JPH1135560A - Piperidine-based compound, intermediate therefor, production thereof and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound usable as a stabilizer for an organic material excellent in bleeding resistance. SOLUTION: This compound is a piperidine-based compound of formula I [R1 is a 1-6C alkyl; R3 is H or a 1-6C alkyl; (m) is an integer of 0-2, etc.; R2 , and R4 to R6 are each independently H or a 1-6C alkyl; R7 and R8 are each independently H or a 2-18C acyl, with the proviso that, simultaneously, R7 and R8 are not H; (n) is an integer of 0-2], and for example, N,N'-dibenzoyl -N,N'-bis (2,2,6,6 -tetramethyl-4 -piperidyl)-2 -methyl-1,5 -pentanediamine is cited. The compound of formula I is obtained, for example, by acylating bispiperidinylalkylenediamines of formula II by using at least one kind of carboxylic acids of formula III (R9 is a 1-17C alkyl, etc.; X is a halogen, etc.). The organic material containing the compound of formula I is stable against photodegradation, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel piperidine-based compound, a process for producing the same, and its use as a stabilizer for organic materials.

[0002]

2. Description of the Related Art Organic materials such as thermoplastic resins, thermosetting resins, and natural or synthetic rubbers are degraded by light and are accompanied by phenomena such as softening, embrittlement and discoloration. It is well known that physical properties are significantly reduced.
For the purpose of preventing such deterioration due to light, N, N'-diacyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)
There has been proposed a compound such as -1,6-hexanediamine in which the linking group connecting two Ns substituted with a piperidine ring is a linear alkylene (for example, Japanese Patent Publication No. 6-18927).

[0003] However, such compounds in which the linking group is a straight-chain alkylene have the drawback of bleeding when contained in an organic material, and have not been satisfactory in this respect. The present inventors have conducted intensive studies on a bonding group connecting two Ns in which a piperidine ring has been substituted in order to find a stabilizer for organic materials having excellent bleeding resistance. The present inventors have found that piperidine-based compounds which are alkylenes having a substituent at the β-position have remarkably excellent bleeding resistance, and have completed the present invention.

[0004]

That is, the present invention provides the following formula:
(I)(Where R₁, R_Three, M is R₁Is an alkyl having 1 to 6 carbon atoms
A group represented by R_ThreeIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
M represents an integer of 0 to 2 or R₁And R_Three And those
Is substituted carbon atom and (CH_Two)_mTogether with the carbon number
5 carbon atoms which may be substituted by 1 to 6 alkyl groups
Represents a bivalent cyclic group of 1 to 9; R_Two, R_Four, R_FiveAnd R₆Haso
Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
Represent. R₇And R₈Are each independently a hydrogen atom or carbon number
Represents 2 to 18 acyl groups, and simultaneously being a hydrogen atom
Absent. n represents the integer of 0-2. )
Piperidine compounds with excellent stability
And its use as a stabilizer for organic materials
Things.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
I do. Piperidine compound represented by formula (I) of the present invention
In, R₁, R_Three, M is R ₁Is an alkyl having 1 to 6 carbon atoms
The kill group is represented by R_ThreeIs a hydrogen atom or an alkyl having 1 to 6 carbon atoms
M is an integer of 0 to 2 or R₁And R_ThreeAnd it
And (CH)_Two)_mBut together carbon
Carbon number which may be substituted by the alkyl group of the number 1 to 6
Represents a 5 to 9 divalent cyclic group. R_Two, R_Four, R_FiveAnd R₆Is
Each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
Represents R₇And R₈Are each independently a hydrogen atom or carbon
Represents an acyl group of Formulas 2 to 18, and is a hydrogen atom at the same time
There is no. n represents the integer of 0-2.

Here, typical examples of the alkyl group having 1 to 6 carbon atoms include lower alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl and t-pentyl. Besides the group, hexyl, cyclohexyl and the like can be mentioned. Examples of the divalent cyclic group having 5 to 9 carbon atoms include monocyclic cyclic groups such as cyclopentylene, cyclohexylene, and cycloheptylene; bicyclohexylene;
And polycyclic ring groups such as bicycloheptylene and bicyclononylene. Representative examples of the divalent cyclic group having 5 to 9 carbon atoms which may be substituted by an alkyl group having 1 to 6 carbon atoms include, for example, cyclopentylene-1,2,3,3,5-trimethyl Cyclopentylene-1,2, cyclohexylene-1,2,
Cyclohexylene-1,3, cyclohexylene-1,4,5,5-dimethylcyclohexylene-1,3, bicyclo [2.2.1] heptylene-2,5, bicyclo [2.2.1] heptylene-2,6, 4,7,7
-Trimethylbicyclo [3.1.1] heptylene-2,3,4,7,7-trimethylbicyclo [3.1.1] heptylene-2,6,4,7,7-trimethylbicyclo [3.1.1] heptylene-3, 6,1,7,7-trimethylbicyclo [2.2.1] heptylene-2,3,1,7,7-trimethylbicyclo [2.1.1] heptylene-2,5,1,7,7-trimethylbicyclo [2.1 .1] heptylene-2,6 and the like. Examples of the acyl group having 2 to 18 carbon atoms include, for example, a compound represented by the formula (III) R ₉ -C (O)-(III) (wherein R ₉ is an alkyl group having 1 to 17 carbon atoms or
Represents a phenyl group which may be substituted with an alkyl group of from 6 to 6. ) And the like. Here, typical examples of the alkyl group having 1 to 17 carbon atoms include, for example, hexyl, cyclohexyl, octyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, , 1,3,3-tetramethylbutyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, heptadecyl and the like. Representative examples of the phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms include, for example, phenyl and the same 1 to 4 carbon atoms as described above.
And phenyl substituted with an alkyl group of 6.

Among them, R ₁ is preferably a lower alkyl group, and R ₃ is preferably hydrogen, a lower alkyl group, particularly hydrogen or methyl. In addition, R ₁ and R ₃ , a carbon atom substituted by them and (CH ₂ ) _m may be combined with each other to form a divalent cyclic group having 5 to 9 carbon atoms, which may be substituted by a lower alkyl group. 3,3,5-trimethylcyclopentylene-1,2,5,5-
Dimethylcyclohexylene-1,3, bicyclo [2,2,1] heptylene-2,5, bicyclo [2,2,1] heptylene-2,6 and the like are also preferable. R ₂ is preferably hydrogen or a lower alkyl group, and R ₄ is preferably hydrogen.
R ₅ and R ₆ are preferably hydrogen or a lower alkyl group, more preferably hydrogen or methyl, especially hydrogen. R ₇ and R ₈ are preferably the same or different acyl groups represented by the formula (III), and among them, R ₉ is a lower alkyl group, phenyl, substituted by a lower alkyl group such as 4-t-butylphenyl. It is preferably an acyl group selected from a phenyl group or the like which may be present,
In particular, it is preferable that R ₉ is an acyl group selected from t-butyl, t-pentyl, phenyl and the like.

