WO2013089280A1

WO2013089280A1 - Fiber and method for producing same

Info

Publication number: WO2013089280A1
Application number: PCT/JP2012/083171
Authority: WO
Inventors: 木村　由和
Original assignee: 住友化学株式会社
Priority date: 2011-12-16
Filing date: 2012-12-14
Publication date: 2013-06-20
Also published as: TW201331434A; JP2013231266A

Abstract

A fiber contains at least one compound selected from the following: (A) a thermoplastic polymer; (B) a compound represented by formula (1); and (C) a compound group (S) [glucose, fructose, trehalose, sucrose, lactose, maltose, melezitose, stachyose, curdlan, glycogen, a compound represented by formula (S1), a compound represented by C_pH_p+2 (OH)_p, and a compound represented by C_rH_2rO_r and having the hydroxy group thereof substituted by an alkoxy group]. (In the formulas, the meanings of the symbols are as described in the description.)

Description

Fiber and production method thereof

The present invention relates to a fiber and a method for producing the same.

In JP2011-144491-A, a polyurethane elastic yarn or a polyurethane spinning is added to Sumitizer GA-80 manufactured by Sumitomo Chemical Co., Ltd. (ie, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy- 5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane) and the like.

3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane is an effective antioxidant. However, when used alone, it may not be possible to sufficiently suppress the decrease in mechanical properties (elastic recovery rate, tensile strength, etc.) of the fiber after heat treatment. there were. The present invention has been made paying attention to such circumstances, and an object of the present invention is to provide a fiber having a small decrease in mechanical properties after heat treatment.

As a result of extensive studies by the present inventors, a compound represented by the following formula (1) (3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] } -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane) and at least one selected from the following compound group S is used in combination. Found that it can be achieved. The present invention based on this finding is as follows.

[1] (A) a thermoplastic polymer;
(B) Formula (1):

(In the formula, each R ¹ independently represents a C _1-8 alkyl group, a C _6-12 aryl group, or a C _7-18 aralkyl group.
Each R ² independently represents a hydrogen atom or a C _1-3 alkyl group.
L ¹ represents an m-valent C _1-26 organic group.
k represents an integer of 0 to 4.
m represents an integer of 1 to 4. )
A compound represented by
(C) The following compound group S:
(I) glucose,
(Ii) fructose,
(Iii) trehalose,
(Iv) sucrose,
(V) lactose,
(Vi) maltose,
(Vii) meletitol,
(Viii) stachyose,
(Ix) card run,
(X) glycogen,
(Xi) Formula (S1):

(In the formula, n represents an integer of 2 or more.)
A compound represented by
(Xii) C _p H _{p + 2} (OH) _p (wherein p represents an integer of 4 or more) (S2), and (xiii) C _r H _2r O _r (wherein r is 3 And at least one hydroxy group of the compound (S3a) having one aldehyde group or ketone group and r-1 hydroxy group is represented by -OR ^S3 (wherein R ^S3 Represents a C _1-12 alkyl group) and is substituted with an alkoxy group (S3)
At least one compound selected from:
Containing fiber.

[2] The compound represented by the formula (1) is 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl. ] -2,4,8,10-tetraoxaspiro [5.5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene) ] And the fiber according to [1] above, which is at least one selected from the group consisting of tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.

[3] The compound represented by the formula (1) is represented by the formula (1-1):

(In the formula, each R ³ and each R ⁴ independently represent a hydrogen atom or a C _1-6 alkyl group.
L ² represents an m-valent C _1-24 organic group.
m represents an integer of 1 to 4. )
The fiber according to [1], which is a compound represented by the formula:

[4] The above [1], wherein the total amount of the compound represented by the formula (1) and at least one compound selected from the compound group S is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. ~ The fiber according to any one of [3].

[5] In any one of the above [1] to [4], at least one compound selected from the compound group S is at least one selected from the group consisting of trehalose and a compound represented by the formula (S1) The described fiber.

[6] The fiber according to any one of [1] to [5], wherein the thermoplastic polymer is at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyurethane resin, polyamide resin, and polyester resin. .

[7] The fiber according to any one of [1] to [6], wherein n is 5.

[8] (A) a thermoplastic polymer;
(B) Formula (1):

(In the formula, n represents an integer of 2 or more.)
A compound represented by
(Xii) C _p H _{p + 2} (OH) _p (wherein p represents an integer of 4 or more) (S2), and (xiii) C _r H _2r O _r (wherein r is 3 And at least one hydroxy group of the compound (S3a) having one aldehyde group or ketone group and r-1 hydroxy group is represented by -OR ^S3 (wherein R ^S3 Represents a C _1-12 alkyl group) and is substituted with an alkoxy group (S3)
At least one compound selected from:
The manufacturing method of a fiber including discharging the thermoplastic polymer composition containing this from a nozzle | cap | die.

[9] (A) a thermoplastic polymer;
(B) Formula (1-1):

(In the formula, each R ³ and each R ⁴ independently represent a hydrogen atom or a C _1-6 alkyl group.
L ² represents an m-valent C _1-24 organic group.
m represents an integer of 1 to 4. )
A compound represented by
(C) The following compound group S:
(I) glucose,
(Ii) fructose,
(Iii) trehalose,
(Iv) sucrose,
(V) lactose,
(Vi) maltose,
(Vii) meletitol,
(Viii) stachyose,
(Ix) card run,
(X) glycogen,
(Xi) Formula (S1):

[10] The total amount of the compound represented by the formula (1-1) and at least one compound selected from the compound group S is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. 9].

[11] The fiber according to [9] or [10] above, wherein at least one compound selected from the compound group S is a compound represented by the formula (S1).

[12] The fiber according to any one of [9] to [11], wherein the thermoplastic polymer is at least one selected from the group consisting of polyethylene, polypropylene, polyurethane, nylon, and polyester.

[13] The compound represented by the formula (1-1) is octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane or pentaerythritol tetrakis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate]. The fiber according to any one of [9] to [12] above.

[14] The fiber according to any one of [9] to [13], wherein n is 5.

[15] (A) a thermoplastic polymer;
(B) Formula (1-1):

(In the formula, n represents an integer of 2 or more.)
A compound represented by
(Xii) C _p H _{p + 2} (OH) _p (wherein p represents an integer of 4 or more) (S2), and (xiii) C _r H _2r O _r (wherein r is 3 And at least one hydroxy group of the compound (S3a) having one aldehyde group or ketone group and r-1 hydroxy group is represented by -OR ^S3 (wherein R ^S3 Represents a C _1-12 alkyl group) and is substituted with an alkoxy group (S3)
At least one compound selected from:
A method for producing a fiber, in which a thermoplastic polymer composition containing is discharged from a die into a spinning cylinder, and the obtained discharged yarn is wound with a winder.

In the present invention, “C _ab ” means that the carbon number is a to b. In addition, the above-mentioned “compound represented by the formula (1)” or the like may be abbreviated as “compound (1)” or the like below. Similarly, a “divalent group represented by the formula (5a)” to be described later may be abbreviated as “a divalent group (5a)” or the like.

The fiber of the present invention containing the compound (1) and at least one compound selected from the compound group S has a small decrease in mechanical properties (such as elastic recovery rate and tensile strength) after heat treatment.

The fiber of the present invention contains at least one compound selected from a thermoplastic polymer, compound (1), and compound group S. Hereinafter, each component will be described in order.

Only one type of thermoplastic polymer may be used, or two or more types may be used in combination. Examples of the thermoplastic polymer include polyethylene resins [for example, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-vinyl alcohol copolymer (EVOH), ethylene- Ethyl acrylate copolymer, ethylene-vinyl acetate copolymer (EVA)], polypropylene resin (for example, crystalline propylene homopolymer, propylene-ethylene random copolymer, propylene-α-olefin random copolymer, propylene -Ethylene-α-olefin copolymer, etc.), polyurethane resin, polyamide resin (for example, nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 6T, nylon 6I, nylon 9T, nylon M5T, etc.) , Polie Steal resin (for example, polyethylene terephthalate, polytetramethylene terephthalate), biodegradable resin [for example, polylactic acid (PLA), poly-3-hydroxybutyric acid, poly-3-hydroxybutyric acid / 3-hydroxyhexanoic acid, polycaprolactone, Polybutylene succinate] and the like.

