JP3023490B2 - Antioxidant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antioxidant resin composition. More specifically, it relates to an antioxidant resin composition having remarkably excellent thermal stability and weather resistance.

[0002]

2. Description of the Related Art The amount of resin used outdoors is increasing year by year. These resins are required to have weather resistance according to the purpose of use, and many weather resistance imparting agents have been developed so far. Recently, a hindered amine-based weathering agent called HALS (abbreviation for hindered amine light stabilizer) is used to reduce the change in mechanical properties, gloss, and color of a resin composition containing the hindered amine weathering agent when exposed outdoors. Since it can be remarkably improved as compared with the case of (1), it is often used (for example, JP-A-59-86645). In addition, since the processing stability and heat stability of these resins can hardly be imparted by a weathering agent, heat stabilizers (hindered phenol heat stabilizers, sulfur heat stabilizers, phosphite heat stabilizers, etc.) ) Is usually added.

[0003]

However, a resin composition containing a heat stabilizer and a hindered amine-based weathering agent may also have thermal stability such as gelling during processing, seizure or discoloration immediately after processing, depending on the use conditions. Deterioration due to failure, or deterioration due to poor weather resistance such as deterioration of mechanical properties, gloss, change in color tone, etc. during outdoor exposure. It is hard to say that there is. Of course, if the amount of the heat stabilizer or hindered amine weathering agent added to the resin is increased, the thermal stability and weather resistance are improved to some extent, but the resin composition is yellowed,
There is a problem that the heat stabilizer and the hindered amine-based weather resistance imparting agent bleed to the surface to impair the appearance.

An object of the present invention is to provide an antioxidant resin composition containing a heat stabilizer and a hindered amine-based weathering agent, which has remarkably excellent heat stability and weather resistance.

[0005]

Means for Solving the Problems The present inventors have continued to study a resin composition containing a hindered amine-based weathering agent. As a result, it was found that when an alkylphosphinic acid compound was added to a resin composition containing a hindered amine-based weathering agent, an antioxidant resin composition having significantly improved thermal stability and weather resistance was obtained. Was completed.

That is, the present invention relates to an olefin polymer,
0.01 to 1 per 100 parts by weight of the olefin resin
0 parts by weight of a hindered amine-based weathering agent, and
0.1 parts by weight of the hindered amine-based weathering agent.
01 to 10 parts by weight represented by the following general formula (A) or (B)
An antioxidant resin composition comprising an alkylphosphinic acid compound to be used. (Wherein, R represents an alkyl group having 1 to 22 carbon atoms,
X represents a phenyl group, a naphthyl group or an anthracenyl group;
Is metal ion, ammonium ion, phosphonium ion
To indicate ) (Wherein, R ₁ , R ₂ and R ₃ are hydrogen, chlorine, carbon number 1)
An alkyl group of 22 or more, a phenyl group, a naphthyl group,
Shows an anthracenyl group.

The hindered amine weathering agent used in the present invention is a 2,2,6,6-tetraalkylpiperidine derivative having a molecular weight of 250 or more and having a substituent at the 4-position. Examples of the substituent include a carboxylic acid residue, an alkoxy group, an alkylamino group, and various other groups. The N-position may be substituted by an alkyl group, an oxy radical, or the like, and specific examples include compounds represented by the following formulas (1) to (10).

[0008]

The alkylphosphinic acid compound used in the present invention is represented by the general formulas (A) and (B).

Here, R represents an alkyl group having 1 to 22 carbon atoms, a phenyl group, a naphthyl group and an anthracenyl group, and X represents a metal ion, an ammonium ion and a phosphonium ion.

Here, R ₁ , R ₂ and R ₃ are hydrogen,
And chlorine, an alkyl group having 1 to 22 carbon atoms, a phenyl group, a naphthyl group, and an anthracenyl group.

Specific examples include sodium phenylphosphinate, potassium phenylphosphinate, lithium phenylphosphinate, calcium phenylphosphinate, magnesium phenylphosphinate, 9,10-
Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dichloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-
10-oxide and the like.

The resins used in the present invention include polyethylene, polypropylene, poly-1-butene, poly-4
-Methyl-1-pentene, ethylene-propylene block copolymer, ethylene-propylene random copolymer,
Ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-octene copolymer, propylene-
1-butene copolymer, ethylene-vinyl acetate copolymer,
Olefin polymers such as copolymers of olefins and polar vinyl compounds such as ethylene-methyl methacrylate copolymer and ionomer resins, acrylic resins such as polymethyl methacrylate, polyester resins, polyamide resins, polycarbonate resins, phenolic resins, Examples thereof include a polyvinyl chloride resin and a polyurethane resin.

