JPH0753770B2 - Method for producing modified polyolefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a modified polyolefin. More specifically, a specific amount of a phenolic antioxidant, a polyol or a partial ester of the polyol and a fatty acid (hereinafter, referred to as compound A) is added to a polyolefin having a titanium content of the catalyst residue of 5 ppm or more or a vanadium content of 0.5 ppm or more, Radical generator and modifier are added, and the temperature is 15
The present invention relates to a method for producing a modified polyolefin, which comprises melt-kneading at 0 ° C to 300 ° C.

[Conventional technology]

Generally, since polyolefin is relatively inexpensive and has excellent mechanical properties, it is used for producing various molded products such as injection molded products, hollow molded products, films, sheets and fibers. However, the polyolefin is molded and processed at a temperature higher than the melting point of the polyolefin, but is subjected to oxidative deterioration due to heat during melt kneading, and the mechanical strength is reduced due to the cutting of the molecular chain of the polyolefin or the processability due to crosslinking is caused. And deterioration of color and odor caused by oxidative deterioration. In particular, a propylene-based polymer has a tertiary carbon that is easily oxidized in the polymer, and thus is easily subjected to thermal oxidative deterioration due to melt-kneading during molding and also has a thermal stability during practical use. Also has a problem. Therefore, in order to prevent thermal oxidative deterioration during melt kneading, 2,6-di-
Low molecular weight phenolic antioxidants such as t-butyl-p-cresol (BHT), and high molecular weight phenolic antioxidants are widely used in order to impart thermal stability during practical use.

However, when the polyolefin blended with the above-mentioned phenolic antioxidant is melt-kneaded, the phenolic antioxidant used is oxidized by the complex compound of titanium or vanadium, which is the catalyst residue in the polyolefin, at the time of melt-kneading to form a quinone compound. However, it is said that a problem occurs when the obtained polyolefin is colored. For this reason, a polyolefin composition in which a polyol which is a reaction product of pentaerythritol or pentaerythritol and propylene oxide is blended with polyolefin (JP-A-58-213036), polyol, partial or complete ester of polyol and fatty acid, phosphaite, Or polypropylene composition containing one or more compounds of thiophosphite (Journal of Applied Polymer Science, 29, 4421-4426 (1984))
(Journal of Applied Polymer Science, Vol.29, p.44
21-4426 (1984)]) have been proposed.

Further, since polyolefin is difficult to adhere to a metal or polar resin due to the non-polar property of the polyolefin, and printing, painting, hot stamping, and plating are difficult, introduction of a polar group into the polyolefin is particularly aimed at improving these drawbacks. A method of modifying a polyolefin by melt-kneading in the presence of a radical generator using a modifier composed of an unsaturated carboxylic acid or a derivative thereof is well known. For the purpose of further improving properties such as surface processability such as printing and painting, and impact resistance, a specific ethylene-propylene copolymer is graft-copolymerized with an unsaturated dicarboxylic acid or its anhydride with respect to polyolefin. In kneading the modified polymer thus prepared into a composition, one or more polyhydric alcohols selected from trimethylolpropane, 1,6-hexanediol, pentaerythritol, dipentaerythritol and the like are further mixed and kneaded. The obtained polyolefin composition (JP-A-61-89239) has been proposed.

[Problems to be solved by the invention]

In the process of studying the coloring property of a polyolefin containing titanium or vanadium as a catalyst residue, the present inventors have added the above-mentioned phenolic antioxidant to the polyolefin containing a large amount of titanium or vanadium in the catalyst residue. Even if the compound is blended and melt-kneaded, coloring does not occur to a degree that poses a practical problem, but a polyolefin compound containing such a phenolic antioxidant is melt-kneaded in the presence of a radical generator using a modifier. It was found that the modified polyolefin obtained after the modification was markedly colored. This phenomenon is not described at all in JP-A-58-213036 and Journal of Applied Polymer Science, 29, 4421-4426 (1984). Further, the hue of the polyolefin composition obtained by blending the polyolefin and the modified polymer with the polyhydric alcohol proposed in JP-A-61-89239 is not yet sufficiently satisfactory.

The present inventors have prepared a polyolefin containing a titanium-based or vanadium-containing catalyst residue described above and a phenol-based antioxidant with a phenol-based antioxidant, for the purpose of improving the adhesiveness and the like of the radical generator by using a modifier. The present inventors have earnestly studied a method of obtaining a modified polyolefin which is not colored even when modified by melt-kneading in the presence of it. As a result, the titanium content of the catalyst residue is 5 ppm or more or the vanadium content is 0.5 ppm.
When a specific amount of a phenolic antioxidant, a polyol or a partial ester of a polyol and a fatty acid (hereinafter referred to as compound A), a radical generator and a modifier is added to the above-described polyolefin, and the mixture is melt-kneaded, a modification without coloring is obtained. It was found that a polyolefin can be obtained, and the present invention was completed based on this finding.