The piperidine compound (I) of the present invention can be prepared, for example, by reacting a compound of the formula (II) (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , m and n have the same meaning as described above.)

A bispiperidinylalkylenediamine represented by the formula (IV) R ₉ -C (O) -X (IV) (wherein R ₉ has the same meaning as described above, and X is a halogen atom) represents _{-OR 10, -OC (O) R} 9 or -NR ₁₁ R _12,
R _10, R _11, R ₁₂ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )), And acylation using at least one carboxylic acid represented by the formula (1).

The acylation reaction can be carried out by a known method, for example, “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds (II)”, Chapter 11.
It can be carried out in accordance with the method described on pages 36 to 1159 (issued by Maruzen Co., Ltd. on December 20, 1977). The reaction is carried out in a solvent or without solvent, and when a solvent is used, examples of the solvent include benzene, toluene, xylene,
Aromatic hydrocarbons such as ethylbenzene and nitrobenzene,
Aliphatic hydrocarbons such as hexane, heptane and octane; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and 1,4-dioxane; halogenated carbons such as chloroform, carbon tetrachloride, monochlorobenzene, dichloromethane, dichloroethane and dichlorobenzene Hydrogen and the like. When a solvent is used, it is usually 3 to 50 based on the bispiperidinylalkylenediamine (II).
It is used in an amount approximately by weight, preferably approximately 3 to 15 times by weight.

The carboxylic acids (IV) as acylating agents are
For bispiperidinylalkylenediamines (II),
Usually, about 0.2 to 10 equivalents, preferably about 0.5 to 4 equivalents are used. When two or more carboxylic acids having different R ₉ are used, the mixture can be reacted, or they can be sequentially reacted. The acylation reaction is usually performed at 0 to
It is carried out at about 150 ° C, preferably about 20 to 80 ° C. After the reaction, if necessary, the piperidine compound of the present invention can be extracted from the reaction mass by carrying out neutralization, extraction, washing with water, and distillation at a low boiling point. The piperidine compound taken out is recrystallized, by purification means such as distillation,
It can be further purified.

Here, the bispiperidinylalkylenediamines (II), which are the raw materials of the piperidine compound (I) of the present invention, are, for example, the corresponding alkylenediamines (V) H ₂ N—CH ₂ —C (R ₁ ) (R ₂ )-(CH ₂ ) _m -C (R ₃ ) (R ₄ )
_{-C n H 2n -NH 2 (V} ) ( _{wherein, R 1, R 2, R} 3,
R ₄ , m and n have the same meaning as described above. ) And the corresponding piperidones (VI) and / or (VII) (Wherein, R ₅ and R ₆ have the same meanings as described above). The reductive alkylation reaction can be carried out according to a known method, for example, a method described in JP-A-64-50858. The reaction is carried out with or without a solvent. When a solvent is used, examples of the solvent include the same aromatic hydrocarbons as described above,
Aliphatic hydrocarbons as described above, methanol, ethanol, n-propanol, i-propanol, n-butanol,
Examples include alcohols such as i-butanol and sec-butanol. When a solvent is used, it is usually about 2 to 30 times by weight, preferably 2 to 30,
Used about 10 times by weight.

The amount of the piperidone is usually about 2 to 10 times, preferably about 2 to 5 times, more preferably about 2 to 2.5 times the alkylenediamine. Further, as the reductive alkylation catalyst, for example, nickel, copper,
Catalysts such as copper-chromium, ruthenium, rhodium, palladium, platinum and the like are used. These catalysts may be those supported on a carrier such as activated carbon, silica, alumina, silica-alumina and titania. Such a catalyst is generally used in an amount of about 0.05 to 50% by weight, preferably about 0.5 to 15% by weight, based on the alkylenediamine.

The hydrogen pressure of the reductive alkylation reaction is usually 1
To 50 kg / cm ² or so, preferably 2~40Kg / cm ^2, more preferably about 5 to 20 kg / cm ² or so, the temperature is usually 20 to 15
About 0 ° C, preferably about 40 to 120 ° C, more preferably 50 ° C
~ 100 ° C. After the reaction, after removing the catalyst,
By distilling off the solvent, bispiperidinylalkylenediamines (II) can be obtained. The bispiperidinylalkylenediamines (II) thus obtained can be used as a raw material for the acylation reaction as described above, or can be used after purification by a method such as distillation or recrystallization if necessary. . When the solvent in the reductive alkylation step is the same as that in the acylation step, the reaction mass from which the catalyst has been removed can be used as it is.

The thus obtained piperidine compound (I) of the present invention is effective for stabilizing organic materials against photodegradation and the like. Examples of the organic material that can be stabilized by the present invention include the following,
A single substance or a mixture of two or more substances can be stabilized, but not limited to these organic materials.

(1) polyethylene, for example, high density polyethylene (HDPE), low density polyethylene (LDPE),
Linear low density polyethylene (LLDPE), (2) polypropylene, (3) methylpentene polymer, (4) EEA
(Ethylene-ethyl acrylate copolymer) resin, (5) ethylene-vinyl acetate copolymer resin, (6) polystyrenes,
For example, polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), (7) AS (acrylonitrile / styrene copolymer) resin, (8) ABS (acrylonitrile / butadiene / styrene copolymer) resin, (9) AAS
(Special acrylic rubber / acrylonitrile / styrene copolymer) resin, (10) ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin,

(11) chlorinated polyethylene, polychloroprene, chlorinated rubber, (12) polyvinyl chloride, polyvinylidene chloride, (13) methacrylic resin, (14) ethylene-vinyl alcohol copolymer resin, (15) fluororesin , (16) polyacetal, (17) polyphenylene ether resin and polyphenylene sulfide resin, (18) polyurethane, (19) polyamide, (20) polyethylene terephthalate, polybutylene terephthalate,

(21) polycarbonate, (22) polyacrylate, (23) polysulfone, polyetheretherketone, polyethersulfone, (24) aromatic polyester resin, (25) epoxy resin, (26) diallylphthalate prepolymer, (27) Silicone resin, (28) Unsaturated polyester resin, (29) Acrylic modified benzoguanamine resin, (30) Benzoguanamine melamine resin, (31) Urea resin