From the viewpoint of good spinnability, polyethylene resin, polypropylene resin, polyurethane resin, polyamide resin, and polyester resin are preferable, and polyurethane resin, polyamide resin, and polyester resin are particularly preferable.

As the polyethylene resin, high density polyethylene (HDPE) is preferable.
As the polypropylene resin, a crystalline propylene homopolymer is preferable.
As the polyurethane resin, a polyurethane composed of a polymer having two or more terminal hydroxy groups (polyhydroxy polymer) and an organic diisocyanate compound is preferable. The polyhydroxy polymer is preferably polyether glycol or polyester glycol, and the organic diisocyanate compound is 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI). Is preferred.
As the polyamide resin, nylon is preferable, and nylon 6, nylon 12, and nylon 66 are more preferable. Nylon was originally a trade name, but is now used as a general term for polyamide resins containing an aliphatic skeleton.
As the polyester resin, polyethylene terephthalate, polybutylene terephthalate, and polytetramethylene terephthalate are preferable.

When the fiber of the present invention is a monofilament, the melt index (value measured using a melt indexer) of the polypropylene resin is preferably 0.1 to 10, and when the fiber of the present invention is a multi-fragment, 5 ~ 80 is preferred.
The number average molecular weight of the polyurethane resin is preferably 500 to 5,000, and more preferably 1,500 to 4,000.
The polyamide resin preferably has a relative viscosity of 2.0 to 5.0 as measured with an Ostwald viscometer after being dissolved in formic acid.
The viscosity of the polyester resin is preferably 0.5 to 0.9 dl / L in terms of the intrinsic viscosity measured using an Ostwald viscometer after being dissolved in a phenol / tetrachloroethane solution.

Next, compound (1) will be described. Only 1 type may be used for a compound (1) and it may use 2 or more types together.

Each R ¹ in Formula (1) independently represents a C _1-8 alkyl group, a C _6-12 aryl group, or a C _7-18 aralkyl group, and k represents an integer of 0 to 4. k is preferably an integer of 1 to 4, more preferably 2 or 3. When k is 2 or more, or when m is 2 or more, each R ¹ may be the same as or different from each other.

The C _1-8 alkyl group may be either a chain or a ring, and is preferably a chain (straight or branched). As the C _1-8 alkyl group, a linear C _1-8 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group (also referred to as an amyl group)), a branched chain C ₃ , etc. _-8 alkyl groups (eg, isopropyl, isobutyl, sec-butyl, t-butyl, t-pentyl, 2-ethylhexyl, etc.), cyclic C _3-8 alkyl groups (ie, C _3-8 cyclo Alkyl groups such as cyclopentyl group and cyclohexyl group).
Examples of the C _6-12 aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
Examples of the C _7-18 aralkyl group include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, and the like.

R ² in the formula (1) represents a hydrogen atom or a C _1-3 alkyl group. The C _1-3 alkyl group may be linear or branched. Examples of the C _1-3 alkyl group include a methyl group, an ethyl group, a propyl group, and an isopropyl group. R ² is preferably a hydrogen atom or a methyl group.

L ¹ in Formula (1) represents an m-valent C _1-26 organic group, and m represents an integer of 1 to 4. The m-valent C _1-26 organic group is not particularly limited, and examples thereof include an organic group included in the subordinate concept of the compound (1) described later. m is preferably 1 to 3, more preferably 1 or 2.

Preferred compound (1) includes compound (1-1). Only 1 type may be used for a compound (1-1) and it may use 2 or more types together. Hereinafter, the compound (1-1) will be described.

Each R ³ and each R ^{4 in} Formula (1-1) each independently represent a hydrogen atom or a C _1-6 alkyl group. When m is 2 or more, each R ³ may be the same as or different from each other, preferably the same. The same applies to each R ⁴ . As the C _1-6 alkyl group include those described above. Each R ³ and each R ⁴ are each independently preferably a linear C _1-6 alkyl group or a branched C _3-6 alkyl group, more preferably a methyl group or a t-butyl group.

L ² in Formula (1-1) represents an m-valent C _1-24 organic group, and m represents an integer of 1 to 4. m is preferably 1 to 3, more preferably 1 or 2.

Examples of the m-valent C _1-24 organic group include:
The remaining group obtained by removing a hydrogen atom from all of the m hydroxy groups of the C _1-24 alcohol having m hydroxy groups (hereinafter abbreviated as “m-valent C _1-24 alcohol residue”). is there);
In the C _1-24 amine having m amino groups (including imino groups), the remaining groups obtained by removing one hydrogen atom from each of the m amino groups (hereinafter referred to as “m-valent C _1-24”). (May be abbreviated as “amine residue”)
Etc.

Both the m-valent C _1-24 alcohol residue and the m-valent C _1-24 amine residue may contain a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like, and these hetero atoms are carbon atoms in an m-valent C _1-24 alcohol residue and an m-valent C _1-24 amine residue. May be replaced. In addition, each of the m-valent C _1-24 alcohol residue and the m-valent C _1-24 amine residue may be linear or cyclic, or a combination thereof. The chain may be linear or branched.

Examples of the monovalent C _1-24 alcohol residue include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol and the like. Residue.

Examples of the divalent C _1-24 alcohol residue include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, diethylene glycol, triethylene glycol, 3,9-bis ( And residues such as 1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane.

Examples of the trivalent C _1-24 alcohol residue include residues such as glycerol.

Examples of the tetravalent C _1-24 alcohol residue include residues such as erythritol and pentaerythritol.

Examples of the monovalent C _1-24 amine residue include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecyl. Examples thereof include residues such as amine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, and eicosylamine.

Examples of the divalent C _1-24 amine residue include residues such as methanediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, heptamethylenediamine, hexamethylenediamine, octamethylenediamine, diaminodecane, and diaminododecane. Can be mentioned.

Examples of the trivalent C _1-24 amine residue include residues such as diethylenetriamine and 1,2,4-benzenetriamine.

Examples of the tetravalent C _1-24 amine residue include residues such as triethylenetetramine and 1,2,4,5-benzenetetraamine.

As the compound (1-1), for example,
(I) 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid, or 3- (3 , 5-dicyclohexyl-4-hydroxyphenyl) propionic acid and an alcohol having m hydroxy groups (m = 1 to 4),
(Ii) 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid, or 3- (3 , 5-dicyclohexyl-4-hydroxyphenyl) propionic acid and an amide of an amine having m amino groups (including imino groups) (m = 1 to 4). Any of the ester (i) and the amide (ii) may be used alone or in combination of two or more. Further, a mixture of the ester (i) and the amide (ii) may be used.

Examples of the alcohol having m hydroxy groups forming the ester of (i) include methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1 , 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene 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, 3 , 9 Bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-spiro [5.5] undecane.

Examples of the amine having m amino groups forming the amide of (ii) include methanediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, heptamethylenediamine, hexamethylenediamine, octamethylenediamine, and the like. .

As a preferred compound (1-1),
Octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (hereinafter sometimes abbreviated as “compound (1-1-1)”),
3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] Undecane (hereinafter sometimes abbreviated as “compound (1-1-2)”),
Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (hereinafter sometimes abbreviated as “compound (1-1-3)”),
Bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] (hereinafter sometimes abbreviated as “compound (1-1-4)”) , And N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanamide] (hereinafter abbreviated as “compound (1-1-5)”) )
Is mentioned.
Among these, the compound (1-1-2), the compound (1-1-4), and the compound (1-1-5) are more preferable, and the compound (1-1-2) and the compound (1-1-4) Is more preferable.

The compound (1-1-1) is “Irganox (registered trademark) 1076” (manufactured by BASF Japan), and the compound (1-1-2) is “Sumilyzer (registered trademark) GA-80” (manufactured by Sumitomo Chemical). ), Compound (1-1-3) is “Irganox (registered trademark) 1010” (manufactured by BASF Japan), and compound (1-1-4) is “irganox (registered trademark) 245” (BASF Japan). Compound (1-1-5) is commercially available as “Irganox (registered trademark) 1098” (manufactured by BASF Japan).