The mixing ratio of each component of the resin composition of the present invention is, for example, as follows. The hindered amine-based weather resistance imparting agent is usually 0.01 to 100 parts by weight of the resin.
It is used in the range of 10 parts by weight, preferably 0.05 to 1 part.
Parts by weight. If the amount is less than 0.01 part by weight, the effect of imparting weather resistance is poor, and even if the amount exceeds 10 parts by weight, further remarkable improvement of the effect of imparting weather resistance is not seen, so that it is uneconomical. It is not preferable because the agent may bleed or discolor.

The compounding ratio of the alkyl phosphinic acid compound is usually 0.01 part by weight or more and 10 parts by weight or less based on 1 part by weight of the hindered amine weathering agent. 0.
If the amount is less than 01 parts by weight, the effect of improving thermal stability and weather resistance is poor, and even if the amount exceeds 10 parts by weight, no further remarkable improvement is seen in the effect of improving thermal stability and weather resistance. It is not economical and the alkylphosphinic acid compound may bleed.

The resin composition of the present invention can be used as long as it does not impair the object of the present invention, especially when heat stability needs to be enhanced.
Various heat stabilizers can be included. For example, 2,6-
Hindered phenol heat stabilizers such as dialkylphenol derivatives and 2-alkylphenol derivatives, sulfur heat stabilizers having a thiol bond or a thioether bond containing a divalent sulfur atom, or phosphites containing a trivalent phosphorus atom System heat stabilizers and the like.

Examples of the hindered phenol-based heat stabilizer include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,
2'-methylene-bis- (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-
Methylphenyl acrylate, 1,3,5-tris (4
-T-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrakis- [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] -methane, 3,9-bis [2
-[3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, Examples of the sulfur-based heat stabilizer include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaerythritol- Tetrakis- (β-laurylthiopropionate), 2-mercaptobenzimidazole, 4,
Examples of phosphite heat stabilizers such as 4'-thio-bis- (3-methyl-6-t-butylphenol) include:
Trisnonylphenyl phosphite, triphenyl phosphite, tris (2,4-di-t-butylphenyl)
-Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite and the like. Also, these heat stabilizers
It may be used alone or in combination.

Further, the resin composition of the present invention may contain, as a component, an ultraviolet absorber, an anti-fogging agent, an antistatic agent, a lubricant, a filler, a flame retardant, a pigment, etc. within a range not to impair the object of the present invention. Can be. The method of compounding each of the above-mentioned components is not particularly limited, and a Banbury mixer, a mixing roll,
It can be compounded by a general method such as an extruder.

[0019]

The high antioxidant performance of the resin composition of the present invention is expressed by the interaction between an alkylphosphinic acid compound and a compound derived from a hindered amine-based weathering agent in an oxidizing atmosphere in the resin under an oxidizing atmosphere. Conceivable.

[0020]

According to the present invention, an antioxidant resin composition having excellent heat stability and weather resistance can be obtained by adding an alkylphosphinic acid compound to a resin composition containing a hindered amine-based weathering agent. Obtainable.

The resin composition of the present invention comprises a film, a sheet,
It can be formed into various materials such as fibers and molded products and used for various purposes such as agricultural films and automotive materials. In particular, a film obtained from the resin composition of the present invention when a polyethylene, a polyolefin such as an ethylene-1-butene copolymer or an ethylene-vinyl acetate copolymer is used as a resin is a film for packaging or an agricultural house. It is extremely useful as a covering material for tunnels and the like. In addition, the resin composition of the present invention is particularly useful for materials requiring high weather resistance, such as automotive materials such as bumpers and building materials such as garage roofs, for outdoor use.

[0022]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. The test methods in the examples are as follows.

Thermal Stability Test 1 g of a test piece having a thickness of 1 mm was measured in a dark place under an oxygen amount of 40 using a polymer material deterioration measuring device manufactured by Shibayama Scientific Instruments Co., Ltd.
The oxygen absorption induction period was measured at a predetermined tank temperature under mL conditions. In the oxygen absorption induction period, after the temperature in the tank became constant, the amount of oxygen in the system was reduced by 0.9 mL, or in the case of decomposed gas, the time until the oxygen volume in the system showed the minimum value was expressed. The longer the oxygen absorption induction period, the better the oxidation deterioration resistance, that is, the better the thermal stability.