(32) polybutadiene, (33) 1,2-polybutadiene, (34) polyisoprene, (35) styrene / butadiene copolymer, (36) butadiene / acrylonitrile copolymer, (37) ethylene / propylene copolymer Polymer, (3
8) Silicone rubber, (39) Epichlorohydrin rubber, (4
0) acrylic rubber, (41) natural rubber,

(42) Chlorine rubber paint, (43) Polyester resin paint, (44) Urethane resin paint, (45) Epoxy resin paint, (46) Acrylic resin paint, (47) Vinyl resin paint,
(48) amino alkyd resin paint, (49) alkyd resin paint, (50) nitrocellulose resin paint, (51) oil-based paint,

Among them, thermoplastic resins, especially polyethylene, are preferably used for polyolefins such as HDPE, LDPE, LLDPE and polypropylene.
These polyolefins are not particularly limited, for example,
The one obtained by radical polymerization may be used.
It may be produced by polymerization using a catalyst containing a group b, Vb, VIb or VIII metal. The metal-containing catalyst may be a metal complex having one or more ligands, for example, an oxide, a halogen compound, an alcoholate, an ester, an aryl, or the like coordinated by a π or σ bond. May be used as it is or may be supported on a substrate such as magnesium chloride, titanium chloride, alumina, or silicon oxide. As the polyolefin, those produced using, for example, a Ziegler-Natta catalyst, a TNZ catalyst, a metallocene catalyst, a Phillips catalyst, a Brookhart catalyst and the like are preferably used.

When stabilizing an organic material by incorporating the piperidine compound (I) of the present invention, the piperidine compound (I) is usually added in an amount of 0.0 to 100 parts by weight of the organic material.
It is preferable to use in the range of about 1 to 5 parts by weight. 0.01
If the amount is less than 5 parts by weight, the stabilizing effect is not always sufficient, and if the amount is more than 5 parts by weight, the effect corresponding to the improvement cannot be obtained, which is economically disadvantageous.

In incorporating the piperidine compound (I) of the present invention into an organic material, if necessary, other additives such as a phenolic antioxidant, a sulfuric antioxidant, a phosphorus antioxidant, UV absorber, light stabilizer, peroxide scavenger, polyamide stabilizer, hydroxylamine, lubricant, plasticizer, flame retardant, nucleating agent, metal deactivator, antistatic agent, pigment, filler, antiblocking agent , Surfactants, processing aids, foaming agents, emulsifiers, brighteners, calcium stearate, neutralizing agents such as hydrotalcite, and 9,10-dihydro-9-oxa-10-phosphophenanthrene-10- Color improvers such as oxides and U.S. Pat.Nos. 4,325,853, 4,338,244, 5,175,312, 5,216,
053, 5,252,643, 4,316,611, DE-A-4,3
No. 16,622, 4,316,876, EP-A-589,839, 591,10
Co-stabilizers such as benzofurans and indolines described in the specification of JP-A No. 2 can be added. Of course, these additives can be added simultaneously with the piperidine compound (I), or can be added at a different stage from the piperidine compound (I).

Here, examples of the phenolic antioxidant include the following. (1) Examples of alkylated monophenols 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t
-Butylphenol, 2,6-di-t-butylphenol, 2-
t-butyl-4,6-dimethylphenol, 2,6-di-t-butyl
-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2 -(
α-methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecyl-1'-yl) phenol, 2,4- Dimethyl-6- (1′-methyltridecyl-1′-yl) phenol and mixtures thereof.

(2) Examples of alkylthiomethylphenol 2,4-dioctylthiomethyl-6-t-butylphenol,
4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol and mixtures thereof. (3) Examples of hydroquinone and alkylated hydroquinone 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-
Butylhydroquinone, 2,5-di-t-amylhydroquinone,
2,6-diphenyl-4-octadecyloxyphenol, 2,
6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di-t -Butyl-4-
Hydroxyphenyl) adipates and mixtures thereof.

(4) Examples of tocopherol α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof. (5) Examples of hydroxylated thiodiphenyl ethers 2,2'-thiobis (6-t-butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,2'-thiobis (4- Octylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 4,4'-thiobis (3,6-
Di-t-amylphenol), 4,4 '-(2,6-dimethyl-4-hydroxyphenyl) disulfide and the like.

(6) Examples of alkylidene bisphenols and derivatives thereof 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2 , 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2'-methylenebis
(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-
Methylenebis (4,6-di-t-butylphenol), 2,2'-
Ethylidenebis (4,6-di-t-butylphenol), 2,2 '
-Ethylidenebis (4-isobutyl-6-t-butylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-
Nonylphenol], 2,2'-methylenebis [6- (α, α-
Dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (6-t-butyl-2-methylphenol), 4,4'-
Methylenebis (2,6-di-t-butylphenol), 4,4'-
Butylidenebis (3-methyl-6-t-butylphenol),
1,1-bis (4-hydroxyphenyl) cyclohexane, 1,
1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1,3-Tris (5
-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [ 3,3-bis-3'-t-butyl-4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2
-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl) -6-
t-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,
2-bis (3,5-di-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane , 1,1,5,5-
Tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl-6- (3'-t-butyl-5'-methyl
-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-pentyl-6- [1- (2-hydroxy-3,5-
Di-t-pentylphenyl) ethyl] phenyl acrylate and mixtures thereof.

(7) Examples of O-, N- and S-benzyl derivatives 3,5,3 ', 5'-Tetra-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-t
-Butyl-4-hydroxybenzyl) amine, bis (4-t-
Butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-t-butyl-4-hydroxy Benzyl mercapto acetate and mixtures thereof. (8) Examples of hydroxybenzylated malonate derivatives dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-
Butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-t
-Butyl-4-hydroxybenzyl) malonate, bis [4
-(1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis
(3,5-di-t-butyl-4-hydroxybenzyl) malonate and mixtures thereof. (9) Examples of aromatic hydroxybenzyl derivatives 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, 1,4-bis (3,5-di-t
-Butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) phenol and mixtures thereof.

(10) Examples of triazine derivatives 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di
-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2 -n-octylthio-4,6-bis
(4-hydroxy-3,5-di-t-butylphenoxy) -1,3,5-
Triazine, 2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6-dimethyl Benzyl) isocyanurate,
Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxy-4-)
(Hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-
Tris (3,5-di-t-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate, tris
[2- (3 ', 5'-di-t-butyl-4'-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof.

