JPH04348148A - Production of modified propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a propylene polymer composition free from discoloration in modification by blending a propylene polymer containing a large amount of Ti or V of catalyst residue with a phenolic antioxidant, a free radical generator, etc., by adding water to the blend system. CONSTITUTION:In blending (A) 100 pts.wt. propylene-based polymer containing >=5ppm titanium content of catalyst residue or >=0.5ppm vanadium with (B) 0.01-1 pt.wt. phenolic antioxident, (C) C1: 0.001-0.5 pt.wt. free radical generator (e.g. benzoyl peroxide)having >=70 deg.C, preferably >=100 deg.C temperature to give 10 hours half-life and kneading in a molten state at 150-300 deg.C or C2: 0.01-5 pts.wt. thiophosphite (preferably trilauryl trithiophosphite) and kneading in a molten state at 250-350 deg.C, (D) 0.01-1 pt.wt. water (preferably pure water or steam) is added to the mixture, which is blended in a molten state to give a modified propylene polymer free from discoloration.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a modified propylene polymer composition. For further details,
．． A specific amount of a phenolic antioxidant and a radical generator are blended into a propylene polymer containing 5 ppm or more, and a specific amount of water is allowed to coexist when melt-kneading the mixture at a temperature of 150°C to 300°C, or The titanium content of the catalyst residue is 5 ppm or more or the vanadium content is 0.5 p.
A specific amount of phenolic antioxidant and thiophosphite are blended into a propylene polymer containing pm or more, and a specific amount of water is allowed to coexist when melt-kneading the mixture at a temperature of 250°C to 350°C. The present invention relates to a method for producing a modified propylene polymer composition.

0002

[Prior Art] In general, propylene polymers are relatively inexpensive and have excellent mechanical properties, so they are used to manufacture various molded products such as injection molded products, blow molded products, films, sheets, and fibers. . However, propylene-based polymers are molded at temperatures above the melting point of the propylene-based polymer, but are subject to oxidative deterioration due to the heat during melt-kneading, and are processed by cutting the molecular chains of the propylene-based polymer. Problems of coloration and odor caused by a decrease in properties and mechanical strength as well as oxidative deterioration occur. In particular, propylene-based polymers contain tertiary carbon that is susceptible to oxidation, so they are susceptible to thermal oxidative deterioration due to melt kneading during molding, and there are also problems with long-term thermal stability. be. For this reason, in order to prevent thermal oxidative deterioration during melt-kneading, 2.
Low molecular weight phenolic antioxidants such as 6-di-t-butyl-p-cresol (BHT) are widely used, as well as higher molecular weight phenolic antioxidants to provide long-term thermal stability. .

However, when a propylene polymer composition containing the above-mentioned phenolic antioxidant is melt-kneaded, the phenolic antioxidant used is oxidized by a complex compound of titanium or vanadium, which is a catalyst residue in the propylene polymer. The problem arises that the phenolic antioxidant is oxidized to produce a quinone compound, and the resulting propylene polymer composition is colored. In addition, in order to improve the moldability of propylene-based polymers, there are methods of modifying propylene-based polymers by melt-kneading the propylene-based polymers in the presence of a radical generator, or In the presence of phosphite, at a temperature of 250°C
A method for improving the processability of propylene polymers by melt-kneading them at ~350°C for modification, ie, reducing the molecular weight of the propylene polymers, is disclosed in Japanese Patent Publication No. 14166/1983 filed by the same applicant as the present application. Publication, JP-A-47-264
It is well known from Japanese Patent Laid-Open No. 36-36, Japanese Patent Application Laid-Open No. 49-35451, and Japanese Patent Laid-Open No. 109547-1987.

In the process of researching the coloring properties of propylene-based polymers containing a large amount of titanium or vanadium as catalyst residues, the applicant discovered that propylene-based polymers containing large amounts of titanium or vanadium as catalyst residues Even if a phenolic antioxidant is added to the mixture and melt-kneaded, coloring will not occur to the extent that it becomes a practical problem, but
A propylene polymer composition blended with such a phenolic antioxidant is modified by melt-kneading in the presence of a radical generator, or melted at a temperature of 250°C to 350°C in the presence of a thiophosphite. It has been found that when the modified propylene polymer composition is modified by kneading, the resulting modified propylene polymer composition is significantly colored. For this reason, the present applicant first blended a polyol or a partial ester of a polyol with a fatty acid and a phenolic antioxidant into a propylene polymer with the aim of obtaining a modified propylene polymer composition without coloring. A method for producing a modified propylene polymer by melt-kneading in the presence of a radical generator (JP-A-62-252443 and JP-A-63-1265)
0), a method for producing a modified propylene polymer composition in which a zinc salt of a carboxylic acid and a phenolic antioxidant are blended into a propylene polymer and melt-kneaded in the presence of a radical generator (JP-A-Sho 63-308052),
A propylene polymer is blended with a polyol or a partial ester of a polyol and a fatty acid, and a phenolic antioxidant, and heated at 250°C in the presence of thiophosphite.
A method for improving the processability of propylene polymers by melt-kneading at ~350°C (Japanese Patent Application Laid-open No. 170439/1983), and a method for improving the processability of propylene polymers by melt-kneading them at ~350°C, and adding zinc salts of carboxylic acids and phenolic antioxidants to propylene polymers, Method for improving the processability of propylene polymers by melt-kneading at a temperature of 250°C to 350°C in the presence of phosphite (JP-A-63-3)
No. 09543) was proposed.

Furthermore, JP-A-49-87782 discloses that in order to reduce the halogen content of the polyolefin, a polyolefin in the form of small pieces is treated with an alkene oxide, water and optionally nitrogen just before or in the melting zone. A method for finishing polyolefin particles obtained by polymerization using a Ziegler-Natta catalyst is proposed, and the publication describes that the polyolefin can be decomposed, if desired, by additionally selecting special operating conditions. There is also a description that a desired molecular weight can be achieved by However, JP-A No. 49-87782 discloses a special method in which water and a phenolic antioxidant are blended into a propylene polymer containing a large amount of titanium or vanadium in the catalyst residue to decompose the propylene polymer. The operating conditions include melt-kneading treatment in the presence of a radical generator or a temperature of 250°C to 350°C in the presence of thiophosphite.
There is no description or suggestion that a color-free modified propylene polymer composition can be obtained by selecting melt-kneading treatment at .degree.