Compound (1-1) may be a commercially available product, or can be produced according to a known method (for example, the method described in US3330859A, US3644482A, or JPS59-25826-A).

Moreover, as another preferable compound (1), the formula (1-2):

(In the formula, each R ⁵ and each R ⁶ each independently represent a C _1-8 alkyl group, a C _6-12 aryl group, or a C _7-18 aralkyl group.
R ⁷ represents a hydrogen atom or a C _1-3 alkyl group.
R ⁸ represents a hydrogen atom or a methyl group. )
The compound shown by these is mentioned. Only 1 type may be used for a compound (1-2) and it may use 2 or more types together. Hereinafter, the compound (1-2) will be described.

Each R ⁵ and each R ^{6 in} Formula (1-2) each independently represent a C _1-8 alkyl group, a C _6-12 aryl group, or a C _7-18 aralkyl group. _{Examples of the} C _1-8 alkyl group, C _6-12 aryl group, and C _7-18 aralkyl group include those described above. There are two R ^{5 s,} but each R ⁵ may be the same as or different from each other, preferably the same. The same applies to each R ⁶ . Each R ⁵ and each R ⁶ are independently preferably a branched C _3-8 alkyl group, more preferably a C _4-8 alkyl group having a tertiary carbon atom, still more preferably a t-butyl group or A t-pentyl group, particularly preferably a t-pentyl group.

R ⁷ in formula (1-2) represents a hydrogen atom or a C _1-3 alkyl group. The above-mentioned thing is mentioned as a _C1-3 alkyl group. R ⁷ is preferably a hydrogen atom or a methyl group.

R ⁸ in Formula (1-2) represents a hydrogen atom or a methyl group, and preferably a hydrogen atom.

Examples of the compound (1-2) include 2,4-di-t-butyl-6- [1- (3,5-di-t-butyl-2-hydroxyphenyl) ethyl] phenyl (meth) acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate, 2,4-di-t-pentyl-6- [1- ( 3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl (meth) acrylate, 2,4-di-t-butyl-6- (3,5-di-t-butyl-2-hydroxy- (Benzyl) phenyl (meth) acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-ethylphenyl (meth) acrylate, 2-t-pentyl-6 (3-t Pentyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl (meth) acrylate. Here, “(meth) acrylate” means “acrylate or methacrylate”.

As preferred compound (1-2),
2,4-di-t-pentyl-6- [1- (3,5-di-t-pentyl-2-hydroxyphenyl) ethyl] phenyl acrylate (hereinafter abbreviated as “compound (1-2-1)”) 2) -t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (hereinafter abbreviated as “compound (1-2-2)”) Sometimes)
Is mentioned.
The compound (1-2-1) is “Sumilyzer (registered trademark) GS (F)” (manufactured by Sumitomo Chemical Co., Ltd.), and the compound (1-2-2) is “Sumilyzer (registered trademark) GM” (manufactured by Sumitomo Chemical Co., Ltd.). ).

Compound (1-2) may be a commercially available product, or can be produced according to a known method (for example, the method described in JPH01-168643-A or JPS58-84835-A).

Another preferred compound (1) is tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. The compound is commercially available as “Cyanox (registered trademark) CY-1790” (manufactured by Cytec Industries).

Other specific examples of the compound (1) include those described in the following [1] to [8].
[1] 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,4-dimethyl-6- (1′-methylundecyl-1′-yl) phenol, Alkylated mono, such as 2,4-dimethyl-6- (1′-methylheptadecyl-1′-yl) phenol and 2,4-dimethyl-6- (1′-methyltridecyl-1′-yl) phenol Phenol.

[2] 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-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), 2,2'-ethylidenebis (4-isobutyl-6-t-butylphenol), 4,4'-methylenebis (6-t-butyl-2- Methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-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-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3′-t-butyl-4′-hydroxyphenyl) butyrate], bis [2- (3′-t-butyl-2′-hydroxy-5) '-Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-) t-bu Til-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 Bisphenol derivatives such as -t-butyl-4-hydroxy-2-methylphenyl) pentane.

[3] 3,5,3 ′, 5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, 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-hydroxy) Benzyl) sulfide, O-benzyl derivatives such as isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate, N-benzyl derivatives and S-benzyl derivatives.

[4] Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropylene ) Hydroxybenzyl group-containing triazine derivatives such as 1,3,5-triazine and tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[5] Dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) Malonate, didodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl]- Hydroxybenzyl group-containing malonate derivatives such as 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate.

[6] 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5-di-t- Aromatic hydroxybenzyl derivatives such as butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) phenol.

[7] Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t- Butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, etc. Hydroxybenzylphosphonate derivative.

[8] 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] tri Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide such as methylenediamine.

Compound (1) is
Preferably, it is at least one selected from the group consisting of compound (1-1), compound (1-2), and tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid;
More preferably, it is at least one selected from the group consisting of the compound (1-1) and tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid;
More preferably, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5.5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] and tris (4-tert-butyl) -3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid is at least one selected from the group consisting of.

The present invention is characterized in that the compound (1) and at least one compound selected from the compound group S are used in combination. This compound group S is composed of a saccharide (glucose, fructose, trehalose, sucrose, lactose, maltose, meretito, stachyose, curdlan, glycogen) and a compound that can be synthesized from the saccharide [compound (S1) to compound (S3)]. And can be classified. However, compounds (S1) to (S3) may be compounds synthesized from other than sugar. Hereinafter, the compound group S will be described in order.

Glucose and fructose, which are monosaccharides, may be any of D-form, L-form or a mixture thereof, preferably D-form. Glucose and fructose may be any of α-form, β-form or a mixture thereof. Glucose and fructose may be any of a pyranose type, a furanose type or a mixture thereof, preferably a pyranose type. The glucose may be any of anhydride, hydrate, or a mixture thereof. Glucose and fructose are commercially available, and commercially available products can be used as they are.

The disaccharides trehalose, sucrose, lactose and maltose, the trisaccharide meletitol (also called melezitose), and the tetrasaccharide stachyose may be any of anhydrides, hydrates, or mixtures thereof. These are commercially available, and any of these can be used as they are.

Curdlan and glycogen are classified as polysaccharides. Here, curdlan is a glucan (polysaccharide consisting of D-glucose) consisting only of β1-3 glycosidic bonds produced by microorganisms. Glycogen is a polysaccharide that exists in the body of animals (eg, oysters). The weight average molecular weight of the curdlan [measured with a laser diffraction absolute molecular weight measuring apparatus (manufactured by Shoko Tsusho, with Shodex-GPC, Wyatt DAWN type)] is preferably 800 to 800,000. The weight-average molecular weight of glycogen [measured with a laser diffraction absolute molecular weight measuring apparatus (manufactured by Shoko Tsusho, with Shodex-GPC, Wyatt DAWN type)] is preferably 2.4 × 10 ⁶ to 4.4 × 10. ⁶ . Curdlan and glycogen are commercially available, and both can be used as they are.

Next, the compound (S1) will be described. Only 1 type may be used for a compound (S1) and it may use 2 or more types together. In the formula (S1), n represents an integer of 2 or more, preferably 2 to 6, and more preferably 5.

Examples of the compound (S1) include 1,2,3-cyclopropanetriol, 1,2,3,4-cyclobutanetetraol, 1,2,3,4,5-cyclopentanepentaol, 1,2, 3,4,5,6-cyclohexanehexaol, 1,2,3,4,5,6,7-cycloheptaneheptaol, 1,2,3,4,5,6,7,8-cyclooctaneocta Examples include oars. Of these, 1,2,3,4,5,6-cyclohexanehexaol in which n is 5 is preferable. 1,2,3,4,5,6-cyclohexanehexaol is also called inositol. This inositol is synthesized from glucose in vivo. However, in the present invention, artificially synthesized inositol may be used.

