JP2005239839A - Stabilized synthetic resin composition and agricultural film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a synthetic resin composition which maintains an excellent stabilizing effect over a long period even under acidic conditions. <P>SOLUTION: The synthetic resin composition is stabilized by a low basic hindered amine compound having a cyclic acetal skeleton represented by formula (I) (wherein R is a 1-30C alkyl or hydroxyalkyl group or an alkenyl group; R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are each hydrogen, a hydroxy group, a 1-20C alkyl or hydroxyalkyl group, an alkenyl group or the like, provided that at least any one of R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>is a group other than hydrogen, and when R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>, and R<SP>4</SP>are only hydrogen and alkyl groups, the sum of carbon atoms is ≥6). The agricultural film uses the synthetic resin composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a synthetic resin composition excellent in long-term weather resistance by a low basic hindered amine compound having a cyclic acetal skeleton.

  Hindered amine compounds are known to suppress the photodegradation of organic substances such as synthetic resins, and have structures with active hydrogen, active hydrogen due to differences in stabilization effect due to differences in amine structure and the impact from the usage environment. A tertiary amine structure that does not have an alkyl group and a lower basic alkyloxyamine structure than the tertiary amine structure have been studied. In addition, studies have been made to increase the molecular weight by introducing a triazine skeleton for the purpose of improving compatibility with a synthetic resin to be stabilized and extraction resistance.

  In recent years, it has been found that low basic hindered amines maintain a stabilizing effect in applications exposed to acidic environments such as acid rain and agricultural chemicals, and Japanese Patent Application Laid-Open Nos. 8-302063 and 2001-139821. (See Patent Document 1 and Patent Document 2).

  Moreover, since the high molecular weight hindered amine compound proposed in Japanese Patent Publication No. 61-16775 is hardly volatilized, it is used for applications that require a long-term stabilization effect (see Patent Document 3).

  Furthermore, a polymerizable hindered amine compound proposed in Japanese Patent Publication No. 46-42618, a high molecular weight hindered amine compound obtained by adding a nitroxy radical to a high molecular weight substance proposed in Japanese Patent Application Laid-Open No. 2001-139721, and the like. Known (see Patent Document 4 and Patent Document 2).

  On the other hand, as a hindered amine compound having a cyclic acetal skeleton, for example, Japanese Patent Application Laid-Open No. 49-64635 has been proposed. The hindered amine compound may use piperidinol as a raw material or piperidinone. When piperidinone is used as a raw material, a cyclic acetal skeleton is easily synthesized (see Patent Document 5).

Japanese Laid-Open Patent Publication No. 54-42000 proposes a low basic hindered amine compound having a cyclic acetal skeleton. This compound is a polymer compound having the following structure in the main chain of the polymer (see Patent Document 6).
(In the formula, R ¹ represents a methyl group or an ethyl group, and Y represents an alkylene group having 1 to 10 carbon atoms, a phenylene group, or a biphenylene group.)
Another repeating unit is a group having a phenylmethyl structure which is an alkylene group interrupted by an aryl group such as a xylylene group.

JP-A-1-113368 discloses the following structure of a single molecule:
The following compound which is a cyclic acetal having a monoamine structure has been proposed (see Patent Document 7).
(R ¹ and R ² together represent an alkylene group having 2 to 8 carbon atoms, a hydroxyalkylene group, or an acyloxyalkylene group having 4 to 22 carbon atoms.)

Further, claim 5 of JP-A-6-256678 shows a structure having the following cyclic acetal skeleton as a hindered amine compound having an alkyloxyamine structure effective for stabilizing an organic pigment as formula (VII). Has been.
(Wherein R ¹ represents — (CH ₂ ) _p — or — (C ₆ H ₄ ) —).
There is no synthesis example or example in one of the five structural formulas described as a general formula, and there is no description that it is effective for stabilizing synthetic resins, particularly polyolefins (see Patent Document 8).

  Conventionally, various structures have been studied, and hindered amine compounds that have long-lasting excellent stabilizing effects have been studied. However, in agricultural films, etc., a decrease in light transmittance due to resin deterioration inhibits crop growth. There is a need for a hindered amine compound that maintains a stabilizing effect for a longer period of time.

