JPH106376A - Polyolefin extrusion molded object - Google Patents

Abstract

PROBLEM TO BE SOLVED: To markedly prevent oxidation even in the case of use especially under environment containing water by compounding a specific phenol compd. component with a polyolefin resin. SOLUTION: A polyolefin extrusion molded object is an extrusion molded object of a polyolefin resin and the polyolefin resin is prepared by compounding 0.01-3 pts.wt. of a phenol compd. component represented by formula I with 100 pts.wt. of polyolefin. In the formula I, X is a group represented by formula II (wherein R1 and R4 may be same or different and are respectively a 1-8C alkyl group and R2 , R3 , R5 and R6 may be same or different and are respectively a hydrogen atom or a 1-8C alkyl group). Since the phenol compd. having a specific structure is a hindered phenol compd., oxidation preventing effect is developed under environment containing water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyolefin extrudate. More specifically, the present invention relates to an extruded polyolefin resin having excellent durability even in an environment where a solvent such as water is present.

[0002]

2. Description of the Related Art Polyolefins have a problem in that they undergo oxidation during processing and use and their quality deteriorates. For this reason, various antioxidants have conventionally been developed and incorporated into materials for the purpose of preventing oxidative deterioration. Among them,
Hindered phenol compounds (for example, Japanese Patent Publication No. 38-1)
70164, JP-B-39-4620, JP-B-39-
No. 21140, JP-B-42-9651, JP-A-62-965
No. 30134) are particularly useful for preventing oxidative deterioration of synthetic polymer materials such as polyolefins, and are currently in practical use. However, when a material stabilized by various antioxidants is used in an environment where water is present, the effect of preventing oxidation deterioration is significantly reduced, and the quality of the polyolefin resin is significantly reduced. . Conventionally, it has been considered that such a cause is due to the fact that the antioxidant in the synthetic polymer material is extracted with water or extracted after being hydrolyzed. Therefore, materials used in an environment where water is present generally do not contain an ester structure and have a high molecular weight, rigid antioxidant to prevent extraction or hydrolysis by water. A method of compounding an agent has been performed (see Japanese Patent Application Laid-Open No. 2-265939).

[0003]

However, the compounding of an antioxidant having such a special structure does not sufficiently satisfy the required resistance to oxidation deterioration, so that it may be used in an environment where water is present. There is a need for antioxidants that are also particularly effective in preventing oxidation.

[0004]

The present inventors have repeatedly studied the mechanism of oxidative deterioration of polyolefin, the mechanism of preventing oxidative deterioration, and the interaction with water. The present inventors have found that they have excellent ability to prevent oxidative deterioration, and in particular, can exert a remarkable effect even when used in an environment where water is present, and have completed the present invention. That is, the polyolefin extruded product of the present invention is made of polyolefin 10
It is characterized in that 0.01 to 3 parts by weight of a phenol compound component represented by the following general formula [1] is mixed with 0 part by weight. General formula [1] [Wherein, X represents a group represented by the following general formula [2]. General formula [2]

[0005]

Embedded image

(Wherein R ₁ and R ₄ may be the same or different and each represents an alkyl group having 4 to 8 carbon atoms;
R ₂ , R ₃ , R ₅ , and R ₆ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )]

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION

[I] Extruded polyolefin (1) Polyolefin resin composition (a) Constituent polyolefin resin Various polyolefin resins are used as the polyolefin resin used in the polyolefin resin composition as a raw material of the extruded polyolefin of the present invention. can do. Specific examples of such polyolefin resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, poly-α-olefins such as polybutene-1, ethylene-propylene random or block copolymers, ethylene-butene- (1) α-olefin copolymers such as random copolymers, polyolefins such as copolymers of poly-α-olefins with other monomers such as maleic anhydride-modified polypropylene, and polyolefins such as mixtures thereof, and the like. it can. Among these, the effects of the present invention can be remarkably exhibited by using polypropylene. In particular, as the polypropylene,
Propylene homopolymer or propylene and ethylene, butene-1, pentene-1, hexane-1,4-
Α-olefins such as methyl-pentene-1, unsaturated carboxylic acids and derivatives thereof such as acrylic acid, ethyl acrylate and maleic anhydride; vinyl esters such as vinyl acetate; unsaturated aromatic compounds such as styrene and methylstyrene; And a random, block, or graft copolymer.