As is clear from the above description, the object of the present invention is to provide compound A, a phenolic antioxidant, a radical generator and a modifier to a polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of a catalyst residue. It is intended to provide a method for producing a modified polyolefin without coloring by compounding and melt-kneading.

[Means for solving problems]

 The present invention has the following configurations.

Titanium content of catalyst residue is 5 ppm or more or vanadium content is 0.
To 100 parts by weight of polyolefin containing 5 ppm or more, 0.01 to 1 part by weight of a polyol or a partial ester of the polyol and a fatty acid (hereinafter referred to as compound A) and a phenolic antioxidant, and 0.001 to a radical generating agent are added.
0.5 to 50 parts by weight of modifier and 0.01 to 5 parts by weight of 150 to 30
A method for producing a modified polyolefin, which comprises melt-kneading at 0 ° C.

The polyolefin used in the production method of the present invention contains titanium residue of the catalyst residue of 5 ppm or more or vanadium content of 0.5 ppm or more, for example, solution polymerization method using a saturated hydrocarbon solvent, bulk polymerization method, gas phase It is a polyolefin obtained by a polymerization method or a polymerization method combining a bulk polymerization method and a gas phase polymerization method. In the production method of the present invention, it is possible to use a polyolefin having a titanium content of the catalyst residue of less than 5 ppm or a vanadium content of less than 0.5 ppm. Even if it is not blended, the resulting modified polyolefin should give a coloration that is a problem in practical use. As the polyolefin used in the present invention, the titanium content of the catalyst residue is 5 ppm.
Or a polyolefin containing 0.5 ppm or more of vanadium, ethylene, propylene, butene-1,
Pentene-1,4-methyl-pentene-1, hexene-
1, homopolymers of α-olefin such as octene-1,
A crystalline or amorphous random copolymer or a crystalline block copolymer of these two or more α-olefins, an amorphous ethylene-propylene-nonconjugated diene terpolymer, these α-olefins and vinyl acetate , Copolymers with acrylates, or saponified products of the copolymers, copolymers of these α-olefins with unsaturated carboxylic acids or their anhydrides, reaction formation of the copolymers with metal ion compounds Examples thereof include, for example, not only these polyolefins can be used alone, but also two or more kinds of polyolefins can be mixed and used. Further, the above-mentioned polyolefin and various synthetic rubbers (for example, polybutadiene, polyisoprene, chlorinated polyethylene, chlorinated polypropylene, styrene-butadiene rubber, styrene-
Butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-propylene-butylene-styrene block copolymer, etc.) or thermoplastic synthetic resin (for example, Polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyamide, polyethylene terephthalate, polybutylene terephthalate,
It is also possible to use a mixture with polyvinyl chloride). Propylene homopolymer, crystalline or amorphous ethylene-propylene random copolymer, crystalline ethylene-
Propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-13 terpolymer, crystalline propylene-hexene-butene-13 terpolymer and catalyst residue Of titanium
A propylene-based polymer containing 5 ppm or more or vanadium content of 0.5 ppm or more is particularly preferable.