(11) Examples of benzylphosphonate derivatives: dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl- 3,5-di-t-
Calcium salts of butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester and their salts Mixtures and the like. (12) Examples of acylaminophenol derivatives: 4-hydroxylauric anilide, 4-hydroxystearic anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof. (13) β- (3,5-di-t-butyl-4-hydroxyphenyl)
Examples of esters of propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,3
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof.

(14) β- (5-t-butyl-4-hydroxy-3-
Examples of esters of methylphenyl) propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof. (15) Examples of esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3- Propanediol, 1,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof.

(16) Examples of esters of 3,5-di-t-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols: methanol, ethanol, octanol, octadecanol, ethylene glycol, 3-propanediol, 1,
4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N '-Bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
-Phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof. (17) β- (3,5-di-t-butyl-4-hydroxyphenyl)
Examples of amides of propionic acid N, N'-bis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3' ,
5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamine, N, N'-bis [3- (3 ', 5'-di
-t-butyl-4'-hydroxyphenyl) propionyl] trimethylenediamine and mixtures thereof.

Examples of the sulfur-based antioxidant include the following. Dilauryl 3,3'-thiodipropionate, tridecyl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate,
Distearyl 3,3'-thiodipropionate, lauryl
Stearyl 3,3'-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate) and the like. Further, examples of the phosphorus-based antioxidant include the following. Triphenyl phosphite, tris (nonylphenyl) phosphite, tris
(2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite,
Diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-
Methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-triphenyl
-t-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2,2'-methylenebis (4, 6-
Di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6- Methylphenyl) ethyl phosphite, bis
(2,4-di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2 -Oxaphospholinane, 2,2 ', 2''
-Nitrilo [triethyl-tris (3,3 ', 5,5'-tetra-t
-Butyl-1,1'-biphenyl-2,2'-diyl) phosphites and mixtures thereof.

Examples of the ultraviolet absorber include the following. (1) Examples of salicylate derivatives phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t- Octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl
3 ', 5'-di-t-butyl-4'-hydroxybenzoate,
Octadecyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3',
5'-di-t-butyl-4'-hydroxybenzoate and mixtures thereof. (2) Examples of 2-hydroxybenzophenone derivatives 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis ( 5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone and mixtures thereof.

(3) Examples of 2- (2'-hydroxyphenyl) benzotriazole 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ', 5'-di-t-butyl-2) '-Hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-octylphenyl) benzotriazole, 2- (3-t-
Butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3'-s-butyl-2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) Benzotriazole, 2- [2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-[(3'-t-butyl-2'-hydroxyphenyl ) -5 '-(2-Octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-5'-
[2- (2-ethylhexyloxy) carbonylethyl] -2'-
Hydroxyphenyl] -5-chlorobenzotriazole, 2-
[3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2-
[3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl-2'-hydroxy-5- (2-octyloxy Carbonylethyl) phenyl] benzotriazole, 2- [3'-t-butyl
-2'-Hydroxy-5 '-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-
Hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-
Di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [3'-t-butyl
-2'-Hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole mixture, 2,2'
-Methylenebis [6- (2H-benzotriazol-2-yl)-
4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-
Methylenebis [4-t-butyl-6- (2H-benzotriazole
2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3'-t-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole Condensate, poly (3-11) (ethylene glycol) with methyl 3- [3- (2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2- Ethylhexyl 3- [3-t-butyl-5- (5-chloro-2
H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl-5- (5-
Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, methyl 3- [3-t-butyl-5
-(5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- (5-
Chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

Examples of the light stabilizer include the following. (1) Examples of hindered amine light stabilizers bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl)
Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (N
-Benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-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-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4
-Piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6
-Pentamethyl-4-piperidyl decandioate,
2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t-butyl-4-hydroxyphenyl)
Propionyloxy] -1- [2- (3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxy) ethyl] -2,
2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-
Tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, 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, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1 -
Mixed esterified product with tridecanol,

Mixed esterified product of 1,2,3,4-butanetetrabonic acid with 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetra Carboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and
3, 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,
Mixed esterified product with 8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,
6-tetramethyl-4-piperidinol and 3,9-bis (2-
Mixed esterified product with hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2 Polycondensation product with 2,6,6-tetramethylpiperidine, 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)], 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)],
Polycondensate of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 1,2-dibromoethane, N, N ', 4,7-tetrakis [4 , 6-Bis (N-butyl-N- (2,
2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine,
N, N ', 4-Tris [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazine-2
-Yl] -4,7-diazadecane-1,10-diamine, N, N ', 4,7-
Tetrakis [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5-triazine-2-
Yl] -4,7-diazadecane-1,10-diamine, N, N ', 4-tris [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl
-4-piperidyl) amino) -1,3,5-triazin-2-yl]-
4,7-diazadecane-1,10-diamine and mixtures thereof.

(2) Examples of acrylate light stabilizers Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano- β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-
Methoxycinnamate and N- (β-carbomethoxy-
β-cyanovinyl) -2-methylindoline and mixtures thereof. (3) Examples of nickel-based light stabilizers Nickel complexes of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters , Nickel complexes of ketoxime and mixtures thereof.

(4) Examples of oxamide light stabilizers 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di- t-
Butylanilide, 2,2'-didodecyloxy-5,5'-di-t-
Butylanilide, 2-ethoxy-2'-ethyloxanilide,
N, N'-bis (3-dimethylaminopropyl) oxamide, 2
-Ethoxy-5-t-butyl-2'-ethoxyanilide, 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide and mixtures thereof. (5) Examples of 2- (2-hydroxyphenyl) -1,3,5-triazine light stabilizers 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-
Bis (2-hydroxy-4-propyloxyphenyl) -6-
(2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine , 2- (2-hydroxy-4
-Dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-
Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2
-Hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and mixtures thereof.

Examples of the metal deactivator include the following. N, N'-diphenyloxamide, N-salicyral-N'-salicyloylhydrazine, N, N'-
Bis (salicyloyl) hydrazine, N, N'-bis (3,5-di
-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole,
Bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide and mixtures thereof.

Examples of peroxide scavengers include esters of β-thiodipropionic acid, mercaptobenzimidazole, zinc salts of 2-mercaptobenzimidazole, zinc salts of dibutyldithiocarbamic acid, dioctadecyl disulfide, pentaerythritol tetrakis (β -Dodecylmercapto) propionate and mixtures thereof. Examples of the polyamide stabilizer include copper or divalent manganese salts of iodides or phosphorus compounds, and mixtures thereof. Examples of the hydroxyamine include, for example, N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-
Dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-ditetradecylhydroxyamine, N, N-
Examples include dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof. Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium / aluminum / hydroxy / carbonate / hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof. Can be Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, and higher aliphatic acid metals having 8 to 22 carbon atoms (Al, Ca, M
g, Zn) salt, aliphatic alcohol having 8 to 22 carbon atoms, polyglycol, higher fatty acid having 4 to 22 carbon atoms and 4 to 18 carbon atoms
Esters with aliphatic monohydric alcohols, higher aliphatic amides having 8 to 22 carbon atoms, silicone oils, rosin derivatives and the like.