JP-A-8-302063 (Claims) Japanese Patent Laid-Open No. 2001-139821 (Claims) Japanese Patent Publication No. 61-16775 (Claims) Japanese Examined Patent Publication No. 46-42618 (Claims) JP 49-64635 A (pages 14-15, Reference Examples 1-6) JP-A-54-42000 (Claim 1 of the Claims (especially Formula (X) and Formula (XI)) JP-A-1-113368 (Claim 2 of the Claims (especially Formula (C) and upper right column on page 4)) JP-A-6-256678 (Claim 5 of the Claims (especially Formula (VII) and page 5))

  Provided is a synthetic resin composition that has an excellent stabilizing effect for a long time even under acidic conditions.

  As a result of intensive studies in view of the above-mentioned present situation, the present inventors have found that a low basic hindered amine compound having a cyclic acetal skeleton represented by the following general formula (I) provides an excellent long-term stabilization effect. The headline, the present invention has been reached.

More specifically, the first of the present invention provides a synthetic resin composition stabilized by a hindered amine compound represented by the general formula (I).
(In the formula, R represents an alkyl group, a hydroxyalkyl group, or an alkenyl group having 1 to 30 carbon atoms, and R ¹ , R ² , R ^3, and R ⁴ are a hydrogen atom, a hydroxy group, and 1 carbon atom) Represents an alkyl group, a hydroxyalkyl group, an alkenyl group, or a group represented by the following general formula (i) or (ii), or any one of R ¹ and R ² or R ³ and R ⁴ A pair represents a group represented by the following general formula (iii), provided that at least one of R ¹ , R ² , R ³ , and R ⁴ represents a group other than a hydrogen atom, and R ¹ , R ² , When R ³ and R ⁴ are only a hydrogen atom and an alkyl group, the total number of carbon atoms is 6 or more.)
(Wherein R represents the same group as R in formula (I), R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, Or X represents a direct bond, an alkylene group having 1 to 8 carbon atoms, an alkenylene group, a cycloalkylene group having 6 to 18 carbon atoms, or
-(CH ₂ ) _q -O- (CH ₂ ) _p -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O)-(CH ₂ ) _p -C (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -O- (CH ₂ ) _p -OC (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -NH-C (= O)-(CH ₂ ) _p -C (= O) -NH- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -NH- (CH ₂ ) _p -NH-C (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -O- (CH ₂ ) _q- , and
-(CH ₂ ) _q -O- (CH ₂ ) _q- ,
Represents a divalent group selected from the group (p represents a number of 1 to 10 and q represents a number of 0 to 4). )
(Wherein R represents the same group as R in formula (I), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group, and an alkanoyloxyalkyl group having 3 to 30 carbon atoms. Represents.)
In the second aspect of the present invention, R is an alkyl group having 3 to 18 carbon atoms, R ¹ and R ⁴ are hydrogen atoms, R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is a group (i) or ( A synthetic resin composition stabilized by the hindered amine compound according to the first aspect of the present invention, which is ii).
A third aspect of the present invention is the first aspect of the present invention, wherein R represents an alkyl group having 3 to 18 carbon atoms, R ¹ and R ² represent a hydrogen atom, and R ³ and R ⁴ together represent a group (iii). And a synthetic resin composition stabilized by the hindered amine compound.
4th of this invention provides the synthetic resin composition which mix | blended 0.01-10 weight part of the hindered amine compound as described in the 1st or 2 of this invention with 100 weight part of synthetic resins.
5th of this invention provides the polyolefin resin composition which mix | blended 0.05-5 weight part of hindered amine compounds as described in the 1st or 2 of this invention with 100 weight part of polyolefin resin.
6th of this invention provides the film for agriculture using the polyolefin resin composition as described in 5th of this invention.

  ADVANTAGE OF THE INVENTION By this invention, the synthetic resin composition stabilized with the low basic hindered amine compound which has a cyclic acetal frame | skeleton which has a long-term weather-resistance provision effect, especially a polyolefin agricultural film can be provided.

  The present invention is described in detail below.

