JP2003286412A - Synthetic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic resin composition which is excellent in weatherability, does not lose the excellent weatherability even if it is processed at a high temperature, does not suffer weatherability decrease by sulfur fumigation or acid rain, and maintains the weatherability for a long period of time. <P>SOLUTION: This synthetic resin composition comprises (A) a synthetic resin and (B) a high molecular weight stabilizer obtained by adding (b-1) a piperidine compound expressed in general formula (1) to (b-2) a polymer having a molecular weight of not less than 300 (wherein R<SB>1</SB>is a residue obtained by removing two OH groups from a 1-20C polyhydric alcohol). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic resin composition containing a stabilizer having a high molecular weight, and more specifically, a stabilizer having a high molecular weight of a ketalized piperidine compound is added to a synthetic resin. And a synthetic resin composition in which the deterioration of weather resistance due to sulfur fumigation or acid rain is suppressed.

[0002]

2. Description of the Related Art Polyethylene-based thermoplastic resins such as polyethylene and ethylene-vinyl acetate copolymers and polyester films are excellent in transparency, heat-retaining property and mechanical strength. It is used for agricultural films such as. However, these resins have the drawback that they cannot be used for a long period of time due to deterioration due to ultraviolet rays and deterioration or breakage of transparency.

It is known that such deterioration of the film can be suppressed by adding an antioxidant, an ultraviolet absorber, a hindered amine compound, hydrotalcites and the like. For example, Japanese Patent Application Laid-Open No. 63-175072 discloses that
Stabilization by a combination of a hindered amine compound and hydrotalcite has been proposed. Also, US Pat. No. 5,096,950 and Japanese Patent Laid-Open No. 2001-13
In Japanese Patent Publication No. 9821, it is proposed to add a hindered amine compound having a nitroxyalkyl structure to a synthetic resin used for an agricultural film.

However, the stabilizing effect of any of the additives is not yet satisfactory, and in particular, when pesticide spraying or sulfur fumigation is carried out for controlling pests, deterioration of the resin proceeds in a short period of time. Therefore, further stabilization has been desired.

Further, the nitroxy compound of the hindered amine compound has an excellent effect of imparting light resistance, but it violently colors the resin, so that it is not actually used for agricultural films.

Further, from the viewpoint of resource saving, weather resistance higher than ever is required.

Therefore, the object of the present invention is to provide excellent weather resistance,
And its excellent weather resistance is not lost even when processed at high temperatures, and there is no deterioration in weather resistance due to sulfur fumigation or acid rain, and to provide a synthetic resin composition in which the weather resistance is maintained for a long period of time. .

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a synthetic resin is blended with a high molecular weight stabilizer obtained by adding a ketalized piperidine compound to a polymer having a molecular weight of 300 or more. As a result, the inventors have found that even if sulfur fumigation is performed, the deterioration of weather resistance is small, and excellent long-term weather resistance is exhibited, and the present invention has been completed.

That is, according to the present invention, (A) a synthetic resin and (B)
(B-1) A synthetic resin composition containing a piperidine compound represented by the following general formula (1) and (b-2) a high molecular weight stabilizer obtained by adding a polymer having a molecular weight of 300 or more. .

[0010]

[Chemical 2]

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the synthetic resin composition of the present invention will be described in detail below.

The synthetic resin (A) used in the present invention includes polypropylene and low density polyethylene (LDP).
E), linear low density polyethylene (LLDPE), ultra low density polyethylene (VLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), high molecular weight polyethylene (UHPE), polybutene-1, poly-3- Α-olefin polymers such as methylpentene or ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer,
Ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer (EEA), ethylene-ethyl methacrylate copolymer, ethylene-vinyl alcohol copolymer, ethylene-propylene Polyolefin resins such as copolymers, propylene-butene-1 copolymers, ethylene-propylene-butene-1 terpolymers and copolymers thereof, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene,
Chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer A halogen-containing resin such as a vinyl chloride-acrylic acid ester copolymer, a vinyl chloride-maleic acid ester copolymer, a vinyl chloride-cyclohexylmaleimide copolymer,
Petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrenic polymer and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile) Etc.) with a copolymer (for example,
AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate, polybutylene terephthalate, and other linear polyesters, polyphenylene ether,
Polyamide such as polycaprolactam and polyhexamethylene adipamide, polycarbonate polymer compound, polycarbonate / ABS resin, branched polycarbonate,
Examples thereof include thermoplastic resins such as polyacetal, polyphenylene sulfide, polyurethane, and fibrous resin, and blends thereof, or thermosetting resins such as phenol resin, urea resin, melamine resin, epoxy resin, and unsaturated polyester resin. Further, it may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber or styrene-butadiene copolymer rubber.