Examples of the nucleating agent include the following. Sodium 2,2'-methylenebis
(4,6-di-t-butylphenyl) phosphate, [phosphoric acid
-2,2'-Methylenebis (4,6-di-t-butylphenyl)]
Dihydroxyaluminum, bis [2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate] hydroxyaluminum, tris [-2,2'-methylenebisphosphate
(4,6-di-t-butylphenyl)] aluminum, metal salts of benzoic acid such as sodium bis (4-t-butylphenyl) phosphate and sodium benzoate, aluminum p-t-butylbenzoate, 1,3: 2,4-bis (O-benzylidene) sorbitol, 1,3: 2,4-bis (O-methylbenzylidene) sorbitol, 1,3: 2,4-bis (O-ethylbenzylidene) sorbitol, 1,3- O-3,4-dimethylbenzylidene-
2,4-O-benzylidene sorbitol, 1,3-O-benzylidene-2,4-O-3,4-dimethylbenzylidene sorbitol, 1,
3: 2,4-bis (O-3,4-dimethylbenzylidene) sorbitol, 1,3-Op-chlorobenzylidene-2,4-O-3,4-dimethylbenzylidenesorbitol, 1,3-O-3, 4-dimethylbenzylidene-2,4-Op-chlorobenzylidene sorbitol, 1,
3: 2,4-bis (Op-chlorobenzylidene) sorbitol and mixtures thereof. Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and a mixture thereof.

Among these additives, those preferably used are phenolic antioxidants, phosphorus antioxidants,
UV absorbers, hindered amine light stabilizers, peroxide scavengers and neutralizers. Particularly preferred phenolic antioxidants include the following compounds, which may be used in combination of two or more. 2,6-di-t-butyl-4-
Methylphenol, 2,4,6-tri-t-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol, 2,2 '
-Thiobis (6-t-butylphenol), 4,4'-thiobis
(3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2, 2'-
Methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6
-Cyclohexylphenol), 2,2'-methylenebis
(4,6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 4,4′-methylenebis (6-t-butyl-2-methylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1 , 1-bis
(5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3 -
Bis-3'-t-butyl-4'-hydroxyphenyl) butyrate], 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl Acrylate, 2,
4-di-t-pentyl-6- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] phenyl acrylate,

2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris (4-t-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate,
Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate, Diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, di-n-octadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 3,5-di-t-butyl- Calcium salt of 4-hydroxybenzylphosphonic acid monoester, n-octadecyl 3- (3,5-di-t-butyl
-4-hydroxyphenyl) propionate, neopentanetetrayltetrakis (3,5-di-t-butyl-4-hydroxycinnamate), thiodiethylenebis (3,5-di-t-
Butyl-4-hydroxycinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 3,6-dioxaoctamethylene Screw
(3,5-di-t-butyl-4-hydroxycinnamate), hexamethylenebis (3,5-di-t-butyl-4-hydroxycinnamate), triethylene glycol bis (5-t-tyl- 4-hydroxy-3-methylcinnamate), 3,9-bis
[2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,
10-tetraoxaspiro [5.5] undecane, N, N'-bis
[3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionyl] hydrazine, N, N'-bis [3- (3', 5'-di-t-butyl-4 ' -Hydroxyphenyl) propionyl] hexamethylenediamine and the like.

Particularly preferred phosphorus-based antioxidants include the following, and two or more of these can be used. Tris (nonylphenyl) phosphite, tris
(2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis
(2,4-di-t-butylphenyl) pentaerythritol
Diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis
(2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite,
2'-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis
(4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, 2- (2,4,6-tri-t- (Butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane,
2,2 ', 2''-nitrilo [triethyl-tris (3,3', 5,5'-
Tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite and the like.

Particularly preferred UV absorbers include:
The following are mentioned, and these can be used in combination of two or more.
Phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ', 5'-di-t-butyl-4'-hydroxybenzoate, 4-t-octylphenyl salicylate, 2,4 -Dihydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2-hydroxy-
4-octoxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole , 2- (3 ', 5'-di-t-
Butyl-2'-hydroxyphenyl) benzotriazole,
2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3'-t-butyl-2 '-Hydroxy-5'-
Methylphenyl) -5-chlorobenzotriazole, 2- (3'-
s-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t -Amyl-2'-hydroxyphenyl) benzotriazole, 2-
[2'-hydroxy-3 ', 5'-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole and the like.

Particularly preferred light stabilizers include the following, and two or more of them can be used. Screw
(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl)
Sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-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-butylmalonate, bis
(1-Acroyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis ( 2,2,6,6-tetramethyl-4-piperidyl) succinate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6 -Tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetramethyl-4
-Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 -Butanetetracarboxylate

Tetrakis (1,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate,
Mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid And two,
Mixed esterified product of 2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol And a mixed esterified product with 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,2,3,4- Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-
Bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-
Mixed esterified product with tetraoxaspiro [5.5] undecane, polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 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)], poly [(6- (1,1,3,3-tetramethylbutyl) -1,3,5-triazine-2,4-diyl) ((2,2,
6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)] and the like.

In mixing the piperidine compound (I) or other additives used as necessary with the organic material, any known method and apparatus for obtaining a homogeneous mixture can be used. For example, when the organic material is a solid polymer, the piperidine compound (I) or other additives can be directly dry-blended with the solid polymer, or the piperidine compound (I) or other additives can be directly blended. The agent can also be incorporated into the solid polymer in the form of a masterbatch. When the organic material is a liquid polymer, it can also be added to the polymer solution during or immediately after the polymerization in the form of a solution or dispersion of the piperidine compound (I) or other additives. on the other hand,
When the organic material is a liquid such as oil, the piperidine compound (I) or other additives can be directly added and dissolved, or the piperidine compound (I) or other additives can be dissolved. It can also be added in the state of being dissolved or suspended in a liquid medium.

[0050]

The piperidine compound (I) of the present invention is
It has excellent bleed resistance and shows excellent performance as a light stabilizer for various organic materials including thermoplastic resins such as polyolefins.The organic materials containing this compound are:
It is stable against light deterioration and the like, and becomes a high quality product.

