JPH0632946A - Weather-resistant polyolefinic resin composition - Google Patents

Abstract

PURPOSE:To provide a polyolefinic resin composition having a weather resistance that is not impaired even in the presence of both an antiblocking agent and a weatherproofing agent. CONSTITUTION:This resin composition comprises 100 pts.wt. polyolefinic resin, 0.01-2.0 pts.wt. antiblocking agent containing 200mumol/g or below surface hydroxyl groups and 0.01-1.0 pt.wt. weatherproofing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition having improved weather resistance.

[0002]

BACKGROUND OF THE INVENTION Polyolefin resins are used in a wide range of applications such as food packaging, fiber packaging, pharmaceutical packaging, fertilizer packaging, as well as agricultural materials and construction materials. There is. In recent years, in particular, the outdoor use of polyolefin resins has tended to increase year by year, and is expected to continue to increase in the future, and weather resistance is required according to the purpose of use. Therefore, UV absorber,
Many studies have been conducted on the improvement and development of hindered amine light stabilizers and quenchers, and the study of additive formulations (for example, JP-A-54-21450, JP-A-54-70347, and JP-A-59-133239). Japanese Patent Laid-Open No. 59-2
No. 7936, Japanese Patent Publication No. 45-22625, Japanese Patent Publication No. 60-16459).

However, these weather resistance-imparting agents generally have a large migration to the surface of the molded article, and therefore their effects are not sustained, and therefore, as an improvement, they are polymerized (for example, JP-A-55-54312). And volatilization prevention (for example, JP-A-59-155405) are being studied. On the other hand, from the viewpoint of cost, researches for higher performance have been made (for example, JP-A-52-71486, JP-A-52-73886, JP-A-53-67749, and JP-A-59-). 86645 publication). Among these, hindered amine compounds having a piperidine derivative in the molecule are known to have a great effect on polyolefin resins, and the amount used thereof tends to increase.

By the way, an anti-blocking agent such as silica, zeolite or talc is added to the polyolefin resin in order to improve workability. When the anti-blocking agent and the weather resistance-imparting agent are used together, there is a disadvantage that the weather resistance-imparting agent often impairs the original performance. Therefore, in order to obtain the weather resistance according to the intended use of the polyolefin resin, it is necessary to increase the addition amount of the weather resistance-imparting agent, which causes an economic disadvantage.

[0005]

In view of the present situation, the present inventors have found that even when an antiblocking agent and a weather resistance-imparting agent are used in combination, the weather resistance-imparting agent does not impair the original performance of the polyolefin resin. As a result of diligent studies on the composition, a polyolefin resin composition having improved weather resistance and good handling workability was found, and various studies were further conducted to complete the present invention.

That is, according to the present invention, the amount of OH groups on the surface of (a) is 20 with respect to 100 parts by weight of the polyolefin resin.
An anti-blocking agent having a concentration of 0 μmol / g or less was added to 0.
01-3.0 parts by weight, 0.01-
The present invention provides a weather resistant polyolefin-based resin composition characterized by containing 1.0 part by weight.

The present invention will be described in detail below. The production method of the polyolefin resin used in the present invention is not limited, and it can be produced by, for example, an ionic polymerization method or a radical polymerization method. Examples of the polyolefin resin obtained by the ionic polymerization method include homopolymers such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and ethylene copolymers obtained by copolymerizing ethylene and α-olefin. Examples thereof include polymers. Examples of the α-olefin include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1, octadecene-
C3-C18 alpha-olefins, such as 1, are used, These alpha-olefins can be used not only 1 type but 2 or more types. In addition, a propylene-based copolymer and the like such as a copolymer of propylene and butene-1 can be exemplified. Examples of the polyolefin resin obtained by the radical polymerization method include ethylene homopolymers and ethylene copolymers obtained by copolymerizing ethylene with a monomer capable of radical polymerization. Examples of the radical-polymerizable monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, and their esterified products, acid anhydrides, vinyl esters such as vinyl acetate, and the like. Specific examples of the esterified product of unsaturated carboxylic acid include ethyl acrylate, methyl methacrylate, glycidyl methacrylate and the like. These radically polymerizable monomers may be used alone or in combination of two or more.