  Examples of the alkyl group having 1 to 30 carbon atoms represented by R in the general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, sec-butyl, pentyl, sec-pentyl, Tertiary pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, behenyl are hydroxyalkyl groups , Hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-2-methylpropyl and the like.

  Examples of the alkenyl group having 2 to 30 carbon atoms represented by R in the general formula (I) include alkenyl groups corresponding to the above alkyl groups such as vinyl, allyl, butenyl, pentenyl, oleyl and the like.

As the alkyl group having 1 to 20 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (I), among the alkyl groups in the group R, those having the corresponding number of carbon atoms are Examples of the hydroxyalkyl group include those having the corresponding number of carbon atoms among the hydroxyalkyl groups in the group R.

Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (I) include those having the corresponding number of carbon atoms in the examples of the group R. However, when the groups represented by R ¹ , R ² , R ³ , and R ⁴ are selected from any one of a hydrogen atom, an alkyl group, a hydroxyalkyl group, and an alkenyl group, they are not all hydrogen atoms. In the case of only a hydrogen atom and an alkyl group, the total number of carbon atoms is 6 or more. If all are hydrogen atoms or the total number of carbon atoms is less than 6, long-term stabilization effects cannot be obtained.

  Examples of the alkylene group having 1 to 8 carbon atoms represented by X in the general formulas (i) and (ii) include methylene, ethylene, propylene, tetramethylene, 1,2-butylene, 1,3-butylene, Pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, octamethylene and the like, and alkenylene groups include ethylene, propylene, butylene and the like.

  Examples of the cycloalkylene group having 6 to 18 carbon atoms represented by X in the general formula (I) include 1,3-cyclohexylene, 1,4-cyclohexylene, 4,4′-bicyclohexylene, and bis. Examples include cyclohexylmethane-4,4′-diyl.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁵ in the group (iii) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl 2-hydroxyhexyl and the like, and hydroxyalkyl includes hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, hydroxybutyl, 2-hydroxy-2-methylpropyl and the like.

Examples of the alkanoyloxyalkyl group having 3 to 30 carbon atoms represented by R ⁵ in the group (iii) include acetyloxymethyl, octanoyloxymethyl, stearoyloxymethyl, acetyloxyethyl, octanoyloxyethyl, stearoyl Examples include oxyethyl.

  More specifically, examples of the compound represented by the general formula (I) include the following compound Nos. 1-No. 10 is mentioned. However, the present invention is not limited by the following compounds.

  The method for synthesizing the above compound is not particularly limited, and can be synthesized by a general organic synthesis method. For example, the compound having 2,2,6,6-tetramethylpiperidin-4-one and 1,3-diol structure can be synthesized. As the purification method, a method using distillation, recrystallization, reprecipitation, column, filter agent / adsorbent, or the like can be used as appropriate as a synthesis method by dehydrating a monohydric alcohol with a catalyst such as p-toluenesulfonic acid. The quality, such as purity, acid value, and transmittance at a specific wavelength, of the hindered amine compound obtained is not particularly limited, and can be synthesized at a low cost as long as the final performance of the synthetic resin composition to be stabilized satisfies the required performance in the application. A manufacturing method is appropriately selected.

  Synthetic resins stabilized by the hindered amine compound represented by the general formula (I) include polypropylene, low density polyethylene, linear low density polyethylene, high density polyethylene, polybutene-1, poly-3-methylpentene, poly- Α-olefin homopolymer or copolymer such as 4-methylpentene, ethylene-propylene copolymer, polyunsaturated compounds such as α-olefin and conjugated diene or non-conjugated diene, acrylic acid, methacrylic acid, Copolymers with vinyl acetate, etc., polyethylene terephthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / paraoxybenzoate, polybutylene terephthalate and other linear polyesters, acid-modified polyesters, polycaprolactam and polyhexamethylene adipamide Such as polyamide, polyimide, polystyrene, styrene and / or α-methylstyrene and other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (eg, AS Resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.), 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, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride- Halogen-containing resins such as cyclohexylmaleimide copolymers Polymers of (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, octyl (meth) acrylate, polyether ketone, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polyvinyl alcohol, straight chain Thermosetting resins such as branched polycarbonate, petroleum resin, coumarone resin, polyphenylene oxide, polyphenylene sulfide, polyurethane, fiber-based resin, etc., epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, etc. Resin, further isoprene rubber, butadiene rubber, butadiene-styrene copolymer rubber, butadiene-acrylonitrile copolymer rubber, acrylonitrile-butadiene-styrene copolymer rubber, ethylene and propylene, butene It may be a copolymer rubber with an α-olefin such as 1 or an elastomer such as a terpolymer rubber with a non-conjugated diene such as ethylene-α-olefin and ethylidene norbornene or cyclopentadiene, or a silicone resin. These resins and / or elastomers may be alloyed or blended.