[0006]

[Problems to be Solved by the Invention] The present inventors have previously disclosed Japanese Patent Application Laid-open No. 62-252443 and Japanese Patent Application Laid-Open No. 63-12650.
No. 1, JP-A-63-308052, JP-A-63
-170439 publication and JP-A-63-309543
Unsatisfied with the method for producing a modified propylene polymer composition proposed in the publication, we developed a propylene polymer in which a phenolic antioxidant was blended with a propylene polymer containing a large amount of titanium or vanadium in the catalyst residue. Even if the combined composition is melt-kneaded in the presence of a radical generator or melt-kneaded in the presence of a thiophosphite at a temperature of 250°C to 350°C for the purpose of improving its moldability, no coloring occurs. Further intensive research was conducted on methods for obtaining high-quality propylene-based polymer compositions. As a result, the present inventors found that: (i) a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue was blended with specific amounts of a phenolic antioxidant and a radical generator, and melted. When kneading, a specific amount of water is allowed to coexist, or the titanium content of the catalyst residue is reduced to 5pp.
A propylene polymer containing 0.5 ppm or more of vanadium or 0.5 ppm or more of vanadium is blended with specific amounts of a phenolic antioxidant and thiophosphite, and heated at a temperature of 25%.
The inventors discovered that a modified propylene polymer composition without coloration can be obtained by coexisting a specific amount of water during melt-kneading treatment at 0°C to 350°C, and based on this knowledge, the present invention was completed. . As is clear from the above description, an object of the present invention is to provide a method for producing a modified propylene polymer composition without coloring.

[0007]

Means for Solving the Problems The present invention has the following configuration. (1) No phenolic antioxidant was added to 100 parts by weight of a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue.
．． 0.01 to 1 part by weight and 0.001 to 1 part by weight of the radical generator
When modifying the propylene polymer by blending 0.5 parts by weight and melt-kneading at 150°C to 300°C, 0.01 to 1
1. A method for producing a modified propylene polymer composition, which comprises melt-kneading in the coexistence of parts by weight of water. (2) No phenolic antioxidant was added to 100 parts by weight of a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue.
．． 01 to 1 part by weight and 0.01 part of thiophosphite
~5 parts by weight is blended and melt-kneaded at 250°C to 350°C to modify the propylene polymer, characterized in that the melt-kneading process is carried out in the coexistence of 0.01 to 1 part by weight of water. A method for producing a modified propylene polymer composition.

The propylene polymer used in the production method of the present invention contains 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue, for example, by solution polymerization using a saturated hydrocarbon solvent. It is a propylene polymer obtained by bulk polymerization, gas phase polymerization, or a combination of bulk polymerization and gas phase polymerization. In the production method of the present invention, there is no problem in using a propylene polymer whose catalyst residue has a titanium content of less than 5 ppm or a vanadium content of less than 0.5 ppm, but in this case, the above-mentioned Even if water is not present, the resulting modified propylene polymer composition will not be colored to the extent that it poses a practical problem. The propylene polymer used in the present invention is a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue, a crystalline homopolymer of propylene, and a propylene component of 70 wt. % or more of propylene and ethylene, butene-1, pentene-
Crystalline random copolymer or crystalline block copolymer with one or more α-olefins such as 1,4-methyl-pentene-1, hexene-1, octene-1, propylene and vinyl acetate or A copolymer with an acrylic acid ester, a saponified product of the copolymer, a copolymer of propylene with an unsaturated silane compound, a copolymer of propylene with an unsaturated carboxylic acid or its anhydride, a copolymer with the copolymer Examples include reaction products with metal ion compounds, and these propylene polymers can be used alone or in combination of two or more propylene polymers.

[0009] Furthermore, the above-mentioned propylene polymers and various synthetic rubbers (for example, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, polybutadiene, polyisoprene, polychloroprene, chlorinated polyethylene, chlorinated polypropylene, fluororubber,
Styrene-butadiene rubber, acrylonitrile-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 resins (such as ultra-low density polyethylene, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polybutene, poly-4-methylpentene-1) Polyolefins other than propylene polymers, polystyrene, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, polyethylene terephthalate, polybutylene terephthalate, polycarbonates, polyvinyl chloride, fluororesins, petroleum resins (e.g. C5-based petroleum resin,
hydrogenated C5 petroleum resin, C9 petroleum resin, hydrogenated C9 petroleum resin, C5-C9 copolymer petroleum resin, hydrogenated C5-C9 copolymer petroleum resin, acid-modified C9 petroleum resin, etc.), DCPD resin (e.g. Cyclopentadiene petroleum resin, hydrogenated cyclopentadiene petroleum resin, cyclopentadiene-C5
Copolymerized petroleum resin, hydrogenated cyclopentadiene-C5 copolymerized petroleum resin, cyclopentadiene-C9 copolymerized petroleum resin,
(DCPD resin with a softening point of 80 to 200°C) such as hydrogenated cyclopentadiene-C9 copolymer petroleum resin, cyclopentadiene-C5-C9 copolymer petroleum resin, hydrogenated cyclopentadiene-C5-C9 copolymer petroleum resin, etc.) They can also be used in combination. Crystalline propylene homopolymer, crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, crystalline propylene-butene-1 random copolymer, crystalline ethylene-propylene-butene-1 ternary Copolymers, crystalline propylene-hexene-butene-1 ternary copolymers, and mixtures of two or more of these, with a titanium content of catalyst residue of 5pp.
When a propylene polymer containing vanadium of 0.5 ppm or more is used, the effect of preventing coloring is remarkable.

[0010] The water used in the present invention preferably does not contain impurities, such as acidic substances, that have an adverse effect on the quality of the propylene polymer and the corrosion of materials used in the melt-kneading device described below. Most preferred is pure water or steam. As a phenolic 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-butylphenol, 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-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 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), 4,4'-thio-bis(6-t-butyl-3-methylphenol), 4
, 4'-thio-bis(2,6-di-t-butylphenol), 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-di-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, calcium-bis[O-ethyl-(
3,5-di-t-butyl-4-hydroxybenzyl) phosphonate], 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate , 2-t-butyl-6-[3
-t-butyl-2-hydroxy-5-methyl(α-methylbenzyl)]-4-methylphenylacrylate, 2
, 4-di-t-butyl-6-[3,5-di-t-butyl-2-hydroxy(α-methylbenzyl)]phenylacrylate, 2,4-di-t-amyl-6-[3, 5-
di-t-amyl-2-hydroxy(α-methylbenzyl)] phenyl acrylate, tocopherol, 2,6-
diphenyl-4-octadecyloxyphenol, 2,4
-bis(n-octylthio)-6-(4-hydroxy-
3,5-di-t-butylanilino)-1,3,5-triazine, 2,4,6-tris(2'-hydroxy-4'
-octoxyphenyl)-1,3,5-triazine, 2
,4,6-tris[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)ethyl]-1,3,5-
triazine, 2,4,6-tris(3',5'-di-t
-butyl-4'-hydroxybenzylthio)-1,3,
5-triazine, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzylacetyl)hexahydro-1,3,5-triazine, 1,1,3-tris(5 -t-butyl-4-hydroxy-2-methylphenyl)-butane, triethylene glycol-bis[3
-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-
Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-bis[3-(
3,5-di-t-butyl-4-hydroxyphenyl)propionyl]-hexamethylenediamine, 3,5-di-
t-Butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,2-thio-diethylenebis[
3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid]ethylene glycol ester, Bis[3,3-bis(4'-hydroxy-3'-methyl-5'-t-butylphenyl)butyric acid]ethylene glycol ester, bis[3,3-bis(4'-hydroxy-3
',5'-di-t-butylphenyl)butyric acid] ethylene glycol ester, bis[3,3-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid]-2,2- bis(hydroxyethoxyphenyl)propane ester,