The component (a) antiblocking agent used in the present invention has a surface OH group content of 200 μm.
It is an anti-blocking agent having an ol / g or less, such as silica, clay, talc, diatomaceous earth, feldspar, kaolin,
Examples thereof include zeolite, kaolinite, wollastonite, sericite, amorphous aluminosilicate, and amorphous calcium silicate. The compounding amount of the anti-blocking agent is 100 parts by weight of the polyolefin resin,
It is 0.01 to 3.0 parts by weight. If the compounding amount is less than 0.01 part by weight, the effect of improving workability after molding is small and 3.0
If it exceeds the amount by weight, optical properties such as transparency deteriorate.
From the viewpoint of antiblocking effect and transparency, these antiblocking agents have an average particle size of 0.3 to 8
Those having a particle size of 10 μm or more and having a particle size of 5 μm or less are preferable. The particle size of the anti-blocking agent is a value measured by using a Coulter counter to disperse the sample in the electrolytic solution by ultrasonic waves for 2 minutes.

The surface OH group content of the antiblocking agent was measured by the following method. The anti-blocking agent was vacuum dried at 120 ° C. for 2 hours, allowed to cool to room temperature in a silica gel desiccator, weighed 2 g, put in a dry 100 ml three-necked flask, and added 40 ml of dehydrated toluene. Next, after replacing the inside of the system with dry nitrogen gas, a 11% by volume toluene solution of triethylaluminum was added with stirring with a magnetic stirrer, and the amount of ethane gas generated by the reaction between the OH groups on the antiblocking agent surface and triethylaluminum was adjusted. The amount was quantified and the surface OH group amount (n) was calculated by the following formula. n = PV / RTW [where n is the amount of OH groups on the surface (mol / g, P is the pressure (a
tm), V: ethane gas generation amount (l), R: gas constant (atm · l / mol · degree K), W: sample weight (g)]

The weather resistance-imparting agent of the component (b) used in the present invention is not particularly limited, and examples thereof include those usually used. Examples of the weather resistance imparting agent include benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, oxalic acid amide-based UV absorbers, nickel-based, hindered amine-based light stabilizers, and the like.

Specific examples of the ultraviolet absorber include:
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
n-octoxybenzophenone, 2-hydroxy-4-
Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-hydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-
4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2)
-Methoxyphenyl) methane, 2-hydroxy-4-n
-Dodecyloxybenzophenone, 2-hydroxy-4
-Methoxy-2'-carboxybenzophenone, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-octylphenyl) benzotriazole, 2 −
(2′-hydroxy = 5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-t-butylmethylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- [2′-hydroxy-
3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2'-hydroxy-
4'-octoxyphenyl) benzotriazole, 2,
2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole-2-
Ill) phenol], phenyl salicylate, 4-t-
Butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate salicylate, 4-t-octylphenyl salicylate, 1-methyl (β, β- Diphenyl)
Cyanoacrylate, 2-ethylhexyl (β, β-diphenyl) cyanoacrylate, 2-ethoxy-2′-
Examples thereof include ethyl oxalic acid bisanilide and 2-ethoxy-5-t-butyl-2′-ethyl oxalic acid bisanilide.

Specific examples of the nickel-based light stabilizer include nickel dibutyldithiocarbamate and [2,2 ′].
-Thiobis (4-t-octylphenolate)]-2-
Ethylhexylamine nickel salt (II), [2, 2 '
-Thiobis (4-t-octylphenolate)]-n-
Butylamine nickel salt (II), 3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate nickel complex salt, nickel bis (octylphenyl) sulfide, 2,2'-thiobis (4-t-octylphenolate) ) Triethanolamine nickel salt (II) and the like can be mentioned.

Specific examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4).
-Piperidyl) sebacate, bis (1,2,2,6,6)
-Pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4-hydroxy-2,2,6,6-tetramethyl- Polyester of 1-piperidine ethanol and succinic acid, [4- (4-hydroxy-3,5-di-
t-butylphenyl) propionyl] -N- (4-hydroxy-3,5-di-t-butylphenyl) methyl-
2,2,6,6-tetramethylpiperidine, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-
4-piperidyl) -1,2,3,4-butanetetracarboxylate, 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]}, poly {[6-morpholino-1,3,5-triazine-2,
4-diyl] [(2,2,6,6-tetramethyl-4-
Piperidyl) imino] hexamethylene [(2,2,6,
6-Tetramethyl-4-piperidyl) imino]}, phenyl-4-piperidyl carbonate, 1,1 ′-(1,
2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 2,2,6,6-tetramethyl-
4-piperidyl / tridecyl (mixed) -1,2,3,4
-Butanecarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl (mixed) -1,
2,3,4-butanetetracarboxylate, 2,2,
6,6-tetramethyl-4-piperidyl / β, β,
β ′, β′-tetramethyl-3,9,-[2,4,8,
10-Tetraoxaspiro (5.5) undecane] diethyl (mixed) -1,2,3,4-butanetetracarboxylate, 1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9
-[2,4,8,10-Tetraoxaspiro (5,5)
Undecane] diethyl (mixed) -1,2,3,4-butanetetracarboxylate and the like.