  The synthetic resin is a lamella measured by stereoregularity, specific gravity, type of polymerization catalyst, presence / absence or degree of polymerization catalyst removal, degree of crystallization, polymerization conditions such as temperature or pressure, type of crystal, X-ray small angle scattering. The copolymer size, crystal aspect ratio, solubility in aromatic or aliphatic solvents, solution viscosity, melt viscosity, average molecular weight, degree of molecular weight distribution, how many peaks in molecular weight distribution, Although it may be a block or random, the expression of the stabilizing effect may vary depending on the blending ratio of each monomer, etc., but it can be applied when any resin is selected.

A method for blending the hindered amine compound represented by the general formula (I) into the resin is not particularly limited, and a known blending technique of a stabilizer into the resin is used. Any of a method of adding to a polymerization system in advance when polymerizing a synthetic resin, a method of adding during polymerization, and a method of adding after polymerization may be used. In addition, when adding after polymerization, a method of kneading a synthetic resin powder or pellets mixed with a Henschel mixer or the like with an extruder or the like, a method of spraying and impregnating a synthetic resin as a solution, a master batch The type of processing machine to be used, the processing temperature, the cooling conditions after processing, etc. are not particularly limited, and it is preferable to select conditions that make the obtained resin properties suitable for the application. Further, the hindered amine compound of the present invention may be used alone or in the form of granules together with other additives.
A preferable blending amount of the hindered amine compound of the present invention is 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin.

  When the hindered amine compound represented by the general formula (I) of the present invention is used for the stabilization of a synthetic resin, various compounding agents usually used for each resin are used as necessary. For example, phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, UV absorbers, other hindered amine compounds, nucleating agents, flame retardants, flame retardant aids, lubricants, fillers, fibrous fillers , Metal soap, hydrotalcite, antistatic agent, pigment, dye, antibacterial agent, antifungal agent, antiseptic agent, antifouling agent, rust inhibitor, surfactant, compatibilizer, antisettling agent, polymerization inhibitor , Thickeners, antifoaming agents, coupling agents, leveling agents, drying agents, anti-sagging agents, dehydrating agents, curing catalysts, adhesion-imparting agents, and foaming agents.

  Examples of the phenol type include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4-hydroxybenzyl). ) Phosphonate, 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-m-) Cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol) 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditertiary Butyl-4-hydroxyphenyl) propionate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [ 3,5-ditertiarybutyl-4-hydroxyphenyl) propionate], tetrakis (3- (3,5-ditertiarybutyl-4-hydroxyphenyl) propionyloxymethyl) methane, bis [3,3-bis ( 4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] Terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3- Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] unde And triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin, more preferably 0.05-5 parts by weight are used.

  Examples of the sulfur-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-dodecyl mercaptopropionate). Β-alkyl mercaptopropionic acid esters of polyols such as 0.001 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin.

  Examples of the phosphorus antioxidant include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, and tris (2,4-ditert-butyl-5- Methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenylphos Phyto, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-ditert-butyl-4-methylphenyl) penta Thritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol Diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4- Hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide, 2,2'-methylenebis (4,6-tert-butylphenyl)- -Ethylhexyl phosphite, 2,2'-methylenebis (4,6-tert-butylphenyl) -octadecyl phosphite, 2,2'-ethylidenebis (4,6-ditert-butylphenyl) fluorophosphite, tris ( 2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphospin-6-yl) oxy] ethyl) amine, 2-ethyl-2 -Phosphites of butyl propylene glycol and 2,4,6-tritert-butylphenol, etc., and 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the resin Is used.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- 2- (2′-hydroxyphenyl) benzotriazoles such as 2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butyl Phenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl Benzoates such as -4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2′-ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl Acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, etc. Anoacrylates; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) ) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-ditert-butylphenyl) -s-triazine, etc. Of triaryltriazines, and 0.001 to 10 parts by weight, more preferably 0.05 to 5 parts by weight is used with respect to 100 parts by weight of the resin.