Bis[3,3-bis(4'-hydroxy-
3'-Methyl-5'-t-butylphenyl)butyric acid]-2,2-bis(hydroxyethoxyphenyl)propane ester, bis[3,3-bis(4'-hydroxy-3',5'- di-t-butylphenyl)butyric acid]-2,2-bis(hydroxyethoxyphenyl)propane ester, bis[2-(3'-t-
Butyl-2'-hydroxy-5'-methylbenzyl)-
6-tert-butyl-4-methylphenyl] terephthalate, 3,9-bis(3,5-di-t-butyl-4-hydroxyphenyl)-2,4,8,10-tetraoxaspiro[5.5 ] undecane, 3,9-bis[1,1-dimethyl-2-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5. 5] undecane, 3,9-bis[1,1-
Dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]
undecane, 3,9-bis[1,1-dimethyl-2-{
β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}ethyl]-2,4,8,10
-Tetraoxaspiro[5.5]undecane, 3,9-
Bis[1,1-dimethyl-2-{β-(3,5-diphenyl-4-hydroxyphenyl)propionyloxy}
ethyl]-2,4,8,10-tetraoxaspiro[5
．． 5] Undecane, 3,9-bis[1,1-dimethyl-
2-{β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionyloxy}ethyl]-2,4,
8,10-tetraoxaspiro[5.5]undecane,
1,3,5-trimethyl-2,4,6-tris(3,5
-di-t-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris(4-t-butyl-
3-hydroxy-2,6-dimethylbenzyl)isocyanurate, tris[3-(3,5-di-t-butyl-4
-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2,2-bis[4-[2-(3-methyl-5-t-butyl-4-hydroxyphenylpropionyloxy)ethoxy]phenyl]propane, 2,2-
Bis[4-[2-(3,5-di-t-butyl-4-hydroxyphenylpropionyloxy)ethoxy]phenyl]propane, tetrakis[methylene-3-(3'-methyl-5'-t-butyl- 4'-hydroxyphenyl)
propionate] methane and tetrakis [methylene-
Examples include 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane.

Not only can these phenolic antioxidants be used alone, but also two or more phenolic antioxidants can be used in combination. The mixing ratio of water is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, per 100 parts by weight of the propylene polymer. If the amount is less than 0.01 part by weight, the coloring prevention effect of the modified propylene polymer composition will not be sufficiently exhibited, and if it is more than 1 part by weight, it is expected that the coloring prevention effect will be further improved. This is not practical because foaming becomes noticeable. The blending ratio of the phenolic antioxidant is 0.01 to 1 part by weight, preferably 0.05 parts by weight, per 100 parts by weight of the propylene polymer.
~0.5 parts by weight. If the amount is less than 0.01 part by weight, the effect of preventing thermal oxidative deterioration of the modified propylene polymer composition will not be sufficiently exhibited. Not only is it impractical as no improvement in the prevention effect can be expected, but it is also uneconomical.

For the radical generator used in the present invention, in order to obtain a uniform composition, it is preferable that the decomposition temperature is not too low, and the temperature to obtain a half-life of 10 hours is 70°C.
Above, preferably 100°C or higher, benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5-di(benzoyl peroxy)hexane, 2,5-di-methyl-
2,5-di(benzoylperoxy)hexyne-3,t
-butyl-di-peradipate, t-butylperoxy-3,5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di(t-
butylperoxy)hexane, 2,5-di-methyl-2
,5-di(t-butylperoxy)hexyne-3,1,
3-bis(t-butylperoxyisopropyl)benzene, t-butylcumylperoxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, -butylperoxy)
Cyclohexane, 2,2-bis(t-butylperoxy)butane, p-menthane hydroperoxide, di-
Isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide,

p-cymene hydroperoxide, 1
, 1,3,3-tetra-methylbutyl hydroperoxide, 2,5-di-methyl-2,5-di(hydroperoxy)hexane, trimethylsilyl-cumyl peroxide, 2,5-di-methyl- Organic peroxides such as 2,5-bis(trimethylsilylperoxy)hexane, 2,5-di-methyl-2,5-bis(trimethylsilylperoxy)hexyne-3 and 1,3-bis(trimethylsilylperoxyisopropyl)benzene Examples include oxides, particularly 2,5-di-methyl-2,5-di(t-butylperoxy)hexane, 2,5-di-methyl-2,5
-di(t-butylperoxy)hexyne-3 and 1,
3-bis(t-butylperoxyisopropyl)benzene is preferred. Not only can these radical generators be used alone, but also two or more radical generators can be used in combination. The ratio of the radical generator to 100 parts by weight of the propylene polymer is usually 0.001 to 0.5.
Part by weight, preferably 0.01 to 0.2 part by weight. The melt-kneading process is carried out at 150°C to 300°C, preferably 180°C to 270°C, using various melt-kneading apparatuses described below.
Perform at a temperature of If the melt-kneading treatment temperature is less than 150°C, sufficient modification will not be carried out, and if it exceeds 300°C, thermal oxidative deterioration of the propylene polymer will be accelerated and coloration of the propylene polymer will become noticeable, which is not preferable.