The blending amount of these weather resistance-imparting agents is 0.01 to 1.0 with respect to 100 parts by weight of the polyolefin resin.
Parts by weight. If the blending amount is less than 0.01 part by weight, the effect of improving weather resistance is poor, and if it exceeds 1.0 part by weight, optical properties such as transparency deteriorate due to bleeding. Further, these weather resistance-imparting agents can be used not only in one kind but also in a mixture of two or more kinds.

The method for producing the weather resistant polyolefin resin composition of the present invention is not particularly limited and can be obtained, for example, by uniformly mixing the components used in the present invention. As a mixing method, various known methods within the above range for the respective components, for example, a tumbler blender, a method of dry blending using a mixer such as a Henschel mixer, and after mixing are melted with a single-screw extruder, a multi-screw extruder or the like. A method of kneading and granulating, a method of melt kneading with a Banbury mixer, a kneader, a roll mill or the like and then granulating can be employed. As for the mixing of the respective components, they can be mixed at once, or a part thereof can be premixed and then further mixed with the remaining part.

In the present invention, other known compounding agents usually used, such as antioxidants, neutralizing agents, antifogging agents, lubricants, release agents, pigments, flame retardants, inorganic or organic fillers, etc. May be added within a range that does not impair the object of the present invention.

The prepared composition of the present invention can be obtained by various known molding methods such as extrusion molding, calender molding, injection molding, pressure molding, vacuum molding and blow molding to obtain a product having excellent weather resistance. You can As the molding process, the composition according to the present invention may be molded alone, or may be laminated with another thermoplastic resin composition. However, in the lamination molding process, it is preferable that the composition according to the present invention is laminated on both sides or one side of the outermost layer.
Examples of lamination molding include the composition according to the present invention and polyethylene, polypropylene, ethylene vinyl acetate copolymer,
By co-extrusion inflation molding or co-extrusion cast molding with a suitable other resin such as polyamide or polyester, a co-extruded film having two layers or two or more layers can be obtained. Further, a film or coextruded film obtained by molding the composition according to the present invention alone is stretched or unstretched polypropylene, a film or sheet such as polyamide, a stretched polyester film, an aluminum foil, cellophane, paper, or a composite film or sheet thereof. A laminated film or laminated sheet can be obtained by dry lamination or sandwich lamination with the above.

Further, a laminate can be prepared by extrusion-coating or co-extrusion-coating the composition according to the present invention on various plastic films, aluminum foil, paperboard, paper and other substrates. Further, various containers can be made by pressure-compressing or vacuum-forming a sheet or a coextruded sheet obtained by independently molding the composition according to the present invention. Further, the composition according to the present invention may be used alone or in various containers by co-extrusion hollow molding with polyamide, polyvinyl alcohol or the like.

[0019]

Industrial Applicability As described above in detail, the present invention is a polyolefin-based resin having improved weather resistance, which has been hindered in the past, by containing an anti-blocking agent having a specific amount of OH groups and a weather resistance-imparting agent. A resin composition can be provided.

[0020]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto. The evaluations in Examples and Comparative Examples were carried out by the following methods.