  Examples of the other hindered amine compounds include 2,2,6,6-tetramethyl-4-piperidyl-1-oxy, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2 , 6,6-pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2 , 6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetra Ruboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1, 2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-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 / Bromoethane 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-tert-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-tetraaza Dodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 IL] -1,5,8,12-tetraazadodeca 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] amino Undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] Examples thereof include hindered amine compounds such as aminoundecane.

  Examples of the nucleating agent include aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate; sodium bis (2,4-ditert-butylphenyl) phosphate, bis (2,4- Acid phosphate metal salts such as ditertiarybutylphenyl) lithium phosphate and sodium-2,2′-methylenebis (4,6-ditertiarybutylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, etc. And polyhydric alcohol derivatives thereof.

  Examples of the flame retardant include halogen flame retardants, red phosphorus, melamine phosphate, guanidine phosphate, piperazine phosphate, melamine pyrophosphate, piperazine pyrophosphate, phosphate ester compounds, phosphazene compounds and other phosphorus flame retardants, melamine shear Nitrogen flame retardants such as nurate, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, flame retardant aids include inorganic compounds such as antimony trioxide and zinc borate, and drip prevention such as polytetrafluoroethylene Agents and the like.

Hydrotalcites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment or the presence or absence of crystal water. For example, a basic carbonate represented by the following general formula (II) can be mentioned.
_{M x Mg y Al z CO 3} (OH) xp + 2y + 3z-2 · nH 2 O (II)
(Wherein M is an alkali metal or zinc, X is a number from 0 to 6, y is a number from 0 to 6, z is a number from 0.1 to 4, p is a valence of M, and n is Represents the number of water of crystallization from 0 to 100.)

  Lubricants include fatty acid amides such as lauryl amide, myristyl amide, lauryl amide, stearyl amide, and behenyl amide, metal soaps such as ethylene bisstearyl amide, polyethylene wax, calcium stearate, magnesium stearate, distearyl phosphate magnesium, Examples thereof include phosphate metal salts such as stearyl phosphate magnesium.

  As the filler, inorganic particles such as talc, silica, calcium carbonate, glass fiber, potassium titanate, potassium borate, etc. are appropriately selected for the particle size in the case of spherical materials, and the fiber diameter, fiber length and aspect ratio in the case of fibrous materials. Used. Moreover, it is preferable to use what was surface-treated as a filler as needed.

  In addition, when used for agricultural films, an ultraviolet absorber is added to control the growth of crops, an infrared absorber is added to improve heat retention, or fog is generated in the house. The film surface may condense and light may not reach the crop sufficiently, so an anti-fogging agent or an anti-fogging agent may be added.

  The hindered amine compound of the present invention is suitably used for stabilization of synthetic resins, especially for polyolefin agricultural films, paints and sealants exposed to acid rain outdoors, but due to the influence of acidic components such as melamine pyrophosphate. Long-term stabilization effect of organic substances is required, such as resin compositions containing acidic components that hindered amine compounds have not sufficiently demonstrated stabilization effects, and stabilization of liquid products such as lubricants and electrolytes. It can be used in applications.

(Example)
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.