Examples of the compound A used in the present invention include glycerin, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, sorbitol, mannitol, and other polyols, monoesters of glycerin and fatty acids, and diglycerin. And fatty acid monoesters, sorbitan and fatty acid monoesters, sucrose and fatty acid monoesters, pentaerythritol and fatty acid mono or diesters, trimethylolethane and fatty acid monoesters, trimethylolpropane and fatty acid monoesters, polyoxy Partial ester of polyol and fatty acid such as ethylene glycerin and fatty acid monoester, polyoxyethylene sorbitan and fatty acid monoester (fatty acid Te is, lauric acid, myristic acid,
Palmitic acid, stearic acid, behenic acid, oleic acid, etc.) can be exemplified. Particularly preferred are trimethylolethane, monoesters of glycerin and fatty acids, and mono- or diesters of pentaerythritol and fatty acids. Also, as a phenol-based antioxidant, 2,6-di-
t-butyl-p-cresol, 2-t-butyl-4,6-
Dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-i-butyl-4-n-butyl Phenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6- Tri-cyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, n-octadecyl-β- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate,
2,6-diphenyl-4-octadecyloxyphenol,
2,4,6-Tris (3 ', 5'-di-t-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, 2,6-di-t-butyl-4-methoxyphenol , 2,5-di-t
-Butyl hydroquinone, 2,5-di-t-amyl hydroquinone, 2,2'-thio-bis- (6-t-butyl-4
-Methylphenol), 2,2'-thio-bis- (4-octylphenol), 2,2'-thio-bis- (6-t-
Butyl-3-methylphenol), 4,4'-thio-bis- (6-t-butyl-2-methylphenol), 2,2 '
-Methylene-bis- (6-t-butyl-4-methylphenol), 2,2'-methylene-bis- (6-t-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- [6- (α-methylbenzyl) -4
-Nonylphenol], 2,2'-methylene-bis- [6
-(Α, α-Dimethylbenzyl) -4-nonylphenol], 2,2′-methylene-bis- (4,6-di-t-butylphenol), 2,2′-ethylidene-bis- (4, 6-ge
t-butylphenol), 2,2'-ethylidene-bis-
(6-t-butyl-4-i-butylphenol), 4,
4'-methylene-bis- (2,6-di-t-butylphenol), 4,4'-methylene-bis- (6-t-butyl-2)
-Methylphenol), 4,4'-butylidene-bis-
(6-t-butyl-2-methylphenol), 4,4'-
Butylidene-bis- (6-t-butyl-3-methylphenol), 4,4'-butylidene-bis- (2,6-di-t-)
Butylphenol), 4,4'butylidene-bis- (3,6-
Di-t-butylphenol), 1,1-bis- (5-t-
Butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-di- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-
Tris- (5-t-butyl-4-hydroxy-2-methylphenyl) -butane, bis [3,3-bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] ethylene glycol ester, di -(3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, di- [2- (3'-t-butyl-2'-hydroxy-5'-methylbenzyl) -6-t-butyl −
4-methylphenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,
3,5-Tris-[(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate or tetrakis [methylene-3- (3 ', 5'-
Di-t-butyl-4'-hydroxyphenyl) propionate] methane may be mentioned. The compounding ratio of the compound A and the phenolic antioxidant is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of polyolefin. If the amount is less than 0.01 part by weight, the effect of preventing coloration of the modified polyolefin is not sufficiently exhibited, and if it exceeds 1 part by weight, further improvement of the coloration preventing effect cannot be expected and it is not practical. It is also uneconomical.

As the radical generator used in the present invention, the decomposition temperature is preferably not too low in order to obtain a uniform composition, and the temperature for obtaining a half-life of 10 hours is 70 ° C. or higher, preferably 100.
C. or higher, benzoylper-oxide, t-butylper-benzoate, t-butylperacetate, t
-Butyl per-oxy isopropyl carbonate, 2,5-
Di-methyl-2,5-di- (benzoylpa-oxy) hexane, 2,5-di-methyl-2,5-di- (benzoylpa-oxy) hexyne-3, t-butyl-di-peradipate, t -Butylpa-oxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butylperoxide, diquamylperoxide, 2,5-di-methyl-2,5 -Di- (t-butylperoxy) hexane, 2,5-
Di-methyl-2,5-di- (t-butylpa-oxy) hexyne-3,1,3-bis- (t-butylpa-oxyisopropyl) benzene, t-butylquimylpa-oxide, 1,1-bis- ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydro Peroxide, di-isopropylbenzene hydroperoxide, quinene hydroperoxide, t-butylhydroperoxide, p-cymenhydroperoxide, 1,1,3,3-tetra-methylbutylhydroper Examples thereof include oxides and organic peroxides such as 2,5-di-methyl-2,5-di- (hydroperoxy) hexane. In particular 2,5-di-methyl-2,5-di- (t-
Butylperoxy) hexane, 2,5-di-methyl-2,5-
Di- (t-butylperoxy) hexyne-3 or 1,3
-Bis- (t-butylperoxypropyl) benzene is preferred. The mixing ratio of the radical generator is usually 0.001 to 0.5 parts by weight, relative to 100 parts by weight of polyolefin.
It is preferably 0.01 to 0.2 parts by weight. Further, the method of the melt-kneading process, 150 ℃ ~ 300 by various melt-kneading devices described below.
C., preferably at a temperature of 180.degree. C. to 270.degree. If the melt-kneading temperature is lower than 150 ° C., sufficient modification is not carried out, and if it exceeds 300 ° C., thermal oxidative deterioration of the polyolefin is promoted and the coloring of the polyolefin becomes remarkable, which is not preferable.