Thiophosphites used in the present invention include trioctyltrithiophosphite, tri-i
-Octyltrithiophosphite, tridecyltrithiophosphite, tri-i-decyltrithiophosphite, trilauryltrithiophosphite, tricetyltrithiophosphite, tristearyltrithiophosphite, tricyclohexyltrithiophosphite, triphenyltrithiophosphite , diphenyldecyl trithiophosphite, diphenyl lauryl trithiophosphite, tribenzyl trithiophosphite, trinaphthyl trithiophosphite, tris (octylphenyl) trithiophosphite, tris (p-nonylphenyl) trithiophosphite,
Tris(2,4-dinonylphenyl)trithiophosphite, tris[{4-(α-methylbenzyl)phenyl}]trithiophosphite, tris[{2,4-bis(α-methylbenzyl)phenyl}]trithi Ophosphite, tris[{2,4,6-tris(α-methylbenzyl)phenyl}]trithiophosphite, tris(2,4-di-t-butylphenyl)trithiophosphite, catechyl-2,6-di -t-butyl-4-methylphenyltrithiophosphite, catechyl-2,
4,6-tri-t-butylphenyltrithiophosphite, α-naphthylcatecyltrithiophosphite,
2,2'-methylenebis(4-methyl-6-t-butylphenyl)-2-naphthyltrithiophosphite, tetralauryl-4-oxaheptylene-1,7-tetrathiophosphite, tetrakis(mercaptrauryl)-1, 6-dimercaptohexylene-diphosphite, pentakis(mercaptrauryl)bis(1,6-
hexylene-dimercapto) triphosphite, tetrakis(mercaptrauryl) 2,9-dimercapto-
p-Menthylene diphosphite, diphenyl-di(mercaptrauryl) 1,2-dimercaptoethylene diphosphite, bis(mercaptrauryl) 1,6-
Dimercaptohexylene-bis(benzene phosphite), Diphenoxy-1,6-dimercaptohexylene-bis(benzene phosphite), Di(octylthio)pentaerythritol diphosphite, Di(i-octylthio)pentaerythritol diphosphite Fight,
Di(decylthio)pentaerythritol diphosphite, di(i-decylthio)pentaerythritol diphosphite, di(laurylthio)pentaerythritol diphosphite, di(myristylthio)pentaerythritol diphosphite, di(stearylthio)pentaerythritol Diphosphite, di(oleylthio)pentaerythritol diphosphite, di(cyclohexylthio)pentaerythritol diphosphite, di(phenylthio)pentaerythritol-diphosphite, di(benzylthio)pentaerythritol-
Diphosphite, di(naphthylthio)pentaerythritol-diphosphite and bis(2,4-di-t
-butylphenylthio)pentaerythritol diphosphite can be exemplified, and trilauryltrithiophosphite, tricetyltrithiophosphite and di(laurylthio)pentaerythritol diphosphite are particularly preferred. These thiophosphites can be used alone or in combination of two or more. The blending ratio of the thiophosphite is usually based on 100 parts by weight of the propylene polymer.
The amount is 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight. If the amount is less than 0.01 part by weight, the processability improvement effect of the propylene polymer composition will not be sufficiently exhibited, and 5
Although it is possible to exceed the weight part, no further improvement in processability can be expected, and an unpleasant odor is likely to be generated, which is not only impractical but also uneconomical. The melt-kneading process may be carried out at 250°C to 350°C, preferably from 290°C to 33°C using various melt-kneading devices or molding devices described below.
It is carried out at a temperature of 0°C. If the melt-kneading treatment temperature is less than 250°C, sufficient improvement in processability will not be achieved, and if it exceeds 350°C, thermal oxidative deterioration of the propylene polymer will be accelerated and coloration of the propylene polymer will become noticeable, which is undesirable. .

In the production method of the present invention, the titanium content of the catalyst residue used is 5 ppm or more or the vanadium content is 0.
．． The propylene polymer containing 5 ppm or more contains various additives that are normally added to propylene polymers, such as thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents, lubricants, and antistatic agents. agents, anti-fogging agents, anti-blocking agents, dropless agents, pigments, heavy metal deactivators (copper damage inhibitors), halogen scavengers, dispersants or neutralizing agents for metal soaps, organic and inorganic agents, etc. Antibacterial agents, inorganic fillers (e.g. talc, mica, clay, wollastonite, zeolite, kaolin, bentonite, perlite, diatomaceous earth, asbestos, calcium carbonate, aluminum hydroxide, magnesium hydroxide, silicon dioxide, titanium dioxide, oxide) Coupling agents (such as silanes, titanates, The inorganic filler or organic filler (boron-based, aluminate-based, zircoaluminate-based, etc.) whose surface has been treated with a surface treatment agent such as
For example, wood flour, pulp, waste paper, synthetic fibers, natural fibers, etc.) may be blended and used within a range that does not impair the purpose of the present invention. In particular, when a phosphorus-based antioxidant is used in combination, a synergistic coloring prevention effect is exhibited, so it is preferable to use them together. A preferred phosphorus antioxidant is distearyl-
Pentaerythritol-diphosphite, Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-di-phosphonite, Bis(2,4-di-
t-butylphenyl)-pentaerythritol-diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)-pentaerythritol-diphosphite, bis(2,4,6-tri-t- butylphenyl) pentaerythritol-diphosphite, tris(2,
4-di-t-butylphenyl) phosphite, 2,2
Examples include '-methylene-bis(4,6-di-t-butylphenyl)octylphosphite and 2,2'-ethylidene-bis(4,6-di-t-butylphenyl)fluorophosphite.