Inositol has nine isomers (7 optically inactive substances and a pair of enantiomers) depending on the position of the hydroxy group. As inositol, only one isomer may be used, or two or more isomers may be used in combination. As the inositol isomer, myo-inositol, epi-isoinositol, allo-inositol, muco-inositol, neo-inositol, chiro-inositol, scyllo-inositol and cis-inositol can be used. Among these, myo-inositol and scyllo-inositol represented by the following formula are more preferable, and myo-inositol is more preferable. Chiro-inositol may be D-form (ie, D-chiro-inositol), L-form (ie, L-chiro-inositol), or a mixture of D-form and L-form.

Compound (S1) may be a commercially available product. In addition, compound (S1) may be any of an anhydride, a hydrate, or a mixture thereof.

Next, the compound (S2) will be described. In the formula (S2), p represents an integer of 4 or more, preferably 4 to 8, and more preferably 4 to 6. Only one type of compound (S2) may be used, or two or more types may be used in combination.

The compound (S2) is preferably a sugar alcohol, more preferably tetritol (p = 4), pentitol (p = 5), hexitol (p = 6), heptitol (p = 7), octitol (p = 8). And more preferably tetritol, pentitol, and hexitol. Examples of tetritol include erythritol and threitol. Examples of pentitol include arabinitol and xylitol. Examples of hexitol include sorbitol and mannitol. Compound (S2) is commercially available, and a commercially available product can be used as it is.

Next, the compound (S3) will be described. The compound (S3) is a compound in which at least one hydroxy group of the compound (S3a) is replaced with an alkoxy group (—OR ^S3a ; R ^S3a represents a C _1-12 alkyl group). This compound (S3a) is represented by C _r H _2r O _r (wherein r represents an integer of 3 or more) and is a monosaccharide having r−1 hydroxy groups. r is preferably 3 to 10, more preferably 6. That is, the compound (S3a) is preferably triose (r = 3), tetrose (r = 4), pentose (r = 5), hexose (r = 6), heptose (r = 7), octose (r = 8) Nonose (r = 9) or decourse (r = 10).

The compound (S3a) may be cyclic or chain-like, and preferably cyclic. The cyclic compound (S3a) may be a pyranose type or a furanose type, and is preferably a pyranose type. The compound (S3a) may be D-form or L-form, preferably D-form. Further, the compound (S3a) may be an aldose having an aldehyde group (also referred to as a formyl group) or a ketose having a ketone group (also referred to as a carbonyl group), and is preferably an aldose. Compound (S3a) may be a mixture of the aforementioned compounds.

Examples of the aldose include aldtriose (glyceraldehyde); aldetetrose (erythrose, treose); aldpentose (ribose, arabinose, xylose, lyxose); aldhexose (glucose, mannose, galactose, allose, altrose, And aldoheptose (such as D-glycero-D-galacto-heptose).

Examples of ketose include ketotriose (dihydroxyacetone); ketotetorose (erythrulose); ketopentose (ribulose, xylulose); ketohexose (psicose, fructose, sorbose, tagatose); and ketoheptose (eg, cedoheptulose, D-manno-heptulose). Can be mentioned.

Compound (S3a) is preferably hexose (also called hexose), more preferably aldohexose, and still more preferably glucose. The aldohexose is preferably of the pyranose type. Hereinafter, “a compound in which the hydroxy group of hexose is replaced by an —OR ^S3a group” or the like may be referred to as “hexose-compound (S3)” or the like.

The number of —OR ^S3a groups in the compound (S3) is preferably 5 or less, more preferably 3 or less, and even more preferably 1. When a plurality of -OR ^S3a groups are present, each R ^S3a may be the same as or different from each other, preferably the same. The —OR ^S3a group is preferably bonded to the carbon atom at the 1-position of the compound (S3a). When the —OR ^S3a group is bonded to the carbon atom at the 1-position of the cyclic compound (S3a), the bonding direction of the —OR ^S3a group may be α or β, preferably α. The binding direction and position numbering method follow the standard for monosaccharides.

R ^S3a represents a C _1-12 alkyl group. The C _1-12 alkyl group may be either a chain or a ring, preferably a chain (straight chain or branched chain), more preferably a straight chain. The carbon number of the C _1-12 alkyl group is preferably 1 or more and 8 or less. Examples of the C _1-12 alkyl group include a linear C _1-12 alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group). , Undecyl group, dodecyl group), branched C _3-12 alkyl group (for example, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, etc.), cyclic A C _3-12 alkyl group (that is, a C _3-12 cycloalkyl group, such as a cyclopentyl group, a cyclohexyl group, etc.). The C _1-12 alkyl group is preferably a methyl group, an ethyl group, or an octyl group, and more preferably a methyl group.

Compound (S3) is preferably hexose-compound (S3), more preferably aldohexose-compound (S3) (ie glucose-compound (S3), mannose-compound (S3), galactose-compound (S3), Allose-compound (S3), altrose-compound (S3), growth-compound (S3), idose-compound (S3), or talose-compound (S3)). All of the aldohexoses are preferably of a pyranose type.

Examples of the glucose-compound (S3) include methyl α-D-glucopyranoside, ethyl α-D-glucopyranoside, propyl α-D-glucopyranoside, butyl α-D-glucopyranoside, pentyl α-D-glucopyranoside, hexyl α-D. -Glucopyranoside, heptyl α-D-glucopyranoside, octyl α-D-glucopyranoside, nonyl α-D-glucopyranoside, decyl α-D-glucopyranoside, undecyl α-D-glucopyranoside, dodecyl α-D-glucopyranoside and the like.

Examples of the mannose-compound (S3) include methyl α-D-mannopyranoside, ethyl α-D-mannopyranoside, propyl α-D-mannopyranoside, butyl α-D-mannopyranoside, pentyl α-D-mannopyranoside, hexyl α-D. -Mannopyranoside, heptyl [alpha] -D-mannopyranoside, octyl [alpha] -D-mannopyranoside, nonyl [alpha] -D-mannopyranoside, decyl [alpha] -D-mannopyranoside, undecyl [alpha] -D-mannopyranoside, dodecyl [alpha] -D-mannopyranoside.

Examples of the galactose-compound (S3) include methyl α-D-galactopyranoside, ethyl α-D-galactopyranoside, propyl α-D-galactopyranoside, butyl α-D-galactopyranoside. Pentyl α-D-galactopyranoside, hexyl α-D-galactopyranoside, heptyl α-D-galactopyranoside, octyl α-D-galactopyranoside, nonyl α-D-galactopyranoside Decyl α-D-galactopyranoside, undecyl α-D-galactopyranoside, dodecyl α-D-galactopyranoside, and the like.

Examples of allose-compound (S3) include methyl α-D-allopyranoside, ethyl α-D-allopyranoside, propyl α-D-allopyranoside, butyl α-D-allopyranoside, pentyl α-D-allopyranoside, hexyl α-D. -Allopyranoside, heptyl α-D-allopyranoside, octyl α-D-allopyranoside, nonyl α-D-allopyranoside, decyl α-D-allopyranoside, undecyl α-D-allopyranoside, dodecyl α-D-allopyranoside, and the like.

Examples of the altrose-compound (S3) include methyl α-D-altropyranoside, ethyl α-D-altropyranoside, propyl α-D-altropyranoside, butyl α-D-altropyranoside. Side, pentyl α-D-altropyranoside, hexyl α-D-altropyranoside, heptyl α-D-altropyranoside, octyl α-D-altropyranoside, nonyl α-D-altropira Noside, decyl α-D-altropyranoside, undecyl α-D-altropyranoside, dodecyl α-D-altropyranoside, and the like.

Examples of the growth compound (S3) include methyl α-D-glopyranoside, ethyl α-D-gropyranoside, propyl α-D-gropyranoside, butyl α-D-gropyranoside, pentyl α-D-gropyranoside, hexyl α-D. -Glopyranoside, heptyl α-D-glopyranoside, octyl α-D-gropyranoside, nonyl α-D-gropyranoside, decyl α-D-gropyranoside, undecyl α-D-gropyranoside, dodecyl α-D-glopyranoside and the like.

