JPH01297444A - Ozone-resistant polyolefin molded body - Google Patents

Abstract

PURPOSE:To obtain the subject molded body, consisting of a composition prepared by blending a polyolefin with a specific compound, such as a nickel- containing complex salt-based compound, in a small amount and useful as peripheral members, such as electrostatic copiers, automobiles, mercury or xenon lamps. CONSTITUTION:The objective molded body, consisting of a composition prepared by blending (A) 100 pts.wt. polyolefin (preferably propylene.ethylene-block copolymer) with (B) 0.001-2 pts.wt. compound selected from nickel-containing complex salt-based compounds {e.g., [2,2'-thiobis(4-tert-octylphenol)]-nbntylaminenickel[II], piperidine-based compounds (e.g. bis-2,2,6,6-tetramethyl-4-piperidyl sebacate), piperazine-based compounds {e.g., N,N'-bis[2-(tetradecyloxycarbonyl) ethyl]piperazine}, benzoate-based compounds (e.g., n-hexadecyl-3,5-di-tert-butyl-4- hydroxybenzoate) and tocopherol and in contact with an atmosphere with >=0.1ppm ozone concentration.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a polyolefin molded article, and particularly to a polyolefin molded article with excellent ozone resistance that can be used in an atmosphere containing an ozone concentration of 0.1 ppra or more. It is something.

[Prior art] Polyolefins such as polyethylene and polypropylene are
Due to its excellent material properties, it is widely used in various applications, and some of these applications involve use in atmospheres with high ozone concentrations.

Normal atmospheric ozone concentration is at most 3.5 pph+s
However, when the ozone concentration exceeds 0.1 pprn, it becomes necessary to take into account the deterioration of the properties of polyolefin due to ozone deterioration.

In general, a well-known method for improving the ozone resistance of polymers, especially for polymers having unsaturated bonds such as rubber, is the addition of an aromatic amine stabilizer.

[Problems to be Solved by the Invention] However, the formulation of this aromatic amine stabilizer has problems in terms of significant coloring and safety and hygiene, and a safer and more effective stabilizer is desired.

In addition, particularly for polyolefins, the problem of ozone resistance and its countermeasures have not necessarily been clarified.

[Means for Solving the Problem] The present invention solves the above-mentioned problems regarding polyolefin molded articles, and it has been discovered that an additive having a specific structure is effective in improving the ozone resistance of polyolefin. It is something that

That is, in the present invention, 0.001 parts by weight of a compound selected from fA) to fEl below is added to 100 parts by weight of polyolefin.
It consists of a composition containing ~2 parts by weight, and the ozone concentration is 0.
The present invention provides an ozone-resistant polyolefin molded article, which is characterized by being in contact with an atmosphere of 1 ppa+ or more.

(A) Nickel-containing complex salt compound fBl Piperidine compound fcl Piperazine compound (Dl benzoate compound fEl α-tocopherol.

Polyolefin The polyolefin used in the molded article of the present invention is α-
They are homopolymers and copolymers of olefins. These polyolefins include, for example, low density, medium density and high density polyethylene, propylene homopolymer, propylene/ethylene block copolymer, propylene/ethylene random copolymer, propylene/ethylene/butene-1 copolymer. Coalescence, polybutene-■, poly4-methylbutene-1, poly3-methylbutene-1, poly4-methylpentene-1, propylene/ethylene copolymer rubber, ethylene/butene copolymer rubber, ethylene/butene-I copolymer , ethylene/hexene-1 copolymer, ethylene/octene copolymer, etc., and further modified versions of these polymers, i.e., unsaturated carboxylic acids or derivatives thereof, aromatic unsaturated monomers, Copolymerized vinyl esters, vinyl silanes, etc. may also be used. Also, a blend of these may be used.

Preferred polyolefins include low, medium, and high pressure polyethylene, polypropylene, propylene/ethylene random and block copolymers, propylene/ethylene/butene-1 copolymers, and propylene/ethylene/butene-1 copolymers.
Block copolymers are most preferred.

Among the compounds incorporated into the polyolefin in the present invention, the following compounds can be exemplified as the compounds (compounds (A) to fD other than El).