The production method of the present invention includes (1) (1) The titanium content of the catalyst residue is 5 ppm or more or the vanadium content is 0.5 p.
Predetermined amounts of water, a phenolic antioxidant, a radical generator, and the above-mentioned various additives that are normally added to propylene polymers are added to a propylene polymer containing pm or more using a conventional mixing device such as a Henschel mixer (trade name). , super mixer, ribbon blender, banbari mixer,
Using a tumbler or the like, mix at a temperature that does not decompose the blended radical generator to form a mixture, and then mix the mixture using various melt-kneading devices such as an ordinary single-screw extruder, twin-screw extruder, Brabender or roll, preferably. Using a melt-kneading device with a degassing area, the melt-kneading temperature is 150°C to 300°C.
℃, preferably 180°C to 270°C to form pellets. ① A propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue, a phenolic antioxidant, and radicals. Predetermined amounts of the generator and the above-mentioned various additives that are usually added to propylene polymers were mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, a tumbler, etc. The radical generator is mixed at a temperature that does not decompose to form a mixture, and the mixture is passed through various melt kneading devices such as a conventional single-screw extruder, twin-screw extruder, Brabender or roll,
A predetermined amount of water is added to the mixture immediately before or in the melting zone of the melt-kneading device, preferably using a melt-kneading device having a deaeration zone, and the melt-kneading temperature is 150° C. to 3.
Melt and knead at 00°C, preferably 180°C to 270°C to form pellets, (2)
A propylene polymer containing 0.5 ppm or more of vanadium or 0.5 ppm or more of vanadium is mixed with predetermined amounts of water, a phenolic antioxidant, thiophosphite, and the various additives mentioned above that are usually added to propylene polymers. Using a device such as Henschel mixer (trade name), super mixer, ribbon blender, Banbury mixer, tumbler, etc., mix at a temperature that does not decompose the blended thiophosphite to form a mixture, and then transfer the mixture to a conventional single screw extruder. , a twin-screw extruder, a Brabender or a roll, etc., using various melt-kneading devices, preferably a melt-kneading device having a degassing area, at a melt-kneading temperature of 250°C to 350°C,
Preferably, the propylene polymer is melt-kneaded at 290°C to 330°C to form pellets. A fixed amount is mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, a tumbler, etc., at a temperature that does not decompose the blended thiophosphite, and the mixture is normally mixed. Using various melt kneading devices such as a single screw extruder, a twin screw extruder, a Brabender or a roll, preferably a melt kneading device having a degassing area, immediately before or in the melt zone of the melt kneading device. A predetermined amount of water is added to the mixture and melt-kneaded at a melt-kneading temperature of 250°C to 350°C, preferably 290°C to 330°C to form pellets. Predetermined amounts of the additives, thiophosphite, and the various additives mentioned above that are usually added to propylene polymers are mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, a tumbler, etc. , the blended thiophosphite is mixed at a temperature that does not decompose to form a mixture, and the mixture is subjected to various types of melt kneading equipment such as a conventional single-screw extruder, twin-screw extruder, Brabender or roll, preferably in a degassing area. Using a melt-kneading device with a melt-kneading temperature of 150°C or higher,
The pellets are melt-kneaded at less than 0°C, preferably from 180°C to 230°C, and the pellets are melt-kneaded using various molding devices such as ordinary spinning machines, film-forming machines, injection molding machines, or blow molding machines. The propylene polymer is melt-kneaded and molded at a temperature of 250°C to 350°C, preferably 290°C to 330°C; A predetermined amount of various additives is mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer,
Using a ribbon blender, Banbury mixer, tumbler, etc., mix at a temperature that does not decompose the blended thiophosphite to form a mixture. A predetermined amount of water is added to the mixture immediately before or in the melting zone of the melt-kneading device using various melt-kneading devices, preferably a melt-kneading device having a deaeration zone, and the melt-kneading temperature is 150°C or higher. Below 250°C, preferably from 180°C
The pellets are melt-kneaded at 230°C, and the pellets are melt-kneaded at 250°C using various molding devices such as ordinary spinning machines, film-forming machines, injection molding machines, or blow molding machines.
-350°C, preferably 290°C - 330°C, melt-kneading and molding, or (2) adding a phenolic antioxidant, thiophosphite, and the above-mentioned various additions usually added to propylene-based polymers to the propylene-based polymer. A predetermined amount of the agent is mixed using a conventional mixing device such as a Henschel mixer (trade name), a super mixer, a ribbon blender, a Banbury mixer, a tumbler, etc. at a temperature that does not decompose the blended thiophosphite to form a mixture. The mixture is melt-kneaded using various types of melt kneading equipment such as an ordinary single-screw extruder, twin-screw extruder, Brabender or roll,
Melt-kneading temperature 150°C or higher and lower than 250°C, preferably 1
The pellets are melted and kneaded at 80°C to 230°C, and the pellets are processed using various molding equipment such as a conventional spinning machine, film forming machine, injection molding machine, or blow molding machine, preferably a molding equipment having a degassing area. adding a predetermined amount of water to the pellets immediately before or in the melting zone of the molding device;
Melt kneading temperature 250°C to 350°C, preferably 290°C
This is carried out by melt-kneading and molding at ~330°C.

[0019]

[Function] In the present invention, the phenolic antioxidant acts as a radical chain inhibitor, and the radical generator generates radicals through melt-kneading treatment, that is, heating, and cleaves the main chain of the propylene polymer. It is well known that it reduces the molecular weight of the polymer and improves moldability. Furthermore, thiophosphite has a temperature of 250
The above-mentioned method generates radicals by melt-kneading, that is, heating, at a temperature of 350°C to 350°C, cuts the main chain of the propylene polymer, reduces the molecular weight of the propylene polymer, and improves moldability. JP 42-14166, JP 47-26436, JP 49-35
It is well known as described in Japanese Patent Application Laid-open No. 451 and Japanese Patent Application Laid-Open No. 52-109547. In the production method of the present invention, water melt-kneads a propylene-based polymer composition stabilized with a phenolic antioxidant in the presence of a radical generator or melt-kneads it at a temperature of 2°C in the presence of a thiophosphite.
When melt-kneading at 50°C to 350°C, the mechanism of action on titanium or vanadium complexes is not clear, but water acts on titanium or vanadium complexes to stabilize them. It is presumed that the active titanium or vanadium is deactivated by the formation of a chelate compound.

[0020]

[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The evaluation method used in Examples and Comparative Examples was as follows. Colorability: YI (Yellownes) of the obtained pellets
s Index) (according to JIS K 7103), and the colorability was evaluated based on the magnitude of this YI value. The smaller this number is, the less coloring there is. Molding processability: MFR (Melt
Flow Rate) was measured (based on JISK 6758), and moldability was evaluated based on the magnitude of this MFR value. The larger this value is, the more improved the moldability is.

Examples 1 to 15, Comparative Examples 1 to 7 As propylene polymers, MFR (load at 230°C: 2.1
Discharge amount of molten resin for 10 minutes when adding 6 kg)2
．． To 100 parts by weight of unstabilized powdered crystalline propylene homopolymer (titanium content 30 ppm) at 0 g/10 min, pure water as water and 2,6-di-t-butyl- as phenolic antioxidant. 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, 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-di-methyl-2,5-di(t-butylperoxy)hexane as a radical generator. Predetermined amounts of bis(t-butylperoxyisopropyl)benzene and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 1 below, and after stirring and mixing for 3 minutes,
The mixture was melt-kneaded at 200° C. using a vented single-screw extruder of 1.5 mm to modify the mixture and pelletize it. In addition, as Comparative Examples 1 to 7, unstabilized powdery crystalline propylene homopolymer (titanium content 30 p
Predetermined amounts of each of the additives listed in Table 1 below were blended with 100 parts by weight of pm), and the mixture was melt-kneaded in accordance with Examples 1 to 15 to obtain modified pellets. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 1.