Examples of the idose-compound (S3) include methyl α-D-id pyranoside, ethyl α-D-id pyranoside, propyl α-D-id pyranoside, butyl α-D-id pyranoside, pentyl α-D-id pyranoside, hexyl α-D. -Id pyranoside, heptyl α-D-id pyranoside, octyl α-D-id pyranoside, nonyl α-D-id pyranoside, decyl α-D-id pyranoside, undecyl α-D-id pyranoside, dodecyl α-D-id pyranoside and the like.

Examples of the talose-compound (S3) include methyl α-D-talopyranoside, ethyl α-D-talopyranoside, propyl α-D-talopyranoside, butyl α-D-talopyranoside, pentyl α-D-talopyranoside, hexyl α-D. -Talopyranoside, heptyl α-D-talopyranoside, octyl α-D-talopyranoside, nonyl α-D-talopyranoside, decyl α-D-talopyranoside, undecyl α-D-talopyranoside, dodecyl α-D-talopyranoside and the like.

In the specific examples, the compound (S3) in which the bonding direction of the —OR ^S3a group is α is listed, but an ^aldhexose- compound (S3) having the same —OR ^S3a group and the bonding direction is β is also exemplified. Can be mentioned. Hereinafter, “compound (S3) in which the bonding direction of the —OR ^S3a group is α” or the like may be abbreviated as “α-form” or the like. Similarly, although the D-form is listed in the specific example, an L-form having the same —OR ^S3a group is also exemplified.

Among aldohexose-compounds (S3), glucose-compound (S3) is preferable, C _1-12 alkyl D-glucopyranoside (both α-form and β-form) is more preferred, and methyl α-D-glucopyranoside and octyl β- D-glucopyranoside is more preferable, and methyl α-D-glucopyranoside is particularly preferable.

Compound (S3) may be a hydrate or an anhydrate. Moreover, a compound (S3) may use only 1 type and may use 2 or more types of mixtures. Examples of the mixture of the compound (S3) include a mixture of the compound (S3) obtained by a known production method from an equilibrium mixture of the compound (S3a) (for example, glycerose which is an equilibrium mixture of glyceraldehyde and dihydroxyacetone). Is mentioned. A mixture of α-form and β-form, and a mixture of D-form and L-form can also be used.

Compound (S3) is produced according to a known method (for example, New Experimental Chemistry Lecture 14, Synthesis and Reaction V of Organic Compound and Method V (Maruzen Co., Ltd., issued on July 20, 1978), page 2426). can do. For example, (i) Compound (S3a) (ie, monosaccharide) is dissolved in alkanol corresponding to —OR ^S3a group, and hydrogen chloride gas is passed through the solution at a temperature of −10 ° C. to room temperature. (Ii) a method of alkoxylating compound (S3a), (ii) a method of alkoxylating compound (S3a) by heating and refluxing a mixed solution of alkanol and hydrochloric acid corresponding to -OR ^S3a group; It is done. Compound (S3) is commercially available. For example, methyl α-D-glucopyranoside and the like can be obtained from Tokyo Chemical Industry Co., Ltd.

The at least one compound selected from the compound group S is preferably at least one selected from the group consisting of trehalose and the compound (S1), more preferably the compound (S1), and still more preferably n is 5. A certain compound (S1) (that is, inositol).

The total amount of the compound (1) in the fiber and at least one compound selected from the compound group S is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic polymer, and stable operation during spinning. From the viewpoint of the properties and mechanical properties of the fiber, it is more preferably 0.001 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and particularly preferably 0.02 to 1 part by weight.

The weight ratio of the compound (1) to at least one compound selected from the compound group S (that is, the compound (1): at least one compound selected from the compound group S) depends on the stability of the operation during spinning and the fiber. From the viewpoint of mechanical properties, it is preferably 1000: 1 to 1: 100. This weight ratio is more preferably 1000: 1 to 1:10. The weight ratio is particularly preferably 1000: 1 to 1: 1 in order to suppress discoloration of the fiber.

The fiber of the present invention may contain additives other than the above components (hereinafter may be abbreviated as “other additives”). Other additives include, for example, antioxidants other than the compound (1) (hereinafter may be abbreviated as “other antioxidants”), ultraviolet absorbers, light stabilizers, stabilizers, lubricants, metal additives. Examples include activators, nucleating agents, antistatic agents, flame retardants, fillers, pigments, inorganic fillers, and other antioxidants, ultraviolet absorbers, light stabilizers, stabilizers and lubricants are preferred. More preferred are antioxidants, ultraviolet absorbers and light stabilizers. As for another additive, all may use only 1 type and may use 2 or more types together.

Other antioxidants include, for example, phenolic antioxidants other than compound (1) (hereinafter may be abbreviated as “other phenolic antioxidants”), phosphorus antioxidants, hydroquinone antioxidants. Agents, sulfur-based antioxidants, and the like, and other phenol-based antioxidants and phosphorus-based antioxidants are preferable.

Examples of other phenolic antioxidants include those described in the following [1] to [7].
[1] 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-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,4,6-tricyclohexylphenol, 2,6-dinonyl-4-methyl Alkylated monophenols such as phenol.

[2] 2,4-bis (octylthiomethyl) -6-t-butylphenol, 2,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (octylthiomethyl) -6-ethyl Alkylthiomethylphenols such as phenol and 2,6-bis (dodecylthiomethyl) -4-nonylphenol;

[3] 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- ( α, α-Dimethylbenzyl) -4-nonylphenol], 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, and other bisphenol derivatives .

[4] Acylaminophenol derivatives such as 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

[5] 2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4,4 Bis (hydroxyphenyl) sulfides or bis (hydroxyphenyl) disulfides such as '-thiobis (2-methyl-6-tert-butylphenol), 4,4'-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[6] 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-butyl) Phenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-t-butyl-4-phenoxy) -1,3,5-triazine, tris [2- (3 ′, Triazine derivatives such as 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate.

[7] Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol.

Next, the phosphorus antioxidant will be described. Preferable phosphorus antioxidants include compounds represented by any of the following formulas (2) to (7).

(In the formula, each R ⁹ and each R ¹⁰ are each independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, or a C _7-12 aralkyl group. Or represents a phenyl group.)

(In the formula, each R ¹¹ independently represents a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or a phenyl group. To express.)

(In the formula, each R ¹² independently represents a C _1-18 alkyl group, or a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, and a C _7-12 aralkyl. Represents a phenyl group which may be substituted with at least one selected from the group consisting of groups.)

(In the formula, each R ¹³ and each R ¹⁴ are each independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, or a C _7-12 aralkyl group. Or represents a phenyl group.
Each L ³ independently represents a single bond, a sulfur atom, or formula (5a):

{Wherein R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a C _1-7 alkyl group on condition that the total number of carbon atoms is 7 or less. } Represents a divalent group.
Each L ⁴ independently represents a C _2-8 alkylene group. )

(In the formula, each R ¹⁷ and each R ¹⁸ are each independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, or a C _7-12 aralkyl group. Or represents a phenyl group.
R ¹⁹ is at least one selected from the group consisting of a C _1-8 alkyl group, or a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, and a C _7-12 aralkyl group. Represents an optionally substituted phenyl group.
L ⁵ represents a single bond, a sulfur atom or the formula (6a):

{Wherein R ²⁰ and R ²¹ each independently represent a hydrogen atom or a C _1-7 alkyl group on condition that the total number of carbon atoms is 7 or less. } Represents a divalent group. )

(In the formula, each R ²² , each R ²³ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, a C _1-8 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, C _7-12 represents an aralkyl group or a phenyl group.
Each R ²⁴ independently represents a hydrogen atom or a C _1-8 alkyl group.
L ⁶ represents a single bond, a sulfur atom or the formula (7a):

{Wherein R ²⁷ represents a hydrogen atom, a C _1-8 alkyl group or a C _5-8 cycloalkyl group. } Represents a divalent group.
L ⁷ represents a C _2-8 alkylene group or formula (7b):

{Wherein L ⁸ represents a single bond or a C _1-8 alkylene group. * Represents bonding to the oxygen atom side. } Represents a divalent group.
One of Z ¹ and Z ² represents a hydroxy group, a C _1-8 alkyl group, a C _1-8 alkoxy group or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or a C _1-8 alkyl group. Represents. )

Hereinafter, the compounds (2) to (7) will be described in order from the compound (2).
Only one type of compound (2) may be used, or two or more types may be used in combination. Each R ⁹ and each R ^{10 in} formula (2) are each independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12. Represents an aralkyl group or a phenyl group. There are three R ^{9 s} , and each R ⁹ may be the same as or different from each other, preferably the same. The same applies to each R ¹⁰ . The positions of R ⁹ and R ¹⁰ are preferably the 2nd and 4th positions.