Compound (A) (a-11[2,2-thiobis(4-t-octylphenol)1-n-butylamine nickel [II] (a
-2) Complex or mixture of nickel-dibutyl-dithiocarbamate (a-3) nickel-bisfp-t-octylphenol sulfide) and nickel-bis(2-ethylhexanoate) (a-41 nickel-bis[〇-ethyl(3,5) -dibutyl-4-hydroxybenzyl)1 phosphonate (a-51 nickel hindered amine complex salt compound (B) (b-11bis-2,2,6,6-tetramethyl-4-
Piperidyl Sepacate fb-21 Dimethyl corkate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylbiperidine polycondensate fb-31 Poly[(6-(1, 1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-
diyl) (2,2,6,6-tetramethyl-4-piperidylimino)hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)) (b-4+ 2- +3.5 -di-t-butyl-4-hydroxybenzyl l-2-n-butylmalonate bis f
l.

2,2.6.6-bentamethyl-4-piperidyl) (b-51tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-1,2,:1.4-butanetetracarboxylate fb- 61 poly[2,N, N-di (2,2,6,6
-Tetramethyl-4-piperidyl)hexanediamine-
4-(N-morpholino)simtriazine] fb-71N, N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 1.
Polycondensate with 2-dibromoethane 1b-8) Tris C2,2,6,6-tetramethyl-4-piperidyl)-dodecyl-1,2,3,4-butanetetracarboxylate fb-911-Lis ( 1,2,2,6,6-bentamethyl-4-piperidyl)-dodecyl-C2,3,4-butanetetracarboxylate (b-101bis-1,2,2,6,6-bentamethyl-4-piperidyl sebacate Compound (C1 fc-1) N, N'-bis[2-(tetradecyloxycarbonyl)ethyl 1-piperazine fc-21N, N'-bis[2-(tetradecyloxycarbonyl)-1-methylethyl 1-piperazine fc -3
1N,N'-bis[2-(tetradecyloxycarbonyl)ethyl]-2,5-dimethylpiperazinefc-41N,N-bis[2-(octadecyloxycarbonyl)ethyllpiperazine(c-51N,N'- Bis[2-(octadecyloxycarbonyl)methyl]piperazine 1c-6) N,N-bis[2-f tridecylcarbonyloxy)ethyl 1piperazine(c-71N,N'-bis[2-(2,2, 6,6-tetramethyl-4-piperidyloxycarbonyl)ethyl piperazine (C-8) tetrakis(3-if-piperidyl)propionyloxymethyl 1 methane (c-91tetrakis[3-fl-morpholyl)propionyloxymethyl 1 Methane (c-101tetrakis[3-[4-(2-ftetradecyloxycarbonyl)ethyl)-piperazyl1propionyloxymethyl]methane compound fil fd-11n-hexadecyl-35-di-t-butyl-
4-Hydroxybenzony! - (d-212,4-di-t-butylphenyl-3,5-
Among the compounds (A) to IEI, (
A), fBl, fcl, fE) are preferred, tAli old, (C) are more preferred, and IA) and (C) are particularly preferred. Specifically, (a-
11, fa-2), (b-11, fb-21, +b
-3+, fb-51, (b-10), (c-1) and +d-21 are good examples.

In the present invention, two or more compounds having different structures can be used in combination, and such a combination is preferable in terms of achieving the desired effect.

Blending, crosstalk The blending amount of these compounds is 0.001 to 2 parts by weight, preferably 0.001 to 2 parts by weight, per 100 parts by weight of polyolefin.
．． 0.01 to 1 part by weight, particularly preferably 0.03 to 0.5 parts by weight.

In addition, other additives that are usually added to polyolefins, such as pigments, fillers, foaming agents, antistatic agents, antifogging agents, surface treatment agents, lubricants, as long as they do not significantly impede the effects of the present invention, may also be added.
Flame retardants, metal deactivators, nucleating agents, metal soaps, clarifying agents,
Processing aids, antibacterial agents, ultraviolet absorbers, light stabilizers, mold release agents,
Peroxide etc. can be blended.

The composition of the present invention is manufactured by one conventional resin crossing method or molding method. For example, the essential components of the present invention and other additional components are blended into powder or pellet polyolefin, mixed with a Henschel mixer, etc., and then melted and kneaded with a mixer such as an extruder to form a pellet composition. . At this time, the compounded components may be added to the polyolefin during mixing, or may be added in a master batch method.

The obtained pellets are subjected to various molding processes such as injection molding, extrusion molding, blow molding, film molding, and spinning, and if necessary, are further subjected to secondary processing to obtain the molded product of the present invention.

These molded bodies of the present invention can be deodorized, bleached, sterilized, disinfected,
Containers, equipment, and peripheral parts when ozone is used for purposes such as bleaching and treatment, aircraft parts exposed to ozone at high altitudes, and equipment incorporating high-voltage generators (electrostatic copying machines, automobiles, etc.) It can be used for peripheral materials such as , mercury lamps, and xenon lamps. 2. Injection molded products are preferred and practical for molded products used in these applications.