Examples 16 to 30, Comparative Examples 8 to 14 As the propylene polymer, an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 % by weight, titanium content 35 ppm), pure water as water, and 2,6-di-t-butyl-p- as a phenolic antioxidant.
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, 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-
(butylperoxyisopropyl) benzene and other additives in the proportions listed in Table 2 below in a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then The mixture was melt-kneaded using an extruder at 200° C. to be modified and pelletized. In addition, as Comparative Examples 8 to 14, MFR was 7.0 g/10
unstabilized powdered crystalline ethylene-propylene random copolymer (ethylene content 2.5% by weight,
Example 16
-30 to obtain modified pellets by melt-kneading treatment. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 2.

Examples 31 to 45, Comparative Examples 15 to 21 As the propylene polymer, an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5 % by weight, titanium content 50 ppm), 2,6-di-t-butyl-p-cresol as a phenolic antioxidant,
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, 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-butylperoxy) as a radical generator. oxyisopropyl) benzene and other additives in the mixing ratios listed in Table 3 below into a Henschel mixer (trade name), stirred and mixed for 3 minutes, and then transferred to a vented single-screw extruder with a diameter of 40 mm. When performing melt-kneading treatment at 200°C, a predetermined amount of steam as water is injected into the hopper of the extruder at a blending ratio listed in Table 3 below, and the mixture is melt-kneaded and modified. , pelletized. In addition, as Comparative Examples 15 to 21, MFR is 4
．． 0 g/10 min unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 8
．． 5% by weight, titanium content 50ppm) were blended with predetermined amounts of each of the additives listed in Table 3 below, and the pellets were modified by melt-kneading according to Examples 31 to 45. Obtained. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 3.

Examples 46 to 60, Comparative Examples 22 to 28 As the propylene polymer, an unstabilized powdery crystalline ethylene-propylene-butene-1 ternary copolymer (ethylene Content 2.5% by weight
, butene-1 content 4.5% by weight, vanadium content 0
．． 6ppm), 100 parts by weight of phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxy) phenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3,
5-di-t-butyl-4-hydroxybenzyl)benzene, 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)
Predetermined amounts of hexane or 1,3-bis(t-butylperoxyisopropyl)benzene and other additives are placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 4 below, and mixed by stirring for 3 minutes. After that, when performing melt-kneading treatment at 200°C in a vented single-screw extruder with a diameter of 40 mm, a predetermined amount of pure water is added to the inlet provided in the melting zone between the hopper and the vent of the extruder. were injected in the proportions shown in Table 4 below, modified by melt-kneading, and pelletized. In addition, as Comparative Examples 22 to 28, unstabilized powdery crystalline ethylene-propylene-butene-1 ternary copolymer (ethylene content 2.5
% by weight, butene-1 content 4.5% by weight, vanadium content 0.6ppm) and a predetermined amount of each of the additives listed in Table 4 below were blended into Examples 46 to 60.
Modified pellets were obtained by melt-kneading according to the following. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are summarized in the fourth
Shown in the table.

Examples 61 to 75, Comparative Examples 29 to 35 As the propylene polymer, an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 12.0 % by weight, vanadium content 1.5 ppm), 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, 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- Henschel mixer (product name: ), stirred and mixed for 3 minutes, and then mixed using a vented single-screw extruder with a diameter of 40 mm.
When performing melt-kneading treatment at 0°C, predetermined amounts of water and steam are added to the injection port provided in the melting zone between the hopper and the vent of the extruder so that the mixing ratio is as shown in Table 5 below. It was injected into the liquid, melt-kneaded, modified, and pelletized. In addition, as Comparative Examples 29 to 35, MFR was 4.0 g/10
unstabilized powdered crystalline ethylene-propylene block copolymer (ethylene content 12.0% by weight)
, vanadium content 1.5 ppm) were blended with predetermined amounts of each of the additives listed in Table 5 below, and melt-kneaded according to Examples 61 to 75 to obtain modified pellets. Ta. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 5.

Examples 76 to 90, Comparative Examples 36 to 40 As a propylene polymer, MFR (discharge amount of molten resin in 10 minutes when applying a load of 2.16 kg at 230°C) was 2.0 g/10 minutes. Unstabilized powdered crystalline propylene homopolymer (titanium content 30 ppm) 1
00 parts by weight, pure water as water, and 2,4-bis(n-octylthio)-6-(4-
Hydroxy-3,5-di-t-butylanilino)-1,
3,5-triazine, 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, tris(3,5-di-t-
-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(4'-hydroxy-3
',5'-di-t-butylphenyl)propionate,
As the thiophosphite, predetermined amounts of trilauryl trithiophosphite or di(laurylthio)pentaerythritol diphosphite and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 6 below, and 3 After stirring and mixing for a minute, the mixture was melt-kneaded at 300° C. using a vented single-screw extruder with a diameter of 40 mm, and pelletized. In addition, as Comparative Examples 36 to 40, unstabilized powdery crystalline propylene homopolymer (titanium content 30 p) with an MFR of 2.0 g/10 min
Predetermined amounts of each of the additives listed in Table 6 below were blended with 100 parts by weight of pm), and the mixture was melt-kneaded in accordance with Examples 76 to 90 to obtain pellets. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 6.

Examples 91 to 105, Comparative Examples 41 to 45 As the propylene polymer, an unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 % by weight, titanium content 35 ppm), pure water as water, and 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t- butylanilino)-1,3,5-triazine, 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, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(
Predetermined amounts of 4'-hydroxy-3',5'-di-t-butylphenyl) propionate, trilauryltrithiophosphite or di(laurylthio)pentaerythritol diphosphite as thiophosphite, and other additives are described below. The mixture was put into a Henschel mixer (trade name) at the blending ratio shown in Table 7, stirred and mixed for 3 minutes, and then melt-kneaded at 300°C in a vented single-screw extruder with a diameter of 40 mm to pelletize. In addition, as Comparative Examples 41 to 45, 100 weight of unstabilized powdery crystalline ethylene-propylene random copolymer (ethylene content 2.5 wt%, titanium content 35 ppm) with an MFR of 7.0 g/10 min. A predetermined amount of each of the additives listed in Table 7 below was added to Examples 91 to 1.
Pellets were obtained by melt-kneading treatment in accordance with 05. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 7.