[0051]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Reference Example 1 Production Example of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-1,5-pentanediamine 11.6 g of methyl-1,5-pentanediamine
And 2,2,6,6-tetramethyl-4-piperidone 31.0 g, platinum catalyst (5% supported on activated carbon, 50% wet product) 0.2 g and methanol 100 ml
Was heated to 70 ° C. under a hydrogen pressure of 10 kg / cm ² , and stirring was continued for 10 hours while maintaining the same hydrogen pressure and the same temperature. The mixture was cooled to room temperature, the pressure was restored with nitrogen, the catalyst was separated by filtration, and low-boiling components were distilled off from the filtrate to obtain 40.5 g of a brown viscous liquid.

Reference Example 2 N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2,2,4
Production Example of 1-trimethyl-1,6-hexanediamine In Reference Example 1, 15.8 g of 2,2,4-trimethyl-1,6-hexanediamine was used instead of 2-methyl-1,5-pentanediamine
44.5 by following Reference Example 1 except that
g of a brown viscous liquid was obtained.

Reference Example 3 N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2,2-
Production Example of Dimethyl-1,3-propanediamine Reference Example is the same as Reference Example 1, except that instead of 2-methyl-1,5-pentanediamine, 10.2 g of 2,2-dimethyl-1,3-propanediamine is used. By complying with No. 1, 38.2 g of a brown viscous liquid was obtained. FD-MS M ⁺ = 380

Reference Example 4 N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl- Production Example of 4-Piperidyl) aminomethyl] cyclohexylamine In Reference Example 1, except that 17.0 g of 3-aminomethyl-3,5,5-trimethylcyclohexylamine was used instead of 2-methyl-1,5-pentanediamine. In accordance with Reference Example 1, 44.2 g of a brown viscous liquid was obtained. FD-MS M ⁺ = 448

Reference Example 5 Production Example of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2-ethyl-2-n-butyl-1,5-pentanediamine Reference Example 1, in place of 2-methyl-1,5-pentanediamine, 2-ethyl-2-n-butyl-1,5-pentanediamine 2
Except for using 0.0 g, by complying with Reference Example 1,
49.0 g of a brown viscous liquid was obtained.

Reference Example 6 Instead of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-1,5-pentanediamine, 2,5-bis [( 2,
2,6,6-tetramethyl-4-piperidyl) aminomethyl] bicyclo [2.2.1] heptane and 2,6-bis [(2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] bicyclo [2.2.1] Production Example of Heptane Mixture In Reference Example 1, 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane was replaced with 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane in place of 2-methyl-1,5-pentanediamine. By following Reference Example 1 except that 15.4 g of a mixture of bis (aminomethyl) bicyclo [2.2.1] heptane was used, 43.5 g of a brown viscous liquid was obtained.

Example 1 N, N'-dibenzoyl-N, N'-bis (2,2,6,6-tetramethyl-4
Preparation of -Piperidyl) -2-methyl-1,5-pentanediamine (Compound 1) N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl- 19.7 g of 1,5-pentanediamine and 20 toluene
After 17.6 g of benzoyl chloride was added to 0 ml of the mixture over 30 minutes, the temperature was raised to 80 ° C., and stirring was continued at the same temperature for 1 hour.
After cooling to room temperature, it is added to 20% aqueous sodium hydroxide 10
0 g and 50 ml of toluene were added, and the mixture was stirred, allowed to stand, and separated to obtain an organic phase. Next, the organic phase was washed with 50 ml of water, and the solvent was distilled off. The obtained residue was recrystallized from a mixed solvent of toluene / n-hexane (20/100) to obtain 26.6 g of white crystals. Melting point 122-125 ℃

Example 2 N, N'-dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4
Preparation of (-piperidyl) -2-methyl-1,5-pentanediamine (Compound 2) In Example 1, except that 15.1 g of pivaloyl chloride was used instead of benzoyl chloride, 21.9 g of White crystals were obtained. Melting point 150-152 ℃

Example 3 N, N'-dibenzoyl-N, N'-bis (2,2,6,6-tetramethyl-4
-Piperidyl) -2,2,4-trimethyl-1,6-hexanediamine
Production of (Compound 3) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2, instead of -piperidyl) -2-methyl-1,5-pentanediamine
Using 21.8 g of 2,4-trimethyl-1,6-hexanediamine and using a mixed solvent of toluene / n-hexane (40/60) as the recrystallization solvent,
6.7 g of white crystals were obtained. 239-244 ° C

Example 4 N, N'-dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4
-Piperidyl) -2,2,4-trimethyl-1,6-hexanediamine
Production of (Compound 4) In Example 1, N, N'-bis (2,2,6,6-tetramethyl-4
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2, instead of -piperidyl) -2-methyl-1,5-pentanediamine
21.8 g of 2,4-trimethyl-1,6-hexanediamine was used in accordance with Example 1 except that 15.1 g of pivaloyl chloride was used instead of benzoyl chloride, and n-hexane was used as a recrystallization solvent. g of white crystals were obtained. 153-156 ° C

Example 5 N, N'-dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4
Preparation of -Piperidyl) -2,2-dimethyl-1,3-propanediamine (Compound 5) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2,2 in place of -piperidyl) -2-methyl-1,5-pentanediamine
13.6 g of 1-dimethyl-1,3-propanediamine, 11.6 g of pivaloyl chloride in place of benzoyl chloride, and 23.6 g of white color by using the same procedure as in Example 1 except that n-hexane was used as a recrystallization solvent. Crystals were obtained. 204-207 ° C

Example 6 N, N'-dipropionyl-N, N'-bis (2,2,6,6-tetramethyl
-4-piperidyl) -2,2-dimethyl-1,3-propanediamine
Production of (Compound 6) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -2,2 in place of -piperidyl) -2-methyl-1,5-pentanediamine
By using 19.0 g of -dimethyl-1,3-propanediamine, 11.6 g of propionyl chloride instead of benzoyl chloride, and using n-hexane as a recrystallization solvent, 20.2 g of white Crystals were obtained. 135-139 ° C

Example 7 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) benzamidomethyl] cyclohexyl] benzamide
Production of (Compound 7) In Example 1, N, N'-bis (2,2,6,6-tetramethyl-4
N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-trimethyl-5- [N-(-piperidyl) -2-methyl-1,5-pentanediamine 24.6 g of white crystals were obtained by using 21.7 g of 2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexylamine according to Example 1 except that toluene was used as a recrystallization solvent. Was. Melting point 245 ° C or higher