Phenol compound In the polypropylene resin composition of the present invention, the phenol compound blended in the polypropylene resin is a phenol compound represented by the following general formula [I]. General formula [1] [Wherein, X represents a group represented by the following general formula [2]. General formula [2]

[0009]

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(Wherein R ₁ and R ₄ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms;
R ₂ , R ₃ , R ₅ , and R ₆ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )] Specific examples of each symbol represented by the phenol compound represented by the general formula [I] are as follows. As R ₁ and R ₄ , an alkyl group having 1 to 8, preferably 1 to 5 carbon atoms, each of which is linear,
It may be either branched or cyclic. Specifically, methyl, ethyl, n-propyl, isopropyl, n
-Butyl group, isobutyl group, sec-butyl group, ter
t-butyl group, pentyl group, isopentyl group, sec-
Pentyl group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclohexyl group, heptyl group, n-octyl group, isooctyl group, sec-octyl group, Examples include a tert-octyl group and a 2-ethylhexyl group. R ₂ , R ₃ , R ₅ and R ₆ each represent a hydrogen atom, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, 2-methylbutyl Group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclohexyl group, heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, 2-ethylhexyl group, etc. An alkyl group having 1 to 8, preferably 1 to 5 carbon atoms, which may be linear, branched or cyclic.

X in the compound of the general formula [1]
Is not necessarily the same for all three,
Usually, it is preferable that they are the same. The general formula [1]
Is usually 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) butane or 1,1,3-tris (3-methyl-4-hydroxy-5-tert-butylphenyl) butane and the like;
5-di-tert-butyl-4-hydroxyphenylpropionic acid or 3-methyl-5-tert-butyl-4
It is obtained by a chemical reaction with -hydroxyphenylpropionic acid or the like or the corresponding propionyl chloride, etc., and is a crude product of the reaction (a compound produced as a by-product in the reaction may be mixed at an arbitrary ratio). It may be.

Specific examples of the phenol compound represented by the general formula [1] include 1,1,3-tris [2-methyl-4- (3,5-di-tert-butyl-4-hydroxyphenyl). Propionyloxy) -5-tert-butylphenyl] butane, 1,1,3-tris [3-methyl-4- (3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy) -5-butylphenyl ] Butane, 1,1,3-tris [2-methyl-4-
(3-methyl-5-tert-butyl-4-hydroxyphenylpropionyloxy) -5-tert-butylphenyl] butane, 1,1,3-tris [3-methyl-
4- (3-methyl-5-tert-butyl-4-hydroxyphenylpropionyloxy) -5-tert-butylphenyl] butane. These can be used alone or in combination of two or more.

The feature of the phenol compound represented by the general formula [1] is that it is a hindered phenol compound having a hindered phenyl ester structure. That is, in an environment where water is present, hindered phenol exhibits an antioxidant effect at the beginning of use, and the hindered phenyl ester is deteriorated by the action of water during use.
Since hindered phenol is newly generated and the ability to prevent oxidative deterioration can be continuously exhibited, a long-term effect of preventing oxidative deterioration can be exhibited even in an environment where a solvent such as water is present.

(B) Amount ratio In the polyolefin extruded product of the present invention, the amount of the phenol compound represented by the general formula [1] blended in the polyolefin resin is 0.01 to 100 parts by weight of the polypropylene resin. 3 parts by weight, preferably 0.01 to
1 part by weight, particularly preferably 0.03 to 0.7 part by weight. If the amount of the phenol compound is less than the above range, the effect of preventing deterioration is insufficient. On the other hand, when it exceeds the above range, defects such as bleeding and discoloration occur.

(C) Additional component (optional component) The polyolefin extruded product of the present invention consists essentially of a mixture of the above polyolefin resin and the above-mentioned component (1). Thus, additional components other than these may be added to such an extent that the effects of the compound of the present invention are not significantly impaired. Specific examples of such additional components include antioxidants other than the general formula [1], such as other phenolic antioxidants, phosphorus antioxidants, light stabilizers, ultraviolet absorbers, Deactivator,
Or, flame retardants, ionic, non-ionic antistatic agents,
Lubricants such as silicone oil and amide, processing aids, neutralizers,
Nucleating agents, plasticizers, inorganic and organic pigments, dispersants, fillers such as talc, calcium carbonate, barium sulfate, foaming agents, peroxides, fluorescent whitening agents, and resins other than the polyolefin resin , Rubber and the like. Among the additional components, in particular, a sulfur-based antioxidant, or a hindered amine-based stabilizer is further used in combination with the compound of the present invention, as in the case of using with a normal phenol-based antioxidant. Excellent effects of the present invention can be exhibited.