[Effect] The mechanism of ozone deterioration of rubbers that have unsaturated bonds in their molecular structures has been well analyzed, and the effectiveness of aromatic amine-based antioxidants as anti-deterioration agents has been confirmed. There is.

Furthermore, with regard to ozone deterioration of polymers that are essentially saturated compounds as shown in the present invention, studies have been conducted on the deterioration mechanism in which unsaturated bonds present in trace amounts are involved.

However, it is expected that the limited compounds blended in the present invention will be effective against ozone deterioration of polyolefins that essentially have only saturated bonds, especially propylene-based polymers that are substantially free of unsaturated bonds. However, the mechanism of action is not clear.

[Example] In the following examples and comparative examples, (A) to (
E) Regarding the compounds, the following compounds were used among the above-mentioned exemplified compounds.

Compound fA) (a-11[2,2'-thiobis(Lt-octylphenol)1-0-butylaminenickel[II]
a-2) Nickel-dibutyl-dithiocarbamate compound (b) [b-21 Dimethyl corkate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylbiperidine polycondensation (b-31 poly((6-[,t,:+,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-
diyl)(2,2,6,6-tetramethyl-4-piperidylimino)hexamethylene([2,2,6,6-tetramethyl-4-piperidyl)imino)j Compound fC) (c-1) N , N'-bis[2-(tetradecyloxycarbonyl)ethyl]piperazine compound (D) fd-212,4-di-butylphenyl-3.5-
D-monobutyl-4-hydroxybenzoate compound fEl fe-1) dj-a-tocopherol In addition, the following compounds were added as other formulations.

1f-11tetrakis[methylene-3-(3,5-di-butyl-4-hydroxyphenyl)propionate comethane(f-21 mixed (mono- and di-nonylphenyl)phosphite ff-311,3, 5-Tris(3,5-di-butyl-4-hydroxybenzyl)isocyanurate ff-41 Similystilthiodipropionate (f-5
1 Calcium stearate Examples 1 to 9 and Comparative Examples 1 to 2 The components shown in Table 1 were blended with 100 parts by weight of a propylene/ethylene block copolymer having a liver R of 23 g/10 min and an ethylene content of 3% by weight. The mixture was blended using a Henschel mixer and pelletized using an extruder (230° C.) with a diameter of 30++ m. The obtained pellets were put into an injection molding machine (230°C) to form a sheet with a thickness of 1 mm.

Light up a QGUS type ultraviolet lamp manufactured by Iwasaki Electric ■ to generate ozone, and adjust the air flow rate to bring the ozone concentration to 20 to 2.
It was set to 5 ppm. This air was passed through the container containing the test piece. The temperature was 25-30°C and the specimens were exposed to ozone for one month.

Take out the exposed specimen, cut it, and measure the VFR of the cut specimen.
The ratio fR1 to l was used as a measure of ozone deterioration. The smaller this ratio is, the more the deterioration caused by ozone is suppressed.

The results are shown in Table 1.

(Leaving space below) Examples 1O to 12 and Comparative Examples 3 to 4 Based on a propylene-ethylene block copolymer having a VFR of 30 g 710 minutes and an ethylene content of 3% by weight, pelletized with the formulation shown in Table 2, and heated at 240°C. A sheet with a thickness of 2 mm was made by injection molding.

Ozone deterioration was measured by exposing the sample to an ozone concentration of 1 to 13 ppm for 2 months.

The results are shown in Table 2.

[Effects of the Invention] The present invention improves ozone resistance by blending a specific compound into a molded article of polyolefin resin, whose ozone resistance has not been a problem because it has virtually no unsaturated bonds. It has improved ozone properties.

The polyolefin molded article of the present invention can be deodorized, bleached, sterilized,
Containers, equipment, and peripheral parts used when ozone is used for purposes such as disinfection, bleaching, and treatment, aircraft parts exposed to ozone at high altitudes, and equipment incorporating high-voltage generators (electrostatic copying machines, automobiles, etc.) etc.), mercury lamps, xenon lamps, etc.).

Claims (1)

[Claims] (1) Add the following (A) to 100 parts by weight of polyolefin.
An ozone-resistant polyolefin molded article comprising a composition containing 0.001 to 2 parts by weight of a compound selected from (E) and being in contact with an atmosphere having an ozone concentration of 0.1 ppm or more. (A) Nickel-containing complex salt compound (B) Piperidine compound (C) Piperazine compound (D) Benzoate compound (E) α-tocopherol.