Example 8 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) pivalamidomethyl] cyclohexyl] pivalamide
Production of (Compound 8) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-trimethyl-5- [N-(-piperidyl) -2-methyl-1,5-pentanediamine 2,2,6,6-Tetramethyl-4-piperidyl) aminomethyl] cyclohexylamine 21.7 g, pivaloyl chloride 15.1 g instead of benzoyl chloride, and the procedure of Example 1 was repeated except that toluene was used as a recrystallization solvent. As a result, 21.9 g of white crystals were obtained. Melting point 193-195 ° C

Example 9 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Preparation of trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) propionylamidomethyl] cyclohexyl] propionylamide (Compound 9) In Example 1, N, N'-bis (2 , 2,6,6-tetramethyl-4
N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-trimethyl-5- [N-(-piperidyl) -2-methyl-1,5-pentanediamine 2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexylamine (21.7 g) was used in place of benzoyl chloride, and propionyl chloride (11.6 g) was used. Toluene / n-hexane (30/70 21.6 g according to Example 1 except that the mixed solvent
Was obtained as white crystals. 136-138 ° C

Example 10 N, N'-Dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4
Preparation of -Piperidyl) -2-ethyl-2-n-butyl-1,5-pentanediamine (Compound 10) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)-2-instead of -piperidyl) -2-methyl-1,5-pentanediamine
Using 23.9 g of ethyl-2-n-butyl-1,5-pentanediamine, 15.1 g of pivaloyl chloride instead of benzoyl chloride, and toluene / n-hexane (20/8
According to Example 1 except that the mixed solvent of 0) was used, 25.9 g of white crystals were obtained. Melting point 164-167 ° C

Example 11 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexyl] pivalamide and N-
(2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) pi Preparation of a mixture of (valamidomethyl) cyclohexyl] amine (compound 11) In Example 1, N, N'-bis (2,2,6,6-tetramethyl-4
N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-trimethyl-5- [N-(-piperidyl) -2-methyl-1,5-pentanediamine According to Example 1, except that 22.4 g of 2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexylamine and 6.0 g of pivaloyl chloride were used in place of benzoyl chloride and recrystallization was not performed By doing, 2
6.8 g of a brown viscous liquid was obtained. This is N-(2,2,6,6
-Tetramethyl-4-piperidyl) -N- [3,3,5-trimethyl-5-
[N- (2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexyl] pivalamide and N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3, 3,5-trimethyl-5- [N-
In addition to (2,2,6,6-tetramethyl-4-piperidyl) pivalamidomethyl] cyclohexyl] amine, N
-(2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl)
Pivalamidomethyl] cyclohexyl] pivalamide and unreacted N- (2,2,6,6-tetramethyl-4-piperidyl) -3,3,5-
It contains trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] cyclohexylamine, and the former of impurities is crystallized by crystallization from n-hexane, The latter impurity was removed to the aqueous phase by extraction with water to give 10.8 g of the title white crystal. Melting point 64-69 ° C FD-MS MH ⁺ = 533

Example 12 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) propionylamidomethyl] cyclohexyl] pivalamide and N-(2,2,6,6-tetramethyl-4-piperidyl)- N-
Preparation of a mixture of [3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) pivalamidomethyl] cyclohexyl] propionylamide (Compound 12) Example 1 In, N, N'-bis (2,2,6,6-tetramethyl-4
-Piperidyl) -2-methyl-1,5-pentanediamine, N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,
3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) propionylamidomethyl] cyclohexyl] pivalamide and N- (2,2,6,6-tetramethyl-4 -Piperidyl)-
N- [3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-
Mixture of piperidyl) pivalamidomethyl] cyclohexyl] propionylamide (prepared according to Example 11) 5.
3 g, propionyl chloride 1.2 g instead of benzoyl chloride
And 5.9 g of white crystals were obtained according to Example 1, except that recrystallization after distilling off the solvent was not carried out. 87-95 ° C SIMS MH ⁺ = 589

Example 13 N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,3,5-
Trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) benzamidomethyl] cyclohexyl] pivalamide and N-(2,2,6,6-tetramethyl-4-piperidyl) -N -[3,3,5
Preparation of a mixture of -trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) pivalamidomethyl] cyclohexyl] benzamide (Compound 13) In Example 1, N, N'- Bis (2,2,6,6-tetramethyl-4
-Piperidyl) -2-methyl-1,5-pentanediamine, N- (2,2,6,6-tetramethyl-4-piperidyl) -N- [3,
3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-piperidyl) propionylamidomethyl] cyclohexyl] pivalamide and N- (2,2,6,6-tetramethyl-4 -Piperidyl)-
N- [3,3,5-trimethyl-5- [N- (2,2,6,6-tetramethyl-4-
Mixture of piperidyl) pivalamidomethyl] cyclohexyl] propionylamide (prepared according to Example 11) 5.
3 g, using 1.7 g of benzoyl chloride, and following the procedure of Example 1 except that recrystallization after distilling off the solvent was not carried out.
6.4 g of white crystals were obtained. 110-115 ° C SIMS MH ⁺ = 637

Example 14 2,5-Bis [N-pivaloyl- (2,2,6,6-tetramethyl-4-piperidyl) amidomethyl] bicyclo [2.2.1] heptane and 2,6-
Preparation of a mixture of bis [N-pivaloyl- (2,2,6,6-tetramethyl-4-piperidyl) amidomethyl] bicyclo [2.2.1] heptane (compound 14) In Example 1, N, N'-bis (2,2,6,6
2,5-bis [(2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] bicyclo [instead of -tetramethyl-4-piperidyl) -2-methyl-1,5-pentanediamine 2.2.1] Heptane and 2,6-bis [(2,2,6,6-tetramethyl-4-piperidyl)
21.6 g of a mixture of aminomethyl] bicyclo [2.2.1] heptane
Was obtained according to Example 1 except that 15.1 g of pivaloyl chloride was used instead of benzoyl chloride, and no recrystallization was performed after the solvent was distilled off, to obtain 31.5 g of white crystals. 73-78 ° C SIMS MH ⁺ = 601

Example 15 2,5-bis [N-propionyl- (2,2,6,6-tetramethyl-4-piperidyl) amidomethyl] bicyclo [2.2.1] heptane and 2,6
-Bis [N-propioni- (2,2,6,6-tetramethyl-4-piperidyl) amidomethyl] bicyclo [2.2.1] heptane
Production of (Compound 15) In Example 1, N, N′-bis (2,2,6,6-tetramethyl-4
-Piperidyl) -2-methyl-1,5-pentanediamine, instead of 2,5-bis [(2,2,6,6-tetramethyl-4-piperidyl)
Aminomethyl] bicyclo [2.2.1] heptane and 2,6-bis [
21.6 g of a mixture of (2,2,6,6-tetramethyl-4-piperidyl) aminomethyl] bicyclo [2.2.1] heptane was used, and 11.6 g of propionyl chloride was used in place of benzoyl chloride. By following the procedure of Example 1 except that the crystallization was not performed, 30.5 g of a light brown viscous liquid was obtained. FD-MS M ⁺ = 544