Of these synthetic resins, ethylene polymers which are polyolefin resins, especially ethylene homopolymers, or ethylene homopolymers and blends of ethylene vinyl acetate copolymer (EVA) are used to obtain various polymers. It is preferable because a synthetic resin composition having excellent mechanical properties can be obtained.

The synthetic resin composition of the present invention comprises (B) (b-
1) A piperidine compound represented by the following general formula (1) (hereinafter referred to as (b-1) compound) is (b-2) molecular weight 300.
High molecular weight stabilizer (hereinafter referred to as (B) high molecular weight stabilizer) added to the above polymer (hereinafter referred to as (b-2) polymer)
R ₁ in the above general formula (1) containing ₁ has 1 carbon atom
Is a residue obtained by removing two OH groups from a polyhydric alcohol of 20 to 20. Examples of the polyhydric alcohol include methylene glycol, ethylene glycol, 1,2-propanediol,
1,3-propanediol, 2,2-dimethyl-1,3
-Propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-
Pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4
-Diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1 Examples thereof include polyhydric alcohol compounds such as 9,9-nonanediol, 1,10-decanediol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and tetramethylolpropane.

As the compound (b-1), more specifically, the following compound No. 1-No. 12 is mentioned. However, the present invention is not limited to the following examples.

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

[0026]

[Chemical 13]

[0027]

[Chemical 14]

The method for synthesizing the compound (b-1) is not particularly limited, and any known method may be used.

Examples of the above-mentioned (b-2) polymer used in the present invention include polyolefins such as polypropylene, polyethylene such as high density polyethylene, low density polyethylene and linear low density polyethylene, ethylene-propylene-diene rubber, polybutadiene, acrylonitrile. Examples thereof include polymers having an unsaturated bond such as a butadiene-styrene copolymer. The above-mentioned (b-2) polymer has a molecular weight of 300.
Above, preferably 500 to 500,000, more preferably 1000 to 300,000.

Examples of the method for adding the compound (b-1) to the polymer (b-2) include a method using a peroxide and a method using radiation. Above (b-1)
The addition of the compound to the polymer (b-2) means a highly active radical generated from a peroxide or a polymer radical generated by irradiation of a polymer with a hydrogen atom or the like removed as a radical from the polymer ( That is, the nitroxyl radical of the compound (b-1) is added to give a structure in which the hindered amine compound is added to the polymer (b-2) through an oxygen atom. The amount of the compound (b-1) added to the polymer (b-2) is 100 parts by mass of the polymer (b-2).
The nitrogen atom contained in the compound (b-1) is preferably 0.
005 to 5 parts by mass, more preferably 0.05 to 1 part by mass.

In producing the synthetic resin composition of the present invention,
The amount of the high molecular weight stabilizer (B) added to 100 parts by mass of the synthetic resin (A) is preferably 0.0005 to 1 part by mass, more preferably 0, nitrogen atom contained in the high molecular weight stabilizer (B) to be added. Add 0.005 to 1 part by mass. When it is 0.0005 parts by mass or more, deterioration of weather resistance of the synthetic resin composition due to fumigation of sulfur and acid rain is suppressed, while when it is 1 part by mass or less, both effects and economy are satisfied. .

The method for producing the synthetic resin composition of the present invention is not particularly limited, and a known method of blending a synthetic resin with (A) a synthetic resin and (B) a high molecular weight stabilizer, for example,
A method of mixing with a ribbon blender or a Henschel mixer can be adopted, and an extruder, a Banbury mixer, or the like may be used if necessary.

The synthetic resin composition of the present invention further contains various additives used as additives for synthetic resins, for example, phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and ultraviolet rays. Absorbents, other hindered amine light stabilizers, nucleating agents, hydrotalcites, anti-fog agents, anti-fog agents, drip-proof agents, metal soaps, epoxy compounds, perchlorates,
It is preferable to add additives such as a lubricant, a modifier, an infrared absorber, a filler, a pigment and an antistatic agent.