Weather resistance test A test piece punched out with a JIS No. 1 dumbbell was subjected to black panel temperature 83 using a standard sunshine super long life weather meter manufactured by Suga Test Instruments Co., Ltd.
The mixture was aged at a temperature of 2 ° C. for 18 minutes every 2 hours under a water spray condition. For the aged test specimen, a tensile test was performed using an Autograph DSS100 manufactured by Shimadzu Corporation to measure the elongation (%), and the elongation was reduced to half that of the original test specimen. Weather resistance test time (hereinafter,
"Weather resistance half-life"). The greater the value of this time, the better the weather resistance.

Example 1 As shown in Table 1, an ethylene-vinyl acetate copolymer (Evatate D20 manufactured by Sumitomo Chemical Co., Ltd.) was used as a resin.
11) 2,6-Di-t-butyl-
0.08 parts by weight of 4-methylphenol (Sumitomo Chemical Co., Ltd., Sumilizer BHT), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate]- 0.2 parts by weight of methane (Sumilyzer BP-101, manufactured by Sumitomo Chemical Co., Ltd.), 0.3 parts by weight of stearamide, 2.0 parts by weight of sorbitan sesquipalmitate, silica (Shilton PF-, manufactured by Mizusawa Chemical Co., Ltd.) 06) 5.0 parts by weight, and a hindered amine-based weathering agent and a phenylphosphinic acid compound shown in Table 1 were further added thereto.
After kneading at 150 ° C for 5 minutes with a Banbury mixer,
Pellets were obtained by granulation with an extruder. The pellets were formed into a sheet having a thickness of 1 mm by a press molding method and a film having a thickness of 75 μm by an inflation molding method, and subjected to a weather resistance test. As shown in Table 1, the results had excellent weather resistance.

Comparative Example 1 A film was formed in the same manner as in Example 1 except that the phenylphosphinic acid compound was not used, and a weather resistance test was performed. As shown in Table 1, the results were inferior to Example 1 in weather resistance.

Example 2 A film was formed in the same manner as in Example 1 except that the types and amounts of the hindered amine-based weathering agent and the phenylphosphinic acid compound were as shown in Table 1, and a weather resistance test was conducted. went. As shown in Table 1, the results showed excellent weather resistance.

Comparative Example 2 A film was formed in the same manner as in Example 2 except that the phenylphosphinic acid compound was not used, and a weather resistance test was performed. As shown in Table 1, the result was inferior to Example 2 in weather resistance.

[0029]

Examples 3 to 5 As a resin, 100 parts by weight of low-density polyethylene (Sumikasen F208-0, manufactured by Sumitomo Chemical Co., Ltd.) was used.
0.1 part by weight of 2,6-di-t-butyl-4-methylphenol (Sumitomo Chemical Co., Ltd., Sumilizer BHT) is blended, and further, a hindered amine-based weathering agent as shown in Table 2, and A phenylphosphinic acid compound was blended, kneaded with a laboratory plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd. at 160 ° C., 60 rpm for 5 minutes, formed into a sheet having a thickness of 1 mm by a press molding method, and subjected to a thermal stability test. The results, as shown in Table 2, had excellent antioxidant performance.

Comparative Example 3 Except that no phenylphosphinic acid compound was used,
A sheet having a thickness of 1 mm was formed in the same manner as in Examples 3 to 5, and a thermal stability test was performed. The results are shown in Table 2,
The antioxidant performance was poor.

[0032]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-95650 (JP, A) JP-A-52-110750 (JP, A) JP-A-53-137239 (JP, A) JP-A-1- 141943 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/14 C08K 3/00-13/08

Claims (1)

(57) [Claims] 1. An olefin polymer, said olefin resin
0.01 to 10 parts by weight of hinder per 100 parts by weight of fat
Doamine-based weathering agent, and the hindered amine
0.01 to 10 parts by weight per part by weight of the system weathering agent
An alkylphosphor represented by the following general formula (A) or (B)
An antioxidant resin composition comprising a finic acid compound . (Wherein, R represents an alkyl group having 1 to 22 carbon atoms,
X represents a phenyl group, a naphthyl group or an anthracenyl group;
Is metal ion, ammonium ion, phosphonium ion
To indicate ) (Wherein, R ₁ , R ₂ and R ₃ are hydrogen, chlorine, carbon number 1)
An alkyl group of 22 or more, a phenyl group, a naphthyl group,
Shows an anthracenyl group.