Synthesis Examples 1-5
(Synthesis of 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one)
15.0 g (86.6 mmol) of 4-hydroxy-1-oxy-2,2,6,6-tetramethylpiperidine was dissolved in 40.0 g of chlorobenzene, and 27.6 g of dilauroyl peroxide (69. 3 mmol) in 125 g of chlorobenzene was added dropwise over 3 hours. Thereafter, the reaction was performed for 6 hours, and it was confirmed by gas chromatography that the raw material had disappeared from the obtained reaction product. To this reaction solution, 0.1 g of 4-acetyl-1-oxy-2,2,6,6-tetramethylpiperidine was added and cooled to 0 ° C., and then 48.3 g of 10% aqueous sodium hypochlorite solution (64.64 g). 9 mmol) was added dropwise over 3 hours. After a further 3 hours of reaction, 15 ml of 15% aqueous sodium thiosulfate solution was added, and the mixture was heated to 40 ° C. and reacted for 1 hour. After separating the organic layer and the aqueous layer, the aqueous layer was extracted twice with 70 ml of toluene, and dehydrated with anhydrous magnesium sulfate together with the organic layer. Magnesium sulfate was removed by filtration, the filtrate was concentrated under reduced pressure, 50 g of hexane was added, 17.3 g (86.6 mmol) of a 20% aqueous sodium hydroxide solution was added at 55 ° C., and 15 g of methanol was added and left standing. did. The aqueous layer was removed and washed twice with 15 g of water. The mixture was dehydrated by heating, dissolved in 40 g of desolvent and methanol, and cooled to −40 ° C. to precipitate crystals. A white powder (yield 50%) of 1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one was obtained by filtration. It was a colorless liquid at room temperature.

(Synthesis of cyclic acetal skeleton compound)
1-undecyloxy-2,2,6,6-tetramethylpiperidin-4-one 8.00 g (24.58 mmol), polyhydric alcohol shown in Table 1 (34.41 mmol), paratoluenesulfonic acid 0 .54 g and 76.00 g of cyclohexane were added to the flask, and 25 g of methanol was added dropwise at 70 to 80 ° C. over 7 hours, and the mixture was further maintained for 2 hours. Methanol and water were removed azeotropically, cooled to 40 ° C., 40 ml of ethyl acetate, 0.15 g of sodium carbonate and 30 ml of water were added and stirred for 30 minutes. After standing, the aqueous layer was removed, washed with 20 ml of water twice, the organic layer was dried over anhydrous magnesium sulfate, and magnesium sulfate was removed by filtration. The filtrate was desolvated under reduced pressure to obtain a single yellow viscous liquid. The resulting liquid was purified by column chromatography (silica gel). Table 1 shows the diol used, yield, properties, and purity measured by liquid chromatography. The compound obtained in Synthesis Example 1 is Comparative Compound 1 in the following Reference Example, and the compound obtained in Synthesis Example 2 is the compound No. 1 described above. 1.

Synthesis Example 6 (Synthesis of Compound No. 3)
1,5-Dioxa-9-aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-9-undecyloxyspiro [5,5] undecane 6 obtained in Synthesis Example 3 .50 g (14.7 mmol), 1.85 g (8.64 mmol) of diphenyl carbonate and 0.64 g of potassium carbonate were added to 80.0 g of mineral spirits, and reacted at 170 ° C. for 6 hours. The reaction solution was cooled to 80 ° C. and washed three times with 30 ml of water. The mixture was dehydrated under reduced pressure at 80 ° C., further desolvated with an evaporator and concentrated. The concentrate is purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 5/1), and further, the target product is isolated by preparative gel permeation chromatography and the solvent is removed. As a result, 2.79 g (yield 41.7%) of colorless crystals at 8 ° C. was obtained.

Synthesis Example 7 (Synthesis of Compound No. 2)
1,5-Dioxa-9-aza-3-ethyl-3-hydroxymethyl-8,8,10,10-tetramethyl-9-undecyloxyspiro [5,5] undecane 8 obtained in Synthesis Example 3 .10 g (18.3 mmol), 1.15 g (6.60 mmol) of dimethyl adipate and 0.65 g of tetraisopropyl titanate were dissolved in 80.0 g of mineral spirit, and the reaction was carried out at 170 ° C. for 6 hours. The reaction solution was cooled to 80 ° C. and washed three times with 30 ml of water. The mixture was dehydrated under reduced pressure at 80 ° C., further desolvated with an evaporator and concentrated. The concentrate is purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 5/1), and the target product is isolated by preparative gel permeation chromatography to remove the solvent and have a melting point of 61.1. As a result, 2.87 g (yield: 43.8%) of colorless crystals having a purity of 99.2% was obtained.