The modifier used in the present invention is an unsaturated carboxylic acid or its derivative. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, nadic acid (trade name; endocis-bicyclo [2,2,1] hept-5- Enene-2,3-dicarboxylic acid), hymic acid, angelic acid, tetrahydrophthalic acid, sorbic acid, mesaconic acid and the like can be exemplified. In addition, as the derivative of unsaturated carboxylic acid, acid anhydride, ester, amide,
There are imides, acid halides, metal salts, etc., maleic anhydride, itaconic anhydride, citraconic anhydride, nadic acid anhydride, hymic acid anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid- n-butyl, methacrylic acid-n-butyl, acrylic acid-i-butyl, methacrylic acid-i-butyl, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid Acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid dimethyl ester, acrylamide, methacrylamide,
Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid Acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butylmaleimide, N-fumaric acid Examples thereof include enyl maleimide, maleoyl chloride, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. Maleic anhydride is particularly preferable. The modifier is used in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of polyolefin. If the amount is less than 0.01 parts by weight, the effect of improving the adhesiveness of the modified polyolefin is not sufficiently exerted, and if it exceeds 5 parts by weight, the effect of improving the adhesiveness is little improved and the modified polyolefin remains in the modified polyolefin. The amount of the unreacted modifier increases, and the resulting molded article has disadvantages such as deterioration in hue and generation of bubbles, which is not preferable.

In the production method of the present invention, various additives such as thioether-based and phosphorus-based antioxidants that are usually added to polyolefin in the polyolefin containing 5 ppm or more of titanium content or 0.5 ppm of vanadium content of the catalyst residue used are antioxidants. Agents, light stabilizers, clarifying agents, nucleating agents, lubricants, antistatic agents,
Anti-fog agent, anti-blocking agent, non-dripping agent, pigment, heavy metal deactivator (copper damage inhibitor), dispersant or neutralizing agent for metal soaps, inorganic filler (eg talc, mica, clay) , Wollastonite, zeolite, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, calcium silicate, glass fiber, carbon fiber, etc. or coupling agent (for example, silane-based, titanate-based, boron-based, aluminate) The above-mentioned inorganic fillers or organic fillers (for example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) surface-treated with a surface treating agent such as those of It can be used by blending it in a range that does not exist. In particular, when a phosphorus-based antioxidant is used in combination, a coloring preventing effect is synergistically exhibited. Preferred phosphorus-based antioxidants are distearyl-pentaerythritol-diphosphite and tetrakis (2,4-di-t-
Butylphenyl) -4,4'-biphenylene-di-phosphonite, bis (2,4-di-t-butylphenyl)-
Pentaerythritol-diphosphite, bis (2,6
Examples include -di-t-butyl-4-methylphenyl) -pentaerythritol-diphosphite and tris (2,4-di-t-butylphenyl) phosphite.

In the production method of the present invention, the compound A, the phenol-based antioxidant, the radical generator, the modifier and the usual polyolefin added to the polyolefin containing 5 ppm or more of titanium content or 0.5 ppm or more of vanadium content of the catalyst residue. Using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, or a Banbury mixer, each predetermined amount of each of the various additives is mixed at a temperature at which the blended radical generator is not decomposed. Single screw extruder, twin screw extruder, Brabender or roll etc., melt kneading temperature 150 ℃ ~ 300 ℃, preferably 180 ℃
It is carried out by melt-kneading treatment at ˜270 ° C.

[Action]

In the present invention, the phenol-based antioxidant is a radical chain inhibitor, and the radical generator is a melt-kneading treatment, that is, a radical is generated by heating, a hydrogen atom of the polyolefin is abstracted to generate a radical of the polyolefin, and the modifier is It is well known that the radical of the polyolefin is grafted, that is, the polyolefin is modified to improve the adhesiveness.

In the production method of the present invention, the compound A is a polyolefin stabilized by a phenolic antioxidant,
When melt-kneading in the presence of a radical generator using a modifier, the mechanism of action itself is not clear what kind of action it has on the complex compound of titanium or vanadium, but it is a complete ester of polyol and fatty acid. Since the effect of the present invention is not exhibited when the above is used, it is presumed that the alcoholic hydroxyl group of the compound A acts on the complex compound of titanium or vanadium to form a stable chelate compound.

〔effect〕

The modified polyolefin obtained by the production method of the present invention is obtained by a method of modifying with a radical generator and a modifier using a conventionally known phosphorus-based inhibitor or a polyolefin prepared by blending a polyol and a complete ester of a fatty acid. Compared with the modified polyolefin, there is no coloring and the adhesiveness is improved. Therefore, the modified polyolefin alone or mixed with the unmodified polyolefin, injection molding method, extrusion molding method (especially laminated extrusion molding method), blow molding method, etc. It can be preferably used for the production of a target molded article by the various molding methods of.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited thereto.