Example 16 Each composition having the following composition was melt-kneaded with an extruder having a diameter of 30 mm at 210 to 230 ° C., and granulated.
Using a 30-ton injection molding machine, molding was performed at 220 to 240 ° C. to produce a flat sheet having a length of 60 mm, a width of 40 mm, and a thickness of 1 mm. This sheet was stored for one week in a gear oven maintained at 80 ° C. The gloss value of the sheet surface before and after storage was measured, and the bleed resistance was evaluated based on the retention, and the results are shown in Table 1. The higher the retention, the better the bleed resistance.
The gross value was measured with a digital variable-angle gloss meter (incident angle, light receiving angle: 60 °) in accordance with JIS K 7105.

<Formulation> Unstabilized polypropylene 100 parts by weight Calcium stearate 0.05 parts by weight Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane 0.05 Parts by weight Tris (2.4-di-t-butylphenyl) phosphite 0.05 parts by weight Test compound 0.2 parts by weight Chemical-1: Compound 1 (produced in Example 1) Chemical-2: Compound 2 (Example Compound-3: Compound 3 (manufactured in Example 3) Compound-4: Compound 4 (manufactured in Example 4) Compound-5: Compound 5 (manufactured in Example 5) Compound-6: Compound 6 (manufactured in Example 5) Compound-7: Compound 7 (manufactured in Example 7) Compound-8: Compound 8 (manufactured in Example 8) Compound-9: Compound 9 (manufactured in Example 9) Compound-10: Compound 10 (manufactured in Example 10) Compound 11: Compound 11 (manufactured in Example 11) Compound -13: Compound 13 (manufactured in Example 13) Compound -14: Compound 14 (manufactured in Example 14) Compound -15: Compound 15 (manufactured in Example 15) LS-1: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate LS-2: N, N'-dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4- Piperidyl) -1,6-hexanediamine LS-3: N, N'-dipivaloyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,12-dodecanediamine LS -4: N, N'-dipropionyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,12-dodecanediamine

[0075]

[Table 1] Example 1 2 3 4 5 6 7 8 9 10 10 Test compound Chemical-1 Chemical-2 Chemical-3 Chemical-4 Chemical-5 Chemical-6 Chemical-7 Chemical-8 Chemical-9 Chemical-10 gloss retention (%) 84 60 83 84 83 72 65 86 82 66 implementation example comparisons example 11 12 13 14 15 1 2 3 4 test compound of -11 of -12 of -13 of -12 of -13 LS -1 LS-2 LS-3 LS-4 Gloss retention (%) 87 81 75 80 75 29 50 50 18

Claims (12)

[Claims] (1) Formula (I)(Where R₁, R_Three, M is R₁Is an alkyl having 1 to 6 carbon atoms
A group represented by R_ThreeIs a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
M represents an integer of 0 to 2 or R₁And R_Three And those
Is substituted carbon atom and (CH_Two)_mTogether with the carbon number
5 carbon atoms which may be substituted by 1 to 6 alkyl groups
Represents a bivalent cyclic group of 1 to 9; R_Two, R_Four, R_FiveAnd R₆Haso
Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
Represent. R₇And R₈Are each independently a hydrogen atom or carbon number
Represents 2 to 18 acyl groups, and simultaneously being a hydrogen atom
Absent. n represents the integer of 0-2. Piperidi
Compounds. (2) R ₁ is a lower alkyl group, R ₃ is hydrogen or a lower alkyl group, or R ₁ and R ₃ together with the carbon atom substituted by them and (CH ₂ ) _m lower alkyl group is a divalent alkylene group also 5 to 9 carbon atoms that is substituted, R ₂ is a hydrogen atom or a lower alkyl group, R ₄
Is a hydrogen atom, The piperidine compound according to claim 1, wherein 3. The piperidine compound according to claim 1, wherein R ₅ and R ₆ are groups selected from a hydrogen atom and a lower alkyl group. 4. The piperidine compound according to claim 1, wherein R ₇ and R ₈ are groups selected from acyl groups having 2 to 18 carbon atoms. 5. The formula (II) (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , m and n have the same meanings as described above), by converting a bispiperidinylalkylenediamine represented by the formula (IV) R ₉ -C (O) -X (IV) (wherein R ₉ is an alkyl group having 1 to 17 carbon atoms or 1 carbon atom)
Represents a phenyl group which may be substituted with an alkyl group of from 6 to 6. X represents a halogen atom, —OR ₁₀ , —OC (O) R ₉ or —NR ₁₁ R ₁₂ , and R ₁₀ , R ₁₁ ,
R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Acylation using at least one carboxylic acid represented by the formula (1):
5. The method for producing a piperidine compound according to 4. 6. The formula (II) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , m and n have the same meanings as described above). 7. R ₁ is a lower alkyl group, R ₃ is hydrogen or a lower alkyl group, or R ₁ and R ₃ together with the carbon atom which they substitute and (CH ₂ ) _m together lower alkyl group is a divalent alkylene group also 5 to 9 carbon atoms that is substituted, R ₂ is a hydrogen atom or a lower alkyl group, R ₄
Is a hydrogen atom, The bispiperidinyl alkylenediamine according to claim 6, wherein 8. The bispiperidinyl alkylenediamine according to claim 6, wherein R ₅ and R ₆ are groups selected from a hydrogen atom and a lower alkyl group. 9. Formula (V) H ₂ N—CH ₂ —C (R ₁ ) (R ₂ ) — (CH ₂ ) _m —C (R ₃ ) (R ₄ )
_{-C n H 2n -NH 2 (V} ) ( _{wherein, R 1, R 2, R} 3,
R ₄ , m and n have the same meaning as described above. )) And an alkylenediamine represented by the formula (VI) and / or the formula (VI)
I) (Wherein, R ₅ and R ₆ have the same meanings as described above), wherein the piperidone is subjected to reductive alkylation, and the bispiperidinyl alkylenediamine (II) according to claim 6 to 8, wherein Manufacturing method. 10. A stabilizer for organic materials comprising the piperidine compound according to claim 1 as an active ingredient. 11. A method for stabilizing an organic material, comprising the piperidine compound according to claim 1. Description: 12. A stabilized organic material composition comprising the piperidine compound according to claim 1.