Examples and Comparative Examples (Polyethylene Stabilized Resin Composition)
100 parts by weight of a linear low density polyethylene resin (manufactured by Nippon Unicar Co., Ltd .: PES120), 0.05 parts by weight of calcium stearate, tetrakis (3- (3,5-ditert-butyl-4-hydroxyphenyl) Propionyloxymethyl) methane 0.05 part by weight, tris (2,4-ditert-butylphenyl) phosphite 0.05 part by weight and the hindered amine compound described in Table 2 were added, and 200 ° C. by a single screw extruder. Pellets were made at 25 rpm. A film having a thickness of 80 microns was prepared from the obtained pellets by a 180 ° C. press.

The obtained test piece was fumigated with 2 g of sulfur on a hot plate in a 1 m × 1 m × 1 m cardboard container and allowed to stand for 24 hours. Further, the temperature was measured at 63 ° C. with a sunshine weatherometer (every 2 hours) The carbonyl index after 600 hours was measured in an 18 minute rain cycle. The results are shown in Table 2. The carbonyl index is defined by [log (Io / I)] / d using infrared absorption spectrum analysis data of the film. Here, Io is the transmittance (%) before deterioration at 1710 cm ⁻¹ , I is the transmittance (%) after deterioration, and d is the thickness (cm) of the film.

Claims (6)

A synthetic resin composition stabilized by a hindered amine compound represented by formula (I).
(In the formula, R represents an alkyl group, a hydroxyalkyl group, or an alkenyl group having 1 to 30 carbon atoms, and R ¹ , R ² , R ^3, and R ⁴ are a hydrogen atom, a hydroxy group, and 1 carbon atom) Represents an alkyl group, a hydroxyalkyl group, an alkenyl group, or a group represented by the following general formula (i) or (ii), or any one of R ¹ and R ² or R ³ and R ⁴ A pair represents a group represented by the following general formula (iii), provided that at least one of R ¹ , R ² , R ³ , and R ⁴ represents a group other than a hydrogen atom, and R ¹ , R ² , When R ³ and R ⁴ are only a hydrogen atom and an alkyl group, the total number of carbon atoms is 6 or more.)
(Wherein R represents the same group as R in formula (I), R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group, Or X represents a direct bond, an alkylene group having 1 to 8 carbon atoms, an alkenylene group, a cycloalkylene group having 6 to 18 carbon atoms, or
-(CH ₂ ) _q -O- (CH ₂ ) _p -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O)-(CH ₂ ) _p -C (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -O- (CH ₂ ) _p -OC (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -NH-C (= O)-(CH ₂ ) _p -C (= O) -NH- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -NH- (CH ₂ ) _p -NH-C (= O) -O- (CH ₂ ) _q- ,
-(CH ₂ ) _q -OC (= O) -O- (CH ₂ ) _q- , and
-(CH ₂ ) _q -O- (CH ₂ ) _q- ,
Represents a divalent group selected from the group (p represents a number of 1 to 10 and q represents a number of 0 to 4). )
(Wherein R represents the same group as R in formula (I), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyalkyl group, and an alkanoyloxyalkyl group having 3 to 30 carbon atoms. Represents.) 2. R is an alkyl group having 3 to 18 carbon atoms; R ¹ and R ⁴ are hydrogen atoms; R ² is an alkyl group having 1 to 4 carbon atoms; and R ³ is a group (i) or (ii). A synthetic resin composition stabilized by the hindered amine compound described in 1. The synthesis stabilized by the hindered amine compound according to claim ¹ , wherein R represents an alkyl group having 3 to 18 carbon atoms, R ¹ and R ² represent a hydrogen atom, and R ³ and R ⁴ together represent a group (iii). Resin composition.   The synthetic resin composition which mix | blended 0.01-10 weight part of the hindered amine compound of Claim 1 or Claim 2 with 100 weight part of synthetic resins.   The polyolefin resin composition which mix | blended 0.05-5 weight part of hindered amine compounds of Claim 1 or Claim 2 with 100 weight part of polyolefin resin.   An agricultural film using the polyolefin resin composition according to claim 5.