The evaluation methods used in Examples, Comparative Examples and Reference Examples were as follows.

Colorability: YI (Yellowness Index) of the obtained pellets was measured (in conformity with JIS K 7103), and the colorability was evaluated from the magnitude of this YI value.

The smaller this value is, the less the coloring is.

Examples 1 to 16 and Comparative Examples 1 to 3 As polyolefins, MFR (load at 230 ° C. 2.16 kg
Discharge of molten resin for 10 minutes when added) 2.0g / 10min powdery propylene homopolymer (titanium content 30ppm) 1
To 100 parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di-t-butyl-p-cresol, tetrakis as a phenolic antioxidant [Methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,
4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t- as a radical generator
Butylpa-oxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in the respective prescribed amounts in a Henschel mixer (trade name) at the blending ratios shown in Table 1 below, after stirring and mixing for 3 minutes. The mixture was melt-kneaded at 200 ° C. with a single-screw extruder having a diameter of 40 mm to be modified and pelletized. Further, as Comparative Examples 1 to 3, MFR having a powdery propylene homopolymer of 2.0 g / 10 min (titanium content 30 ppm) 100
A predetermined amount of each of the additives shown in Table 1 described later was mixed in parts by weight, and the mixture was stirred and mixed according to Examples 1 to 16 and melt-kneaded to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 1.

Examples 17-32, Comparative Examples 4-6 As polyolefin, powdery crystalline ethylene-propylene random copolymer (ethylene content of MFR 7.0 g / 10 min)
2.5 wt%, titanium content 33 ppm) 100 parts by weight, compound A as trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol-based antioxidant t-butyl-p-cresol, tetrakis [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxyphenyl) propionate]
Methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,
3,5-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-
β- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-as radical generator
Predetermined amounts of di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxyisopropyl) benzene, maleic anhydride as a modifier and other additives Are put in a Henschel mixer (trade name) in the mixing ratio shown in Table 2 below, and mixed by stirring for 3 minutes, and then melt-kneaded at 200 ° C with a single screw extruder with a diameter of 40 mm to modify and pelletize. did. Further, as Comparative Examples 4 to 6, powdery crystalline ethylene having MFR of 7.0 g / 10 min.
100 parts by weight of a propylene random copolymer (ethylene content: 2.5% by weight, titanium content: 33 ppm) was blended with a predetermined amount of each of the additives shown in Table 2 below, and in accordance with Examples 17-32. Then, the mixture was stirred and mixed, and melt-kneaded to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 2.

Examples 33 to 48, Comparative Examples 7 to 9 As a polyolefin, powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (ethylene content:
16.0 wt%, titanium content 33 ppm) 100 parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol-based antioxidant t-butyl-p-cresol, tetrakis [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxyphenyl) propionate]
Methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,
3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β
-(4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1, as a radical generator 3-bis- (t-butylpa-oxyisopropyl) benzene, maleic anhydride as a modifier, and other additives were added to Henschel Mixer (trade name) in predetermined proportions shown in Table 3 below. After stirring and mixing for 3 minutes, the mixture was melt-kneaded at 200 ° C. in a single-screw extruder having a diameter of 40 mm to modify and pelletize. In addition, Comparative Example 7
As a powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (ethylene content 16.0% by weight, titanium content 33 ppm) in 100 parts by weight of the additives shown in Table 3 below. Predetermined pellets were obtained by blending the respective prescribed amounts and stirring and mixing and melt-kneading according to Examples 33 to 48.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 3.

Examples 49-64, Comparative Examples 10-12 As a polyolefin, powdery crystalline ethylene-propylene-butene-13 terpolymer of MFR 7.0 g / 10 min (ethylene content 2.5 wt%, butene-1 content 4.5. %, Titanium content 33 ppm) 100 parts by weight of compound A as trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6 as a phenol-based antioxidant
-Di-t-butyl-p-cresol, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2 , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-
Di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-di-as a radical generator Methyl-2,5-di-
(T-Butylpa-oxy) hexane or 1,3-bis- (t-butylpa-oxyisopropyl) benzene, maleic anhydride as a modifier and other additives in predetermined amounts shown in Table 4 below. Put in a Henschel mixer (trade name) at a ratio and stir and mix for 3 minutes, then caliber 40
mm uniaxial extruder at 200 ° C for melt-kneading to modify
Pelletized. Further, as Comparative Examples 10 to 12, the MFR is 7.0 g /
10 minutes powdery crystalline ethylene-propylene-butene-13
100 parts by weight of the original copolymer (ethylene content: 2.5% by weight, butene-1 content: 4.5% by weight, titanium content: 33 ppm) was mixed with a predetermined amount of each of the additives shown in Table 4 below. The modified pellets were obtained by stirring, mixing and melt-kneading according to Examples 49 to 64.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 4.

