).

The results are shown in Table 3. Each resin composition has excellent antioxidant properties.

[Comparative Examples 5-9]

Except using the component of the composition of Table 3, a sheet | seat is manufactured by a method similar to Examples 5-13, and a thermal stability test is done.

The results are shown in Table 3. None of the resin compositions have excellent antioxidant properties.

TABLE 3

Note: EVA: Ethylene-vinylacetate copolymer (manufactured by Evatate H 2020 Sumitomo Chemical Co., Ltd.)

PEG 400: polyethylene glycol 400 (manufactured by Nakaraitesk, molecular weight: 380-420).

LDPE, BHT, HALS 944 and 1010: see Table 2.

HALS 622: Tinuvin (trade name) 622 LD (manufactured by Ciba Geigy)

Example 14

Prepare a mullet by mixing the resin, heat stabilizer, blocking amine based weathering stabilizer, fog inhibitor and hypophosphite compound solution shown in Table 4, kneading with a half-blow mixer at 150 ° C. for 5 minutes, and then granulating with an extruder. . The pellet is molded by in-plate molding to form a 75 μm thick film. The film is subjected to a weather resistance test.

The results are shown in Table 4. The resin composition has excellent antioxidant properties.

Comparative Example 10

A film was prepared and subjected to a weather resistance test in the same manner as in Example 14 except that the components of the composition of Table 4 were used.

The results are shown in Table 4. The antioxidant property of the resin composition is insufficient.

TABLE 4

Note: EVA: ethylene-butyl acetate copolymer (Evatate, manufactured by Sumitomo Chemical Co., Ltd.).

BHT and HALS 944: see Table 2.

Claims (4)

A resin composition having high antioxidant properties, comprising a resin, a solution of a hypophosphite compound in an organic solvent, a heat stabilizer and a weathering stabilizer based on a blocking amine. The high antioxidant composition of the resin of Claim 1 whose resin is an olefin polymer. The hypophosphite compound according to claim 1, wherein the hypophosphite compound is lithium hypophosphite, sodium hypophosphite, potassium hypophosphite, hypophosphite magnesium, hypophosphite zinc, hypophosphite titanium, hypophosphite vanadium, hypophosphite, molybdenum hypophosphite, Hypophosphoric acid manganese, hypophosphite cobalt, hypophosphite ammonium hypophosphite, ammonium hypophosphite, diethylammonium hypophosphite, triethylammonium hypophosphite, tetraethylammonium hypophosphite, tetrabutyl phosphonium hypophosphite and tetraphenylphosphonium hypophosphite Highly antioxidant resin composition selected from the group consisting of. The resin composition having high antioxidant resistance according to claim 1, wherein the organic solvent is a polyhydric alcohol having a molecular weight of 50,000 or less.