Examples of the phosphorus-based antioxidant include
Triphenyl phosphite, tris (2,4-ditertiary butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) -ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyldecyl phosphite, Phenyldiisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol)
1,4-cyclohexanedimethyldiphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-)
Methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl-4,4′-isopropylidene diphenol pentaerythritol diphosphite, tetra (C
12-15 mixed alkyl) -4,4'-isopropylidene diphenylphosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)]-isopropylidene diphenylphosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, bis (octylphenyl) -bis [4,4'-n-butylidene bis (2
-Tert-butyl-5-methylphenol)], 1,6-hexanediol diphosphite, tetratridecyl
4,4'-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
・ 1,1,3-Tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphonite,
Examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol-2,4,6-tri-tert-butylphenol monophosphite. The addition amount of the above phosphorus-based antioxidant is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the (A) synthetic resin.

Examples of the above-mentioned phenolic antioxidant include 2,6-di-tert-butyl-p-cresol and 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3 , 5-Ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl- m-cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) ), Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidene bis (4,
6-di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 1,1,
3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) ) Phenyl] terephthalate, 1,3,5
-Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3,5-Tris (3,5-
Di-tert-butyl-4-hydroxybenzyl) -2,4,6
-Trimethylbenzene, 1,3,5-tris [(3,5
-Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4 −
Methyl-6- (2-acroyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2
-(3-tert-Butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane], triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned. The amount of the above-mentioned phenolic antioxidant added is preferably 0.001 to 10 parts by mass, and more preferably 0.001 part by mass with respect to 100 parts by mass of the synthetic resin (A).
05 to 5 parts by mass.

Examples of the sulfur-based antioxidant include, for example,
Dialkyl thiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and β-alkylmercaptopropionic acid esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate) Can be mentioned. The amount of the above-mentioned sulfur-based antioxidant added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the (A) synthetic resin.

Examples of the ultraviolet absorber include 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacroyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4) 2-methoxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5-
Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7
~ 9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiaryoctyl-6-benzotriazolylphenol), 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; 2- (2-hydroxy-4)
-Hexyloxyphenyl) -4,6-diphenyl-1,
3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
Acryloyloxyethoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and other 2- (2-hydroxyphenyl) -1,3,5-
Triazines; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5
Benzoates such as di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- Examples include cyanoacrylates such as β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate. The addition amount of the ultraviolet absorber is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin (A).

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, and 2 , 2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy-2,
2,6,6-Tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-)
Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) .bis (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2-
(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2
6,6-Tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4
-Dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4
-Piperidylamino) hexane / 2,4-dichloro-6
-Tertiary octylamino-s-triazine polycondensate, 1,
5,8,12-Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1, 5,
8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,
2,6,6-Pentamethyl-4-piperidyl) amino)
-S-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6) -Tetramethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6) -Pentamethyl-4-piperidyl) amino-s-triazine-6-
Ilamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-
4-Piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1
-Dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane and the like can be mentioned. The amount of the hindered amine light stabilizer added is
(A) With respect to 100 parts by mass of the synthetic resin, preferably 0.
001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass. .

As the nucleating agent, sorbitols, bis (4-tert-butylphenyl) phosphate alkali metal salt, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate metal salt, aluminum bis (4
-Tert-butyl benzoate) amino acid metal salts and the like. The addition amount of the nucleating agent is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin (A).

The above-mentioned hydrotalcite may be a natural product or a synthetic product, or may be one modified with an alkali metal such as lithium. In particular, a composition represented by the following general formula (2) is preferable, and it can be used regardless of the presence or absence of crystal water or the presence or absence of surface treatment. Further, the particle size is not particularly limited, but it is desirable that the particle size is small as long as the characteristics as hydrotalcite are not lost. When the particle size is large, the dispersibility is reduced, the stabilizing effect is reduced, and further the physical properties such as mechanical strength and transparency of the obtained synthetic resin composition are reduced.

[0041]

[Chemical 15]

The amount of hydrotalcite added is
(A) With respect to 100 parts by mass of the synthetic resin, preferably 0.
05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

Further, the synthetic resin composition of the present invention can be used irrespective of the processing method, for example, calendar processing, roll processing, extrusion molding processing, melt rolling method, pressure molding processing, paste. It can be suitably used for processing, powder molding, foam molding and the like.