Examples 65 to 80, Comparative Examples 13 to 15 MI as a polyolefin (discharging amount of molten resin for 10 minutes when a load of 2.16 kg at 190 ° C. is added) 15.0 g / 10 minutes powdered Ziegler-Natsuta-based ethylene single weight To 100 parts by weight of the combined product (titanium content 8 ppm), as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,2 as a phenol-based antioxidant,
6-di-t-butyl-p-cresol, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl- 2,4,6-Tris (3,5-di-t-butyl-4-
Hydroxybenzyl) benzene, 1,3,5-tris- (3,5
-Di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,5-di as a radical generator -Methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxypropyl) benzene,
Maleic anhydride and other additives were added as modifiers in the Henschel mixer (trade name) in the proportions shown in Table 5 below, and the mixture was stirred and mixed for 3 minutes.
It was melt-kneaded with a 40 mm single-screw extruder at 200 ° C. to be modified and pelletized. Also, as Comparative Examples 13 to 15, MI is 1
Examples 65 to 80 were prepared by blending 100 parts by weight of powdered Ziegler-Natsuta ethylene homopolymer (titanium content 8 ppm) with 5.0 g / 10 min of each predetermined amount of the additives shown in Table 5 below.
Then, the mixture was stirred and mixed and melt-kneaded to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 5.

Examples 81-96, Comparative Examples 16-18 As polyolefin, powdery crystalline ethylene-propylene block copolymer (ethylene content of MFR 4.0 g / 10 min)
16.0% by weight, vanadium content 0.6 ppm) 100 parts by weight,
Trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate as compound A, 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3-methylene as a phenolic antioxidant (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,
5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4 '-Hydroxy-3', 5'-di-t-butylphenyl) propionate, as a radical generator
2,5-di-methyl-2,5-di (t-butylperoxy) hexane or 1,3-bis- (t-butylperoxypropyl) benzene, maleic anhydride as a modifier and other additives Put the specified amount in the Henschel mixer (trade name) at the blending ratio shown in Table 6 below, and 3
After stirring and mixing for a minute, the mixture was melt-kneaded at 200 ° C. in a single-screw extruder with a diameter of 40 mm to modify and pelletize. Further, as Comparative Examples 16 to 18, 100 parts by weight of a powdery crystalline ethylene-propylene block copolymer having an MFR of 4.0 g / 10 min (ethylene content 16.0% by weight, vanadium content 0.6 ppm) is shown in Table 6 below. The prescribed amount of each of the additives described in
According to 81-96, the mixture was stirred and mixed, and melt-kneaded to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 6.

Examples 97-112, Comparative Examples 19-21 As polyolefins, powdery Ziegler-Natsuta high-density ethylene-propylene copolymer with MI 6.0 g / 10 min (3.0 methyl branches / 1000 carbon, vanadium content 0.6 ppm) 100
In parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di-t-butyl-p-cresol, tetrakis [ Methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,
4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4′-hydroxy-3 ′,
5'-di-t-butylphenyl) propionate, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexane or 1,3-bis- (t- as a radical generator
Butylpa-oxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in the respective prescribed amounts in a Henschel mixer (trade name) at the blending ratios shown in Table 7 below, after stirring and mixing for 3 minutes. The mixture was melt-kneaded at 200 ° C. with a single-screw extruder having a diameter of 40 mm to be modified and pelletized. Further, as Comparative Examples 19 to 21, powdery Ziegler-Natsuta-based high-density ethylene-propylene copolymer (3.0 methyl branches / 1000 carbons, vanadium content 0.6 ppm) having a MI of 6.0 g / 10 min will be described later in 100 parts by weight. Predetermined pellets were obtained by mixing predetermined amounts of the additives shown in Table 7 above and stirring-mixing and melt-kneading according to Examples 97 to 112 to obtain modified pellets.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 7.