Examples 106-120, Comparative Examples 46-50
As a propylene polymer, 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 8.5% by weight, titanium content 50ppm) with an MFR of 4.0 g/10 minutes, phenol 2,4-bis(n-octylthio)-6 as antioxidant
-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 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, tris(3,5
-di-t-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate, trilauryltrithiophosphite as thiophosphite A predetermined amount of diphosphite or di(laurylthio)pentaerythritol diphosphite and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 8 below, and after stirring and mixing for 3 minutes, a mixture with a diameter of 40 mm was added. When performing melt-kneading treatment at 300°C using a vented single-screw extruder, a predetermined amount of steam as water is injected into the hopper of the extruder at the blending ratio shown in Table 8 below, and the mixture is melted. The mixture was kneaded and pelletized. In addition, as Comparative Examples 46 to 50, MFR was 4.0 g.
/10 minutes of unstabilized powdered crystalline ethylene-
100 parts by weight of a propylene block copolymer (ethylene content: 8.5% by weight, titanium content: 50ppm) was blended with a predetermined amount of each of the additives listed in Table 8 below. The mixture was melt-kneaded to obtain pellets. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 8.

Examples 121-135, Comparative Examples 51-55
As a propylene polymer, an unstabilized powdery crystalline ethylene-propylene-butene-1 ternary copolymer (ethylene content 2.5 wt%, butene-1 content 4 2,4-bis(n-octylthio)-6-(2,4-bis(n-octylthio)-6-(
4-Hydroxy-3,5-di-t-butylanilino)-
1,3,5-triazine, 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, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate or n-octadecyl-β-(4'-hydroxy-3',5'-di-t-butylphenyl) ) Propionate, trilauryltrithiophosphite or di(laurylthio)pentaerythritol diphosphite as thiophosphite, and other additives in predetermined amounts at the blending ratios listed in Table 9 below into a Henschel mixer (trade name). After stirring and mixing for 3 minutes,
When performing melt-kneading treatment at 300°C using a vented single-screw extruder with a diameter of 40 mm, a predetermined amount of pure water was added to the inlet provided in the melting zone between the hopper and the vent of the extruder as described below. The mixture was injected at the blending ratio shown in Table 9, melted and kneaded, and pelletized. In addition, as Comparative Examples 51 to 55, unstabilized powdery crystalline ethylene-propylene-butene-13 element copolymer (ethylene content 2.5% by weight,
Butene-1 content: 4.5% by weight, vanadium content: 0.
Predetermined amounts of each of the additives listed in Table 9 below were blended into 100 parts by weight (6 ppm) and melt-kneaded according to Examples 121 to 135 to obtain pellets. The resulting pellets were evaluated for colorability and moldability using the test methods described above. These results are shown in Table 9.

Examples 136-150, Comparative Examples 56-60
As a propylene polymer, 100 parts by weight of an unstabilized powdery crystalline ethylene-propylene block copolymer (ethylene content 12.0% by weight, vanadium content 1.5ppm) with an MFR of 4.0 g/10 min. , 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 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, tris(3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate or n-octadecyl-β-(4'
-hydroxy-3',5'-di-t-butylphenyl)
Trilauryl trithiophosphite or di(laurylthio) as propionate, thiophosphite
Predetermined amounts of pentaerythritol diphosphite and other additives were placed in a Henschel mixer (trade name) at the mixing ratios listed in Table 10 below, mixed for 3 minutes, and then extruded using a vented single-screw extrusion having a diameter of 40 mm. The mixture was melt-kneaded in a machine at 200° C. to obtain pellets (hereinafter abbreviated as pellets ①). Furthermore, using the obtained pellet
When performing melt-kneading treatment at 0°C, predetermined amounts of water and steam are added to the injection port provided in the melting zone between the hopper and the vent of the extruder so that the mixing ratio is as shown in Table 10 below. The pellets (hereinafter abbreviated as pellets) were obtained by repeating the melt-kneading process. In addition, as Comparative Examples 56 to 60, unstabilized powdery crystalline ethylene-propylene block copolymers (ethylene content 12.0 wt%, vanadium content 1.5 ppm) with an MFR of 4.0 g/10 min. A predetermined amount of each of the additives listed in Table 10 below was added to 100 parts by weight, and 20 parts by weight were added.
Pellets (2) were obtained by melt-kneading at 0° C., and melt-kneading was repeated at 300° C. using the obtained pellets (2) in accordance with Examples 136 to 150 to obtain pellets (2). Using the obtained pellets (1) and (2), the colorability and moldability were evaluated using the test method described above. These results are shown in Table 10. The additives shown in Tables 1 to 10 are as follows.

Water [1]: Pure water Water [2]: Steam Phenolic antioxidant [1]: 2,6-di-t-butyl-p-cresol Phenolic antioxidant [2]: 2,4 -bis(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine phenolic antioxidant [3]: Tetrakis[methylene-3-(3 ',5'-di-t-butyl-4'-hydroxyphenyl)propionate] methanephenolic antioxidant [4]: 1,3,5-trimethyl-2,4,6-tris(3,5-di -t-butyl-4
-Hydroxybenzyl)benzenephenolic antioxidant [5]: Tris(3,5-di-
t-Butyl-4-hydroxybenzyl) isocyanurate phenolic antioxidant [6]: n-octadecyl-
β-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate radical generator [1]: 2,5-di-methyl-2,5-
Di(t-butylperoxy)hexane radical generator [2]: 1,3-bis(t-butylperoxyisopropyl)benzene thiophosphite [1]: Trilauryl trithiophosphite Thiophosphite [2]: Di (Laurylthio)pentaerythritol diphosphite phosphorus antioxidant 1: Tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene-di-phosphonite phosphorus antioxidant 2: Bis (2,4-di-t-butylphenyl)-pentaerythritol-diphosphite phosphorus antioxidant 3: bis(2,6-di-
t-Butyl-4-methylphenyl)-pentaerys
Litol-diphosphite phosphorus antioxidant 4: Bis(2,4,6-tri-t-butylphenyl)pentaerythritol-diphosphite phosphorus antioxidant 5
: Tris(2,4-di-t-butylphenyl)phosphite phosphorus antioxidant 6:2,2'-methylene-bis(4,
6-di-t-butylphenyl)octyl phosphite phosphorus antioxidant 7: 2,2'-ethylidene-bis(4,6-di-t-butylphenyl)fluorophosphite GMS: Glyceryl monostearate Zn- St: Zinc stearate Ca-St: Calcium stearate