The synthetic resin composition of the present invention comprises a wall material, a floor material,
Building materials such as window frames and wallpaper; electric wire coating materials; interior and exterior materials for automobiles;
It can be used for agricultural films used in houses, tunnels, etc .; food packaging materials such as wraps and trays; and miscellaneous goods such as paints, hoses, pipes, sheets and toys. Among these, it can be particularly preferably used for applications of agricultural films.

The method for molding an agricultural film using the synthetic resin composition of the present invention is not particularly limited, and depending on the synthetic resin used, an extrusion molding method using a T die, an inflation molding method, etc. The known molding method of is used. Such molding can be performed subsequent to the production of the synthetic resin composition of the present invention.

[0046]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

<Compound No. Synthesis of 6> 2,2,6,6
-Tetramethyl-4-piperidone 2,2 per 1 equivalent
-The compound obtained by reacting 1.4 equivalents of dimethyl-1,3-propanediol is oxidized to give N-oxyl-
A 2,2,6,6-tetramethyl-piperidin-4-one-ketal compound (Compound No. 6) was synthesized.

[Synthesis Example 1] 100 parts by mass of low-density polyethylene having an average molecular weight of 2400 (High Wax NL100: manufactured by Mitsui Chemicals, Inc.) was added with the compound No. synthesized as described above. 10.2 parts by mass of 6 and 315 parts by mass of dichlorobenzene as a solvent were charged, the atmosphere was replaced with nitrogen under reduced pressure at room temperature, and then the pressure was returned to normal pressure and heated to 130 ° C. to obtain peroxide (α, α′-bis (tertiary butylperoxide). 6.8 parts by mass of (oxy) diisopropylbenzene) was gradually added dropwise. The reaction was completed in 3 hours, and changed from reddish brown to slightly yellow. Then, the mixture was cooled to 60 ° C., and methanol was gradually added dropwise to precipitate a polymer, which was further cooled to room temperature and filtered (nitrogen content 0.4% by mass). The obtained polymer was named as adduct 1.

Synthesis Example 2 Compound No. 6 for compound N
o. Adduct 2 was obtained in the same manner as in Synthesis Example 1 except that 1 was used (nitrogen content: 0.2% by mass).

[Synthesis Example 3] Compound No. 6 for compound N
o. Adduct 3 was obtained in the same manner as in Synthesis Example 1 except that 7 was used (nitrogen content: 0.25% by mass).

[Synthesis Example 4] EPDM (ethylene-propylene-diene rubber, EP103AF: manufactured by JSR Corporation)
Compound No. was added to 100 parts by mass. 6 by adding 10 parts by mass of γ
The line was irradiated. After γ-ray irradiation, 24 in an oven at 120 ° C
It was heated for an hour and then extruded at 200 ° C. to obtain pellets. Extraction test and nitrogen content measurement were performed on the obtained pellets, and compound No. It was confirmed that 6 was added to EPDM. The obtained compound No. 6-added EPDM was used as the adduct 4 (nitrogen content: 0.1% by mass).

[Example 1 and Comparative Example 1] Tetrakis [methylene-3- (3,5-di-tert-butyl-) was added to 100 parts by mass of low density polyethylene (YK-30, manufactured by Mitsubishi Chemical Corporation). 4-Hydroxyphenyl) propionate] methane 0.05 part by mass, tris (2,4-ditertiarybutylphenyl) phosphite 0.1 part by mass, calcium stearate 0.5 part by mass and test compound described in [Table 1]. In an amount of 80 μm in a T-die extrusion process at 220 ° C. by mixing the amounts shown in Table 1 (blended so that the nitrogen contents derived from the piperidyl group are the same as in Example 1-1). I got a film. Ten 1 cm × 3 cm square test pieces were cut from the obtained film, placed in a 100 liter container, and 3 g of sulfur was fumigated with a hot plate to obtain 1
Time processed. The obtained sulfur fumigation treatment film is 63 ° C.
Deterioration treatment was carried out in the Sunshine Weatherometer, and 120 hours, 480 hours and 1200 after the deterioration treatment started.
The carbonyl index after the lapse of time was measured to evaluate the weather resistance. The results are shown in [Table 1]. In Comparative Example 1-1 and Comparative Example 1-2, instead of the adduct used in the examples, Comparative Compound No. 1 or No. 2 was blended and the weather resistance was evaluated in the same manner as in the examples.