Yellow antioxidants Examples of the sulfur antioxidants include dialkyl thiodipropionates such as dilauriti dipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, and didocosyl thiodipropionate. Dialkyl disulfides such as pionates and distearyl disulfide; alkylthiopropionic acids such as tetrakis [methylene (laurelthiopropionate)] methane and tetrakis [methylene (stearylthiopropionate)] methane; and polyhydric alcohols And the like,
It is not limited to these. These can be used alone or in combination of two or more. The compounding amount of the sulfur-based antioxidant is preferably 0.1 to 10 times, particularly preferably 1 to 7 times the amount of the phenol compound represented by the general formula [1].

Hindered amine stabilizers Hindered amine stabilizers include, for example, N, N '
-Bis (3-aminopropyl) ethylenediamine-2,
4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-
1,3,5-triazine condensate, poly [｛6- (1,
(1,3,3-tetramethylbutyl) imino-1,3,5
-Triazine-2,4-diyl} (2,2,6,6-
Tetramethyl-4-piperidyl) imino {hexamethylene} (2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2 succinate , 2,6,6-tetramethylpiperidine polycondensate, poly- {2-N, N'-
Di (2,2,6,6-tetramethyl-4-piperidyl)
Hexanediamine-4- (N-monophorino) symtriazine}, but is not limited thereto. These can be used alone or in combination of two or more. The amount of the hindered amine-based stabilizer is preferably 0.2 to 5 times, particularly preferably 0.3 to 4 times the amount of the phenol compound represented by the general formula [1].

Other antioxidants The other antioxidants include 2,6-di-
t-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,
4'-butylenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-
t-butylphenol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), d, l-α-
Hindered phenol compounds such as tocopherol, tris (mixed-mono and di-nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-) Butylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-di-t-butylphenyl) 4-4 '
And aromatic phosphorus compounds such as -biphenylene-diphosphonite. Even if these are one kind,
More than one species can be used. Preferred amounts of the above-mentioned other antioxidants include the polyolefin resin 1
Generally, 0.01 to 3 parts by weight is added to 00 parts by weight.

Filler Examples of the filler include talc, mica, glass fiber and the like. These can be used alone or in combination of two or more. The preferable amount of the filler is generally 0.1 to 50 parts by weight based on 100 parts by weight of the polyolefin resin.

Resins / Rubber The resins and rubbers include polyamide, polyester,
Polystyrene, ethylene-propylene copolymer rubber,
Ethylene-butene-based copolymer rubber can be used. These can be used alone or in combination of two or more. The preferred amount of the resin or rubber is generally 1 to 40 parts by weight per 100 parts by weight of the polyolefin resin.
It is blended by weight.

(2) Extrusion Molding Extrusion molding of the polyolefin resin for extruding the above-mentioned polyolefin resin composition can be carried out in the same manner as generally known polyolefin resin extrusion molding methods. Examples of the extrusion molding method include a blow molding method, an injection blow molding method, a pipe molding method, and a sheet molding method.

[II] Applications The shape of the polyolefin extruded product obtained by the above extrusion molding is substantially determined by its use, and examples include polyolefin resin extruded products of various shapes. Extruded products of polyolefin resin can be particularly affected by the effects of the present invention, water, surfactant aqueous solution, acidic aqueous solution, alkaline aqueous solution, seawater, domestic wastewater, ethylene glycol, products that come into contact with solvents such as propylene glycol, In particular, use in contact with water, and furthermore, a molded article in contact with water at a high temperature are preferable. Specific examples of such suitable products include oil and gas pipes, water pipes, water pipes, hot water distribution, heating equipment pipes, water storage tanks, bathtub parts, floats, buoys, water tanks, pipes. Parts, cosmetic containers, automobile reserve tanks, brake oil tanks,
Gasoline tanks, washer tanks and the like can be mentioned. In these extruded products, the effect of improving the thermal solvent extraction, which is the effect of the present invention, can be effectively exerted, so that the commercial value can be increased.

[0023]

EXAMPLES In order to explain the present invention in more detail, the following will be described.
The present invention will be specifically described with reference to Examples and Comparative Examples. Example 1 MFR 1.0 g / 10 min (JISK6758, 230
C), 100 parts by weight of a propylene / ethylene block copolymer having an ethylene content of 14% by weight were blended with the amount of the compound shown in Table 1 and thoroughly mixed with a mixer. The mixture was melt-kneaded by an extruder and granulated. The obtained pellets are set on a pipe forming machine with a cylinder diameter of 65 mm,
m, a pipe having a thickness of 2 mm was formed. When forming a pipe,
1.0% by weight of a carbon black pigment was dry-blended and colored, and then provided for molding. About the obtained pipe,
A hot water test was performed. That is, the pipe has a length of 5c.
m, and the sample was prepared. The sample was placed in a 300 cc stainless steel pressure-resistant tube containing 30 cc of seawater, heated in a 150 ° C. oven, and released every 24 hours. Was measured until the brittleness became brittle, and the durability was determined. Table 1 shows the obtained results.