The C _1-9 alkyl group may be linear or branched. The carbon number of the C _1-9 alkyl group is preferably 3 or more and 5 or less. Examples of the C _1-9 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a t-pentyl group, and 2-ethylhexyl. Group, nonyl group and the like.

Examples of the C _5-8 cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.

Examples of the C _6-12 alkylcycloalkyl group include a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, and a 1-methyl-4-isopropylcyclohexyl group. .

Examples of the C _7-12 aralkyl group include a benzyl group, an α-methylbenzyl group (also referred to as 1-phenylethyl group), an α, α-dimethylbenzyl group (a 1-methyl-1-phenylethyl group or a cumyl group). Called).

Each R ⁹ and each R ¹⁰ are independently preferably a hydrogen atom or a C _1-9 alkyl group, more preferably a hydrogen atom, a t-butyl group or a nonyl group, and still more preferably a t-butyl group.

Examples of the compound (2) include tris (2,4-di-t-butylphenyl) phosphite (hereinafter sometimes abbreviated as “compound (2-1)”), triphenyl phosphite, tris (4 -Nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,4-dinonylphenyl) phosphite and the like. Among these, the compound (2-1) is preferable. The compound (2-1) is commercially available as “Irgaphos (registered trademark) 168” (manufactured by BASF Japan).

Next, the compound (3) will be described. Only 1 type may be used for a compound (3) and it may use 2 or more types together. Each R ¹¹ in formula (3) is independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12 aralkyl group or phenyl. Represents a group. There are four R ^{11 s} , and each R ¹¹ may be the same as or different from each other, preferably the same. _Examples of the C _1-9 alkyl group, the C _5-8 cycloalkyl group, the C _6-12 alkyl cycloalkyl group, and the C _7-12 aralkyl group of R ¹¹ include those described above. Each R ¹¹ is independently preferably a hydrogen atom or a C _1-9 alkyl group, more preferably a hydrogen atom.

Examples of the compound (3) include tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonite (hereinafter sometimes abbreviated as “compound (3-1)”), tetrakis. (2,4-di-t-butyl-5-methylphenyl) -4,4-biphenylenediphosphonite (hereinafter sometimes abbreviated as “compound (3-2)”) and the like. Among these, the compound (3-1) is preferable. Compound (3-1) is “Sand Stub (registered trademark) P-EPQ” (manufactured by Clariant), and Compound (3-2) is “Yosinox (registered trademark) GSY-P101” (manufactured by API). It is commercially available.

Next, the compound (4) will be described. Only one type of compound (4) may be used, or two or more types may be used in combination. Each R ¹² in formula (4) independently represents a C _1-18 alkyl group or a phenyl group. The phenyl group of R ¹² is at least one selected from the group consisting of a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkylcycloalkyl group, and a C _7-12 aralkyl group as a substituent. You may have. In addition, the above-mentioned thing is mentioned as a substituent of these phenyl groups. Two R ¹² exist, and each R ¹² may be the same as or different from each other, preferably the same.

The C _1-18 alkyl group may be linear or branched. The carbon number of the C _1-18 alkyl group is preferably 12 or more and 18 or less. Examples of the C _1-18 alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group. Group, octadecyl group and the like.

Examples of the phenyl group substituted with a C _1-9 alkyl group include a 2-methylphenyl group, a 4-methylphenyl group, a 2-t-butylphenyl group, a 4-t-butylphenyl group, and 2-nonylphenyl. Group, 4-nonylphenyl group, 2,4-di-t-butylphenyl group, 2,4-di-nonylphenyl group, 2,6-di-t-butylphenyl group, 2-t-butyl-4- Examples include methylphenyl group, 2-t-butyl-4-ethylphenyl group, 2,5-di-t-butylphenyl group, 2,6-di-t-butyl-4-methylphenyl group.

Examples of the phenyl group substituted with a C _5-8 cycloalkyl group include a 2-cyclopentylphenyl group, a 2-cyclohexylphenyl group, a 4-cyclohexylphenyl group, and a 2,4-dicyclohexylphenyl group.

Examples of the phenyl group substituted with a C _6-12 alkylcycloalkyl group include 2- (2-methylcyclohexyl) phenyl group, 4- (2-methylcyclohexyl) phenyl group, and 2,4-di- (2 -Methylcyclohexyl) phenyl group and the like.

Examples of the phenyl group substituted with a C _7-12 aralkyl group include a 2-benzylphenyl group, a 2-cumylphenyl group, a 4-cumylphenyl group, and a 2,4-dicumylphenyl group.

Examples of the phenyl group substituted with a C _1-9 alkyl group and a C _5-8 cycloalkyl group include a 2-methyl-4-cyclohexylphenyl group. Examples of the phenyl group substituted with a C _1-9 alkyl group and a C _6-12 alkylcycloalkyl group include a 2-methyl-4- (2-methylcyclohexyl) phenyl group. Examples of the phenyl group substituted with a C _1-9 alkyl group and a C _7-12 aralkyl group include a 2-benzyl-4-methylphenyl group.

Each R ¹² is preferably independently an octadecyl group (also called a stearyl group), a 2,6-di-t-butyl-4-methylphenyl group, a 2,4-di-t-butylphenyl group, or 2 , 4-Dicumylphenyl group.

Examples of the compound (4) include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter sometimes abbreviated as “compound (4-1)”), bis (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite (hereinafter sometimes abbreviated as “compound (4-2)”), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (hereinafter “compound (4)”) -3) ”, distearyl pentaerythritol diphosphite (hereinafter sometimes abbreviated as“ compound (4-4) ”), diisodecylpentaerythritol diphosphite, bis (2,4-di-t-). Butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6) Methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri -t- butylphenyl) pentaerythritol diphosphite, and the like. Among these, the compound (4-1), the compound (4-2), and the compound (4-3) are preferable. Compound (4-1) is “ADK STAB (registered trademark) PEP-36” (manufactured by Adeka), compound (4-2) is “Ultranox (registered trademark) 626” (manufactured by GE Plastics), compound ( 4-3) is commercially available as “Doverfos S9228T” (manufactured by Dover Chemical), and compound (4-4) is commercially available as “Adekastab (registered trademark) PEP-8” (manufactured by Adeka).

Next, the compound (5) will be described. Only one type of compound (5) may be used, or two or more types may be used in combination. In the formula (5), each R ¹³ and each R ¹⁴ are each independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12. Represents an aralkyl group or a phenyl group. _Examples of the C _1-9 alkyl group, the C _5-8 cycloalkyl group, the C _6-12 alkylcycloalkyl group, and the C _7-12 aralkyl group of R ¹³ and R ¹⁴ include those described above. Although there are six R ^{13 s} , each R ¹³ may be the same as or different from each other, preferably the same. The same applies to each R ¹⁴ . The positions of R ¹³ and R ¹⁴ are preferably the 3rd and 5th positions when the position of the carbon atom of the benzene ring to which L ³ is bonded is the 1st position, respectively. Each R ¹³ and each R ¹⁴ are each independently preferably a C _1-9 alkyl group, more preferably a t-butyl group.

Each L ³ in the formula (5) independently represents a single bond, a sulfur atom or a divalent group represented by the formula (5a). R ¹⁵ and R ¹⁶ in the formula (5a) On the condition that the total number of carbon atoms is 7 or less, each independently represents a hydrogen atom or a C _1-7 alkyl group. There are three L ^{3 s,} but each L ³ may be the same as or different from each other, preferably the same.