Examples 113-128, Comparative Examples 22-24 Mooney viscosity ML1 + 4 (100 ° C.) as polyolefin
25 powdery amorphous ethylene-propylene random copolymers (propylene content 25% by weight, vanadium content 0.6 p
pm) 100 parts by weight, as compound A, trimethylolethane, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate, 2,6-di- as a phenol antioxidant.
t-butyl-p-cresol, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di-t
-Butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate,
2,5-di-methyl-2,5-di (t-
Butylperoxy) hexane or 1,3-bis- (t
-Butylpa-oxyisopropyl) benzene, maleic anhydride as a modifier, and other additives in the respective prescribed amounts were placed in a Henschel mixer (trade name) at the compounding ratios shown in Table 8 below, and stirred and mixed for 3 minutes. The mixture was melt-kneaded at 200 ° C. in a single-screw extruder having a rear diameter of 40 mm to be modified and pelletized. Further, as Comparative Examples 22 to 24, Mooney viscosity ML1
+4 (100 ° C) 25 powdery amorphous ethylene-propylene random copolymer (propylene content 25% by weight, vanadium content 0.6 ppm) 100 parts by weight of each of the additives described in Table 8 below. A predetermined amount was mixed, and the mixture was stirred, mixed and melt-kneaded according to Examples 113 to 128 to obtain a modified pellet.

Using the pellets thus obtained, the colorability was evaluated by the test method described above. The results are shown in Table 8.

Reference Examples 1 to 4 and Comparative Examples 25 to 28 70 parts by weight of each pellet obtained in Examples 33 to 36 as Reference Examples 1 to 4, MFR of 4.0 g / 10 minutes, ethylene content
30 parts by weight of a powdery crystalline ethylene-propylene block copolymer (hereinafter abbreviated as EPB) having a content of 16.0% by weight and a titanium content of 33 ppm was put into a Henschel mixer (trade name) and stirred and mixed for 1 minute. 200 with a single screw extruder with a diameter of 40 mm
Melt-kneading was performed at ℃ to obtain pellets. Also, a comparative example
25-28 to 100 parts by weight of EPB, 0.1 part by weight of 2,6-di-t-butyl-p-cresol as a phenolic antioxidant and tetrakis [methylene-3- (3 ', 5'-di-
t-butyl-4'-hydroxyphenyl) propionate] methane 0.05 part by weight, 2,5-
Di-methyl-2,5-di- (t-butylperoxy) hexane 0.2 parts by weight, maleic anhydride as a modifier 0.3 part by weight and calcium stearate 0.1 parts by weight at a blending ratio of Henschel mixer (trade name) ) And stirred and mixed for 3 minutes, and then melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to modify and obtain pellets (hereinafter abbreviated as pellets I). To 70 parts by weight of the obtained pellet I, 30 parts by weight of EPB and trimethylolethane as the compound A, glycerin monostearate, pentaerythritol monostearate or pentaerythritol distearate were added in the respective predetermined amounts shown in Table 9 below. The mixture was put in a Henschel mixer (trade name) at a ratio and mixed for 1 minute with stirring, and then melt-kneaded at 200 ° C. with a single screw extruder having a diameter of 40 mm to obtain a pellet (hereinafter abbreviated as pellet II).

Using the pellets obtained in the reference example and the pellets I and II obtained in the comparative examples, the coloring property was evaluated by the above-mentioned test method. The results are shown in Table 9.

Various compounds and additives shown in Tables 1 to 9 are as follows.

Compound A [I]; trimethylolethane compound A [II]; glycerin monostearate compound A [III]; pentaerythritol monostearate compound A [IV]; pentaerythritol distearate phenolic antioxidant [I]; 2,6-di-t-butyl-p-cresol phenolic antioxidant [II]; tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] Methane phenol antioxidant [III]; 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene phenol antioxidant [IV] 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant [V]; n-octadecyl-β- (4'-hydroxy -3 ', 5'
-Di-t-butylphenyl) propionate radical generator [I]; 2,5-di-methyl-2,5-di- (t-butylperoxy)
Hexane radical generator [II], 1,3-bis- (t-butylperoxypropyl) benzene denaturant; phosphoric acid maleic anhydride antioxidant 1; tetrakis (2,4-di-t-butylphenyl) -4 , 4′−
Biphenylene-di-phosphononite Phosphorus antioxidant 2; Bis (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite polyol compound (complete ester of polyol and fatty acid); pentaerythritol tetrastearate Ca-St; Calcium stearate The examples and comparative examples shown in Table 1 are the cases where a propylene homopolymer was used as the polyolefin. First
As can be seen from the table, in Examples 1 to 16, propylene homopolymer containing 30 ppm of titanium in the catalyst residue according to the present invention was compounded with Compound A, a phenolic antioxidant, a radical generator and a modifier, and melted. It is a mixture that has been kneaded and modified. Comparing Examples 1 to 16 and Comparative Examples 1 and 2, Examples 1 to 16 showed less coloring, and Comparative Examples 1 and 2 in which a phosphorus-based antioxidant was used in place of the compound A showed remarkable coloring. I understand. Comparing Comparative Example 3 and Examples 1 to 16 in which a complete ester of a polyol and a fatty acid is used instead of the compound A, Comparative Example 3 is still not sufficiently satisfactory although the coloring property is improved to some extent. Further, in each of Examples, the compound A according to the present invention, a phenol-based antioxidant, a radical generator, a modifier and a phosphorus-based antioxidant were blended, and the mixture was melt-kneaded and modified. It can be seen that a remarkable synergistic effect by the combined use of the phosphorus-based antioxidant is recognized without inhibiting the excellent coloring preventing effect of the compound A as compared with the above.