The above carbonyl index is calculated by using the infrared absorption spectrum analysis data of the film [log
(Io / I)] / d. Where Io is 17
The transmittance (%) before deterioration treatment at 10 cm ⁻¹ , I is the transmittance (%) after the deterioration treatment, and d is the thickness (cm) of the film.

[0054]

[Table 1]

[Example 2 and Comparative Example 2] The following ingredients to the ingredients described below were kneaded using a Banbury mixer, and then granulated by a granulator to obtain pellets. Mixing and thickness of each pellet obtained by mixing 15
Thickness 1 with outer and inner layers of μm and intermediate layer of thickness 70 μm with pellets obtained by compounding
A 00 μm film was made with an inflation film molding machine. The test compound was added to each of the three layers in the amounts shown in Table 2. <Blending (outer layer)> Low-density polyethylene (density 0.992 g / cm ³ , MFR = 2.5) 100 parts by mass hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate 0.1 parts by mass tetrakis [Methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 0.05 part by mass Tris (2,4-di-tert-butylphenyl) phosphite 0.1 part by mass Table 2 Amount of compound described in Table 2 <blend (intermediate layer)> Ethylene-vinyl acetate copolymer (VA 15%, MFR = 1.5) 100 parts by mass Glycerin monostearate (anti-fogging agent) 2.0 parts by mass Hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate 0.1 parts by mass tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate] Methane 0.05 parts by mass Tris (2,4-ditert-butylphenyl) phosphite 0.1 parts by mass Calcium stearate 0.5 parts by mass Hydrotalcite (Kyowa Chemical Industry Co., Ltd .: Alkamizer 1) 5.0 parts by mass Test compound described in Table 2 Amount described in Table 2 <blend (inner layer)> Low density polyethylene (density 0.992 g / cm ³ , MFR = 2.5) 50 parts by mass ethylene-vinyl acetate copolymer Combined (VA 15%, MFR = 1.5) 50 parts by mass Glycerin monostearate (anti-fog agent) 2.0 parts by mass Hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate 0.1 parts by mass Tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane 0.05 parts by mass tris (2,4-di-tert-butyl) Ruphenyl) phosphite 0.1 part by mass calcium stearate 0.5 part by mass Test compound shown in Table 2 Amount shown in Table 2

Ten 1 cm × 3 cm square test pieces were cut from the obtained film, placed in a 100 liter container, and 3 g of sulfur was fumigated with a hot plate to obtain 1
Time processed.

With respect to the film subjected to the fumigation with sulfur, the residual rate of tensile strength after irradiation with a weatherometer for 1000 hours was measured. The results are shown in [Table 2].

[0058]

[Table 2]

[0059]

INDUSTRIAL APPLICABILITY The synthetic resin composition of the present invention has excellent weather resistance, and its excellent weather resistance is not lost even when processed at high temperatures, and the weather resistance is not deteriorated by sulfur fumigation or acid rain. , Weather resistance is maintained for a long time.

Continued front page    F-term (reference) 4H025 AA52 AC01 AC07                 4J002 AA001 AC031 AC061 AC071                       AC081 AC111 BA011 BB031                       BB051 BB071 BB121 BB151                       BB171 BB201 BB202 BB221                       BC031 BD041 BD051 BD061                       BD081 BD141 BE021 BE061                       BF021 BG041 BG061 BK001                       BL012 BN152 CB001 CC041                       CC161 CC181 CD001 CF061                       CF071 CF211 CG001 CH071                       CK021 CL031 CN021 FD040                       FD050 FD070 FD200 GA01                 4J100 AA02P AA03P AS02P BC69P                       CA03 CA04 CA05 CA31 DA01                       HC63 JA15

Claims (3)

[Claims] 1. A synthetic resin (A) and (B) (b-1) a piperidine compound represented by the following general formula (1) (b-2):
A synthetic resin composition comprising a high molecular weight stabilizer added to a polymer having a molecular weight of 300 or more. [Chemical 1] 2. The synthetic resin composition according to claim 1, wherein the polymer (b-2) having a molecular weight of 300 or more is an ethylene polymer. 3. The synthetic resin composition according to claim 1, which is used for an agricultural film.