(1) Outdoor exposure test A film formed under the same processing conditions was subjected to outdoor exposure for 60 days in sand, and then subjected to JIS K 6781.
A tensile test was performed according to (Agricultural polyethylene film test method), and elongation before and after exposure was measured. Then, the residual elongation rate was calculated by the following formula. L _w = L ₂ x100 / L ₁ [where L _w : residual elongation (%), L ₁ : elongation before exposure (%), L ₂ : elongation after exposure (%)]

(2) Accelerated weather resistance test A sheet molded under the same molding conditions was used with a weather resistance tester (Sunshine Super Long Life Weather Meter WEL-SUN-DCH type manufactured by Suga Test Instruments Co., Ltd.) to obtain a black panel. Temperature 83 ℃, Spray time 18 minutes / 120
A test was performed for 1000 hours under the condition of minutes, and the elongation before and after the test was measured. Then, the residual elongation rate was calculated by the following formula. L _w = L ₂ × 100 / L ₁ [where L _{w is the} residual elongation (%), L _{1 is} the elongation before the test (%), and L _{2 is} the elongation after the test (%)]

Examples 1 to 4, Comparative Examples 1 to 4 Ethylene-butene-1 copolymer (Sumikasen-L FA101-0 manufactured by Sumitomo Chemical Co., Ltd. (MFR = 0.8 g / 10 min
, Density = 0.919 g / cm ³ )) 90% by weight and low density polyethylene (Sumikasen F1 manufactured by Sumitomo Chemical Co., Ltd.)
02-0 (MFR = 0.35g / 10min, density = 0.92)
2 g / cm ³ )) 10 parts by weight of 100 parts by weight of a polyolefin resin, 0.4 parts by weight of an anti-blocking agent having different amounts of OH groups on the surface shown in Table 1 and 0.2 part by weight of erucic acid amide. Parts, 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]} (CHI manufactured by Ciba-Geigy
0.2 parts by weight of MASSORB944 LD) were blended and uniformly melt-mixed at 150 ° C. for 10 minutes with a Banbury mixer, and then pelletized with a 65 mm diameter single screw extruder to obtain respective resin compositions. This composition
125mmφ for Placo EX-50 inflation molding machine
Attach a die with a lip gap of 2 mm at a processing temperature of 200
Inflation film processing was performed under the conditions of ° C, BUR 2.5, and extrusion rate of 25 kg / hr to prepare a film having a thickness of 20 µm. An outdoor exposure test was performed using the obtained film to determine the elongation residual ratio. Further, the film was formed into a sheet having a thickness of 0.5 mm by using a hot press molding machine, and an accelerated weather resistance test was performed to obtain the elongation residual rate. The results are shown in Table 1.

Examples 5-6, Comparative Examples 5-6 100 parts by weight of ethylene-vinyl acetate copolymer (Evatate H2021F (MFR = 1.5 g / 10 min, vinyl acetate content 15% by weight) manufactured by Sumitomo Chemical Co., Ltd.) On the other hand, 0.3 parts by weight of an anti-blocking agent having a different amount of OH groups on the surface shown in Table 2 was used as a weather resistance-imparting agent of 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]} (CHIMAGSOSO manufactured by Ciba Geigy)
RB944 LD) was blended in an amount of 0.2 parts by weight, and the mixture was uniformly melt mixed at 150 ° C. for 10 minutes with a Banbury mixer, and then pelletized with a 65 mm diameter single screw extruder to obtain respective resin compositions. A sheet having a thickness of 0.5 mm is prepared from the obtained resin composition using a hot press molding machine,
An accelerated weathering test was performed to determine the residual elongation. The results are shown in Table 2.

Examples 7 to 9 and Comparative Examples 7 to 10 High-pressure polyethylene (Sumikasen F manufactured by Sumitomo Chemical Co., Ltd.)
208-0 (MFR = 1.5g / 10min, density = 0.92)
2 g / cm ³ )) 100 parts by weight, 0.2 parts by weight of an anti-blocking agent having a different amount of OH groups on the surface shown in Table 2, and 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]} (CHIMAGSORB 94 manufactured by Ciba Geigy)
4 LD) was blended in an amount of 0.2 parts by weight, uniformly melt-mixed at 150 ° C. for 10 minutes with a Banbury mixer, and then pelletized with a 65 mm diameter single-screw extruder to obtain respective resin compositions. A sheet having a thickness of 0.5 mm was prepared from the obtained resin composition using a hot press molding machine, and an accelerated weather resistance test was performed to determine the elongation residual ratio. The results are shown in Table 2.

[0026]

[Table 1]

[0027]

[Table 2]

Claims (1)

[Claims] (1) The amount of OH groups on the surface of (a) is 200 μmol / g with respect to 100 parts by weight of a polyolefin resin.
A weather-resistant polyolefin-based resin composition comprising 0.01 to 3.0 parts by weight of the following anti-blocking agent and 0.01 to 1.0 parts by weight of (b) a weather resistance-imparting agent.