The C _1-7 alkyl group may be linear or branched. The carbon number of the C _1-7 alkyl group is preferably 1 or more and 3 or less. The total number of carbon atoms of R ¹⁵ and R ¹⁶ is preferably 3 or less. Examples of the C _1-7 alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t- A pentyl group, a hexyl group, a heptyl group, etc. are mentioned.

Examples of the divalent group (5a) include —CH ₂ —, —CH (CH ₃ ) —, —CH (C ₂ H ₅ ) —, —C (CH ₃ ) ₂ —, —CH (n—C). ₃ H ₇₎ -, and the like.

Each L ³ is preferably —CH ₂ — or a single bond, more preferably a single bond.

Each L < ⁴ _{> in} Formula (5) represents a _C2-8 alkylene group each independently. Although there are three L ⁴ , each L ⁴ may be the same as or different from each other, preferably the same.

Examples of the C _2-8 alkylene group include an ethylene group, a propylene group (—CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —), a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples include a methylene group, an octamethylene group, and a 2,2-dimethyl-1,3-propylene group.

Each L ⁴ is independently preferably an ethylene group or a trimethylene group, more preferably an ethylene group.

As the compound (5), 6,6 ′, 6 ″-[nitrilotris (ethyleneoxy)] tris (2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] Dioxaphosphepine) (hereinafter sometimes abbreviated as “compound (5-1)”). The compound (5-1) is commercially available as “Irgaphos (registered trademark) 12” (manufactured by BASF Japan).

Next, the compound (6) will be described. Only one type of compound (6) may be used, or two or more types may be used in combination. In the formula (6), each R ¹⁷ and each R ¹⁸ are independently a hydrogen atom, a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, a C _7-12. Represents an aralkyl group or a phenyl group. _Examples of the C _1-9 alkyl group, the C _5-8 cycloalkyl group, the C _6-12 alkylcycloalkyl group, and the C _7-12 aralkyl group of R ¹⁷ and R ¹⁸ include those described above. Two R ¹⁷ exist, and each R ¹⁷ may be the same as or different from each other, and preferably the same. The same applies to each R ¹⁸ . Position of R ¹⁷ and R ^18, it is when the position of the carbon atoms of the benzene ring which L ⁵ is bonded to position 1 which is 3-position and 5-position (i.e., benzene ring O is attached When the position of the carbon atom of each is the 1st position, it is preferably the 2nd position and the 4th position). Each R ¹⁷ and each R ¹⁸ are each independently preferably a C _1-9 alkyl group, more preferably a t-butyl group.

R ¹⁹ in Formula (6) represents a C _1-8 alkyl group or a phenyl group. The phenyl group of R ¹⁹ is at least one selected from the group consisting of a C _1-9 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl group, and a C _7-12 aralkyl group as a substituent. You may have. The phenyl group having a C _1-8 alkyl group and substituents R ^19, include those described above. However, the carbon number of the C _1-8 alkyl group of R ¹⁹ is preferably 4 or more and 8 or less. R ¹⁹ is preferably a C _1-8 alkyl group, more preferably an octyl group.

L ⁵ in formula (6) represents a single bond, a sulfur atom or a divalent group represented by formula (6a), and R ²⁰ and R ^{21 in} formula (6a) have a total carbon number of 7 or less. Each independently represents a hydrogen atom or a C _1-7 alkyl group. _Examples of the C _1-7 alkyl group for R ²⁰ and R ²¹ include those described above. The total carbon number of R ²⁰ and R ²¹ is preferably 3 or less. Specific examples of the divalent group (6a) include the same as the divalent group (5a). L ⁵ is preferably —CH ₂ — or a single bond, more preferably —CH ₂ —.

Examples of the compound (6) include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (hereinafter sometimes abbreviated as “compound (6-1)”), 2,2 Examples include '-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite. Of these, the compound (6-1) is preferable. Compound (6-1) is commercially available as “ADEKA STAB (registered trademark) HP-10” (manufactured by ADEKA).

Next, the compound (7) will be described. Only one type of compound (7) may be used, or two or more types may be used in combination. In the formula (7), each R ²² , each R ²³ , R ²⁵ and R ²⁶ are each independently a hydrogen atom, a C _1-8 alkyl group, a C _5-8 cycloalkyl group, a C _6-12 alkyl cycloalkyl. Represents a group, a C _7-12 aralkyl group or a phenyl group. There are two R ^{22 s,} but each R ²² may be the same as or different from each other, preferably the same. The same applies to each R ²³ .

The C _1-8 alkyl group may be linear or branched. The carbon number of the C _1-8 alkyl group is preferably 1 or more and 5 or less. Examples of the C _1-8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a t-pentyl group, and an isooctyl group (6-methyl group). A heptyl group), a t-octyl group (also called a 1,1,3,3-tetramethylbutyl group), a 2-ethylhexyl group, and the like.

_{Examples of the} C _5-8 cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

Each R ²² and R ²⁵ is preferably independently a C _1-8 alkyl group (more preferably a C _4-8 alkyl group having a tertiary carbon atom) or a C _5-8 cycloalkyl group (more preferably A cyclohexyl group) or a C _6-12 alkylcycloalkyl group (more preferably a 1-methylcyclohexyl group). As the C _4-8 alkyl group having a tertiary carbon atom, a t-butyl group, a t-pentyl group, and a t-octyl group are more preferable.

Each R ²³ is independently preferably a C _1-8 alkyl group, a C _5-8 cycloalkyl group or a C _6-12 alkyl cycloalkyl group, and more preferably a C _1-5 alkyl group. The C _1-5 alkyl group may be linear or branched. _{Examples of the} C _1-5 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and a t-pentyl group. More preferably, each R ²³ is independently a methyl group, a t-butyl group or a t-pentyl group.

R ²⁶ is preferably a hydrogen atom or a C _1-5 alkyl group, more preferably a hydrogen atom or a methyl group. ^As the _{C 1-5} alkyl group ^{R 26} include those described above.

Each R ²⁴ in Formula (7) independently represents a hydrogen atom or a C _1-8 alkyl group. Although there are two R ^{24 s} , each R ²⁴ may be the same as or different from each other, preferably the same. Each R ²⁴ is preferably a hydrogen atom or a C _1-5 alkyl group, more preferably a methyl group or a hydrogen atom. ^As the _{C 1-8} alkyl group and a _{C 1-5} alkyl group ^{R 24} include those described above.

L ⁶ in the formula (7) represents a single bond, a sulfur atom or a divalent group represented by the formula (7a), and R ²⁷ in the formula (7a) represents a hydrogen atom, a C _1-8 alkyl group or C _5-8 represents a cycloalkyl group. R ²⁷ is preferably a hydrogen atom or a C _1-5 alkyl group. ^{Incidentally,} _{C 1-8} alkyl group ^{R _27,} as the _{C 1-5} alkyl and _{C 5-8} cycloalkyl groups include those described above. L ⁶ is preferably a single bond or a divalent group (7a), and more preferably a single bond.

L ⁷ in the formula (7) represents a C _2-8 alkylene group or a divalent group represented by the formula (7b), and L ⁸ in the formula (7b) represents a single bond or a C _1-8 alkylene group. To express. Both the C _2-8 alkylene group and the C _1-8 alkylene group may be linear or branched. Examples of the C _2-8 alkylene group include an ethylene group, a trimethylene group, a propylene group (—CH (CH ₃ ) CH ₂ —, —CH ₂ CH (CH ₃ ) —), a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples include a methylene group, an octamethylene group, a 2,2-dimethyl-1,3-propylene group, and a propylene group is preferable. Examples of the C _1-8 alkylene group include a methylene group and the aforementioned C _2-8 alkylene group.

L ⁷ is preferably a C _2-8 alkylene group, a divalent group (7b) in which L ⁸ is a single bond (ie, a carbonyl group), or a divalent group (7b) in which L ⁸ is an ethylene group. More preferably a C _2-8 alkylene group; still more preferably a trimethylene group.