The Examples and Comparative Examples listed in Table 1 below are cases where a crystalline propylene homopolymer was used as the propylene polymer. As can be seen from Table 1, in Examples 1 to 15, water was added to the crystalline propylene homopolymer containing 30 ppm of titanium in the catalyst residue related to the present invention.
It is blended with a phenolic antioxidant and a radical generator, and modified by melt-kneading. Examples 1-15
Comparing with Comparative Example 1 (containing phenolic antioxidant and not containing water and radical generator),
It can be seen that Examples 1 to 15 have little coloration and improved moldability, whereas Comparative Example 1 has little coloration but has no improvement in moldability. Comparative example 1
Comparing Comparative Example 2 in which water was used in combination with Examples 1 to 15, it can be seen that Comparative Example 2 has less coloring than Comparative Example 1, but like Comparative Example 1, moldability is not improved. Comparing Examples 1 to 15 with Comparative Examples 3 to 5, in which phenolic antioxidants and radical generators were blended but no water, Comparative Examples 3 to 5 had the same moldability as Examples 1 to 15. Although it has been improved, it can be seen that the coloring is significant. In addition, the present applicant previously proposed JP-A-62
The method for producing a modified propylene polymer proposed in Publication No. 252443 is to blend a partial ester of a polyol with a fatty acid, a phenolic antioxidant, and a radical generator into a propylene polymer, and then melt-knead the mixture to modify it. The method for producing a modified propylene polymer composition proposed in Comparative Example 6 and JP-A No. 63-308052, namely, blending a zinc salt of a carboxylic acid, a phenolic antioxidant, and a radical generator into a propylene polymer. , Comparative Example 7 and Examples 1 to 1 modified by melt-kneading treatment
Comparing Example 5, Examples 1 to 15 and Comparative Examples 6 to 7 have the same moldability, but Examples 1 to 15 have even less coloring than Comparative Examples 6 to 7, and water is used as a coloring inhibitor. It is clear that the partial esters of polyols and fatty acids and the zinc salts of carboxylic acids have a superior effect. Furthermore, Examples 9 to 15 in which water, a phenolic antioxidant, a radical generator, and a phosphorus antioxidant according to the present invention were blended and modified by melt-kneading were compared to Example 5. It can be seen that the excellent anti-coloration effect of water is not inhibited, and a remarkable synergistic effect is observed by the combined use of phosphorous antioxidants.

Tables 2 to 5 show crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, and crystalline ethylene-propylene-butene-1 ternary copolymer as propylene polymers, respectively. The same effects as those described above were confirmed for these as well. The examples and comparative examples listed in Table 6 are:
This is a case where a crystalline propylene homopolymer is used as the propylene polymer. As can be seen from Table 6, in Examples 76 to 90, the titanium content of the catalyst residue related to the present invention was 3
A crystalline propylene homopolymer containing 0 ppm was blended with water, a phenolic antioxidant, and thiophosphite, and melt-kneaded at 300°C. Example 7
Comparing Examples 6 to 90 with Comparative Examples 36 to 38 (containing a phenolic antioxidant and thiophosphite and no water), it can be seen that Comparative Examples 36 to 38 are significantly colored. In addition, the present applicant previously
Comparison of the method for improving the processability of propylene polymers proposed in Publication No. 170439, in which partial esters of polyol and fatty acid, phenolic antioxidants, and thiophosphites are blended into propylene polymers, and the mixture is melt-kneaded at 300°C. Example 39 and JP-A-63-309
A method for improving the processability of propylene polymers proposed in Publication No. 543, namely, Comparative Example 4 in which a zinc salt of a carboxylic acid, a phenolic antioxidant, and a thiophosphite were blended into a propylene polymer, and the mixture was melt-kneaded at 300°C.
0 and Examples 76 to 90, Examples 76 to 90
The coloration was even less than that of Comparative Examples 39 to 40, and it is clear that water has a better effect as a coloration inhibitor than partial esters of polyols and fatty acids and zinc salts of carboxylic acids. Furthermore, Examples 84 to 90, in which water, a phenolic antioxidant, a thiophosphite, and a phosphorus antioxidant according to the present invention were blended and melt-kneaded, compared to Example 80, It can be seen that a remarkable synergistic effect is observed due to the combined use of a phosphorus antioxidant without inhibiting the excellent anti-coloration effect.

Tables 7 to 9 show crystalline ethylene-propylene random copolymer, crystalline ethylene-propylene block copolymer, and crystalline ethylene-propylene-butene-1 ternary copolymer as propylene polymers, respectively. The same effects as those described above were confirmed for these as well. Further, the Examples and Comparative Examples listed in Table 10 are cases where a crystalline ethylene-propylene block copolymer was used as the propylene polymer. 10th
As can be seen from the table, in Examples 136 to 150, a phenolic antioxidant and thiophosphite were blended with a crystalline ethylene-propylene block copolymer containing 1.5 ppm of vanadium in the catalyst residue related to the present invention, Pellets (2) were obtained by melt-kneading at 200°C, water was added to the pellets (2), and pellets (2) were obtained by repeating the melt-kneading at 300°C. Also,
In Comparative Examples 56 to 60, pellets (1) and (2) were obtained in the same manner as in Examples 136 to 150 using the same additives as in Comparative Examples 36 to 40. Examples 136-15
Comparing No. 0 with Comparative Examples 56 to 60, pellets ■, which is a propylene-based polymer composition obtained by melt-kneading at 300°C in the presence of thiophosphite, were also found to be No. 6.
It can be seen that the same effect as in the table was confirmed. Therefore, it can be seen that the modified propylene polymer composition obtained by the production method of the present invention is free from coloration and has improved moldability.

[0035]

Effects of the Invention The modified propylene polymer composition obtained by the production method of the present invention is disclosed in JP-A-62-252443 and JP-A-63-12650 filed by the present applicant.
Modified propylene polymer compositions related to No. 63-308052 and JP-A-63-308052, and processability related to JP-A No. 63-170439 and JP-A No. 63-309543 filed by the present applicant. Compared to improved propylene polymers, it is less colored and has improved molding processability, making it suitable for manufacturing desired molded products using various molding methods such as injection molding, extrusion molding, and blow molding. can be used.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

[Table 9]

[0045]

[Table 10]

Claims (2)

[Claims] Claim 1: 0.01 to 1 part by weight of a phenolic antioxidant and a radical generating agent to 100 parts by weight of a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue. 0.
0.001 to 0.5 parts by weight is blended and melt-kneaded at 150°C to 300°C to modify the propylene polymer.
A method for producing a modified propylene polymer composition, which comprises melt-kneading in the coexistence of 1 to 1 part by weight of water. 2. 0.01 to 1 part by weight of a phenolic antioxidant and thiophos per 100 parts by weight of a propylene polymer containing 5 ppm or more of titanium or 0.5 ppm or more of vanadium in the catalyst residue. When modifying a propylene polymer by blending 0.01 to 5 parts by weight of phyto and melt-kneading at 250°C to 350°C, 0.0
1. A method for producing a modified propylene polymer composition, which comprises melt-kneading in the coexistence of 1 to 1 part by weight of water.