Tables 2 to 8 show crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline ethylene-propylene-butene-13 terpolymer, and Ziegler-Nutta ethylene alone as polyolefin. Polymer, crystalline ethylene-propylene block copolymer, Ziegler-Natsuta high-density ethylene-propylene copolymer, amorphous ethylene-propylene random copolymer is used, and these are the same as above. The effect was confirmed.

Further, the reference examples shown in Table 9 are those obtained by blending the modified polyolefin according to the present invention (the pellets obtained in Examples 33 to 36) with the crystalline ethylene-propylene block copolymer and subjecting the mixture to melt kneading. The comparative example is the above-mentioned Japanese Patent Laid-Open No. 61-
A specific ethylene-propylene based copolymer proposed in 89239 is blended with a modified polymer obtained by graft-copolymerizing an unsaturated dicarboxylic acid anhydride with a propylene-based copolymer and a polyhydric alcohol, that is, a polyol, and melt-kneaded. The resulting polyolefin composition. The pellets I of Comparative Examples 25 to 28 were modified by melt-kneading without using the compound A of the present invention, and marked coloring occurred. Further, the pellets II of Comparative Examples 25 to 28 did not improve the remarkable coloring of the pellets I in spite of using the compound A, and like the pellets II, the pellets II were subjected to the melt-kneading treatment twice, that is, the heat history. Compared with the pellets of Examples 1 to 4, the pellets are markedly colored, and it is clear that the effect of the present invention is not exhibited. That is, in the present invention, it is possible to obtain a modified polyolefin without coloring by mixing Compound A, a phenol-based antioxidant and a modifier into the polyolefin, and melt-kneading and modifying the mixture in the presence of a radical generator. It can be said that this is a unique effect found.

It can be seen that the modified polyolefin obtained by the production method of the present invention is a modified polyolefin having no color.

From this, the modified polyolefin obtained by the production method of the present invention is modified with a compound having a conventionally known anti-coloring effect and modified by melt-kneading in the presence of a radical generator using a modifier. In addition, the anti-coloring property is remarkably superior to that obtained by blending the compound A of the present invention with the modified polyolefin modified by melt-kneading in the presence of a radical generator with a modifier and melt-kneading. It was found that the remarkable effect of the present invention was confirmed.

Claims (6)

[Claims] 1. A polyol residue or a partial ester of said polyol and a fatty acid (hereinafter referred to as compound A) and a phenol-based antioxidant are added to 100 parts by weight of polyolefin containing a titanium content of the catalyst residue of 5 ppm or more or a vanadium content of 0.5 ppm or more. 0.01 to 1 part by weight of each agent, 0.001 to 0.5 part by weight of a radical generator, 0.01 to 5 parts by weight of a modifier, and melt kneading at 150 ° C to 300 ° C, and a method for producing a modified polyolefin. . 2. The method for producing a modified polyolefin according to claim 1, wherein trimethylolethane, glycerin and a fatty acid monoester or pentaerythritol and a fatty acid mono or diester are blended as the compound A. 3. As a phenol-based antioxidant, 2,6-di-
t-butyl-p-cresol, tetrakis [methylene-
3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, 1,3,5-tris- (3,5-di-t
-Butyl-4-hydroxybenzyl) isocyanurate or n-octadecyl-β- (4'-hydroxy-
The method for producing a modified polyolefin according to claim 1, wherein 3 ', 5'-di-t-butylphenyl) propionate is blended. 4. A radical generator, 2,5-di-methyl-
2,5-di- (t-butylperoxy) hexane, 2,5-di-methyl-2,5-di- (t-butylperoxy) hexyne-3 or 1,3-bis- (t-butylpar) -The method for producing a modified polyolefin according to claim 1, which further comprises (oxyisopropyl) benzene. 5. The method for producing a modified polyolefin according to claim 1, wherein an unsaturated carboxylic acid or its derivative is blended as a modifier. 6. Polypropylene as propylene homopolymer, crystalline or amorphous ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline The method for producing a modified polyolefin according to claim 1, wherein an ethylene-propylene-butene-13 terpolymer or a crystalline propylene-hexene-butene-13 terpolymer is used.