The details of the compounds indicated by the abbreviations in the table are shown below. Compound A1 of the formula [1] : 1,1,3-tris [2-methyl-4- (3,
5, -Di-tert-butyl-4-hydroxyphenylpropionyloxy) -5-tert-butylphenyl] butane A2 1,1,3-tris [3-methyl-4- (3,
5, -Di-tert-butyl-4-hydroxyphenylpropionyloxy) -5-tert-butylphenyl] butanephenol antioxidant B1: 1,3,5-trimethyl-2,4,6-tris (3 5-di-t-butyl-4-hydroxybenzyl)
Benzene (trade name “IRGANOX 133” manufactured by Ciba-Geigy)
0 ") B2: tetrakis [methylene-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate] methane (trade name “IRGANOX 101” manufactured by Ciba-Geigy)
0 ") B3: 3,9- [2- {3- (3-t-butyl4-hydroxy-5-methylphenyl) propionyloxy}-
1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (Adeka Stab AO80)

Sulfur-based antioxidant C1: tetrakis [methylene (laurylthiopropionate)] methane (Cipro Chemical Co., Ltd. “Seanox 412S”) C2: distearylthiodipropionate (Yoshitomi Pharmaceutical “DSTP Yoshitomi”) hindered amine Stabilizer D1: N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,
6,6-pentamethyl-4-piperidyl) amino] -6
-Chloro-1,3,5-triazine compound (Chiba Geigy “Kimasorb 119FL”)

Phosphorus antioxidant E1: Tris (2,4-di-t-butylphenyl) phosphite (Irgafos 168, Ciba-Geigy) Neutralizer F1: Calcium stearate (Kosaic "Ca-st")

[0027]

[Table 1]

[0028]

As described above, in the polyolefin extruded product of the present invention, the phenol compound having a specific structure blended in the polyolefin resin as a raw material is a hindered phenol compound having a hindered phenyl ester structure. Therefore, in an environment where water exists,
Hindered phenol exhibits an antioxidant effect in the early stage of use, and if the hindered phenyl ester is altered by the action of water during use, hindered phenol is newly generated, and the ability to prevent oxidation deterioration can be continuously exhibited. Therefore, even when used in an environment where water is present,
A long-term effect of preventing the polyolefin resin from being oxidized and degraded can be exhibited, and a polyolefin extruded product having excellent durability can be obtained.

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[Procedure amendment]

[Submission date] July 8, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image (Where R ₁ and R ₄ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms, and R ₂ , R ₃ ,
R ₅ and R ₆ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0005

[Correction method] Change

[Correction contents]

[0005]

Embedded image

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

(Wherein R ₁ and R ₄ may be the same or different and each represents an alkyl group having 1 to 8 carbon atoms;
R ₂ , R ₃ , R ₅ , and R ₆ may be the same or different and each represent an alkyl group having 1 to 8 carbon atoms. )

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

[0009]

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──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C09K 15/18 C09K 15/18 // B29K 23:00 (72) Inventor Kimiho Osegaki Mie 1 Tohocho, Yokkaichi-shi Mitsubishi Chemical Corporation Yokkaichi Research Institute (72) Inventor Sadao Nagase 1 Tohocho, Yokkaichi-shi, Mie Prefecture Mitsubishi Chemical Corporation Yokkaichi Research Institute (72) Inventor Takashi Mori Mie 1 Tohocho, Yokkaichi City Mitsubishi Chemical Corporation Yokkaichi Research Institute

Claims (4)

[Claims] 1. A polyolefin resin extruded product comprising 0.01 to 3 parts by weight of a phenolic compound represented by the following general formula [1] based on 100 parts by weight of a polyolefin resin. A polyolefin extruded product characterized by comprising: General formula [1] [Wherein, X represents a group represented by the following general formula [2]. General formula [2] (Where R ₁ and R ₄ may be the same or different and each represents an alkyl group having 4 to 8 carbon atoms, and R ₂ , R ₃ ,
R ₅ and R ₆ may be the same or different and each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. )] 2. The polyolefin extruded product according to claim 1, wherein the phenol compound represented by the general formula [1] is used in combination with another antioxidant. 3. The extruded polyolefin product according to claim 2, wherein the other antioxidant is a sulfur-based antioxidant. 4. The extruded polyolefin product according to claim 2, wherein the other antioxidant is a hindered amine stabilizer.