In Formula (7), any ^one of Z ¹ and Z ² represents a hydroxy group, a C _1-8 alkyl group, a C _1-8 alkoxy group, or a C _7-12 aralkyloxy group, and the other represents a hydrogen atom or C _1-8 represents an alkyl group. As the _{C 1-8} alkyl group of ^{Z 1} and ^{Z 2} include those described above.

The C _1-8 alkoxy group may be linear or branched. Examples of the C _1-8 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a t-pentyloxy group, and an isooctyloxy group. (Also referred to as 6-methylheptyloxy group), t-octyloxy group (also referred to as 1,1,3,3-tetramethylbutyloxy group), 2-ethylhexyloxy group and the like.

Examples of the C _7-12 aralkyloxy group include benzyloxy group, α-methylbenzyloxy group, α, α-dimethylbenzyloxy group and the like.

It is preferable that ^one of Z ¹ and Z ² is a hydroxy group and the other is a hydrogen atom.

As a preferable combination of the substituents, R ²² and R ²⁵ are each independently a C _4-8 alkyl group, cyclohexyl or 1-methylcyclohexyl group having a tertiary carbon atom, and each R ²³ is independently _Are each a C _1-5 alkyl group, each R ²⁴ is independently a hydrogen atom or a C _1-5 alkyl group, R ²⁶ is a hydrogen atom or a C _1-5 alkyl group, and L ⁶ is a single bond And a combination in which L ⁷ is a C _2-8 alkylene group, one of Z ¹ and Z ² is a hydroxy group, and the other is a hydrogen atom. In this preferred combination, each R ²² is more preferably the same as each other. The same applies to each R ²³ and each R ²⁴ . In this preferred combination, each R ²² , each R ²⁴ and R ²⁵ is more preferably a t-butyl group or a t-pentyl group (particularly a t-butyl group) in common.

Examples of the compound (7) include 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f ] [1,3,2] dioxaphosphine, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-) t-butyl-4-hydroxyphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine, 2,4,8,10-tetra-t-pentyl-6- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -12-methyl -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-dimethyl-4,8-di-t-butyl-6- [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyloxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t-pentyl-6- [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8 , 10-Tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -dibenzo [d, f] [1,3,2] dioxaphos Fepin, 2,10-dimethyl-4,8-di-t-butyl-6 (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,4,8,10-tetra-t- Butyl-6- (3,5-di-t-butyl-4-hydroxybenzoyloxy) -12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10- Dimethyl-4,8-di-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2 Dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 2,10-diethyl -4,8-di-t-butyl-6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propoxy] -12H-dibenzo [d, g] [1,3,2 Dioxaphosphocin, 2,4,8,10-tetra-t-butyl-6- [2,2-dimethyl-3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy]- Examples include dibenzo [d, f] [1,3,2] dioxaphosphine.

Among the compounds (7), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [ 1,3,2] dioxaphosphepine (hereinafter sometimes abbreviated as “compound (7-1)”) is preferred. Compound (7-1) is commercially available as “Sumilyzer (registered trademark) GP” (manufactured by Sumitomo Chemical Co., Ltd.).

Compound (7) may be a commercially available product, or can be produced according to a known method (for example, the method described in JPH10-273494-A).

Among the compounds (2) to (7), the compounds (2) and (7) are preferable. When the fiber of the present invention contains at least one selected from the group consisting of compound (2) to compound (7), these contents in the fiber (in the case of two or more, the total amount thereof) are: From the viewpoint of operation stability during spinning and mechanical properties of the fiber, the content is preferably 0.001 to 3% by weight, more preferably 0.02 to 2% by weight.

Examples of other phosphorus antioxidants include 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- Tri-t-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 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-oxaphosphorinane, 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] and the like.

Examples of the hydroquinone antioxidant include 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-pentylhydroquinone, 2,6 -Diphenyl-4-octadecyloxyphenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl steer Rate, bis (3,5-di-t-butyl-4-hydroxyphenyl), adipate and the like.

Examples of sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, and distearyl 3,3′-. Examples thereof include thiodipropionate, lauryl stearyl, 3,3′-thiodipropionate, neopentanetetrakis (3-laurylthiopropionate), and the like.

Examples of the ultraviolet absorber include those described in the following [1] to [3].
[1] 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, hexadecyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, octadecyl 3 ′, 5′-di-t-butyl-4′-hydroxy Salicylate derivatives such as benzoate, 2-methyl-4,6-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate.

[2] 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy 2-Hydroxybenzophenone derivatives such as -2-methoxyphenyl) methane and 2,2 ′, 4,4′-tetrahydroxybenzophenone.

[3] 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'-sec-butyl-2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2 -(3 ', 5'-di-t-pentyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'- (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-methoxy) Carbonylethyl) phenyl] benzotriazole, 2- [3′-t-butyl-2′-hydroxy-5- (2-octyloxycarbonylethyl) Enyl] 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 A mixture of 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3- Tramethylbutyl) phenol, 2,2′-methylenebis [4-t-butyl-6- (2H-benzotriazol-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) and methyl 3- [3- (2H-benzo Condensate with triazol-2-yl) -5-t-butyl-4-hydroxyphenyl] propionate, 2-ethylhexyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazole-2- Yl) -4-hydroxyphenyl] propionate, octyl 3- [3-tert-butyl-5- (5-chloro-2H-benzotriazole-2- L) -4-hydroxyphenyl] propionate, methyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t 2- (2′-hydroxyphenyl) benzotriazole derivatives such as butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid.

Examples of the light stabilizer include those described in the following [1] to [5].
[1] Hindered amine light stabilizers, for example, those described in the following [a] to [c].
[A] 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-tetra Methyl-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-tert-butyl-4-hydroxybenzyl) 2-butylmalonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2- (3,5-di-tert-butyl-4-hydroxybenzyl) 2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) decanedioate, 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-butanetetra Carboxy Over and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate.

[B] 1,2,3,4-butane mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol Mixed esterified products of tetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6 A mixed esterified product of pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2, , 8,10-mixed ester of tetraoxaspiro [5.5] undecane.

[C] 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) 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)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And 1,2-dibromoethane Polycondensate, 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-triazin-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-triazin-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.

[2] Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, Acrylate-based light stability such as butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline Agent.

[3] Nickel-based light stabilizers such as a nickel complex of 2,2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, and a nickel complex of ketoxime.

[4] 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 -Oxamide light stabilizers such as butyl-2'-ethoxyanilide and 2-ethoxy-5,4'-di-t-butyl-2'-ethyloxanilide.

[5] 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- Triazine light stabilizers such as hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

Examples of the stabilizer include N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, and N, N-ditetradecylhydroxyamine. , N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and the like.

As the lubricant, for example, paraffin, aliphatic hydrocarbons such as _{wax, C 8-22} fatty _{acids, C 8-22} fatty acid metal (Al, Ca, Mg, Zn ) _{salts, C 8-22} aliphatic alcohols, polyglycols , Esters of C _4-22 fatty acids and C _4-18 aliphatic monohydric alcohols, C _8-22 aliphatic amides, silicone oils, rosin derivatives and the like.

The fiber of the present invention is
(A) a thermoplastic polymer;
(B) Compound (1),
(C) at least one compound selected from compound group S;
(D) As needed, it can manufacture by the method including discharging a thermoplastic polymer composition containing another additive from a nozzle | cap | die. Examples of the method for producing the fiber of the present invention include a dry spinning method, a wet spinning method and a melt spinning method, and a melt prevention method is preferred. The fibers or filaments obtained by discharging from the die are preferably received by a spinning cylinder or the like. Moreover, you may extend | stretch the obtained fiber further. It is preferable to wind up the obtained fiber with a winder.

The dry spinning method is a method for producing a fiber by dissolving a thermoplastic polymer composition in a solvent, discharging the obtained solution from a die into a heated atmosphere, and heating and drying the obtained filamentous material. The heating atmosphere is preferably an inert gas atmosphere or a reduced pressure atmosphere. Note that the inert gas may contain moisture or the like.

The wet spinning method is a method of producing a fiber by dissolving a thermoplastic polymer composition in a solvent, discharging the obtained solution from a die, and passing the obtained filamentous material through a coagulation bath. The obtained fiber may be further washed, dried by heating, and stretched. There are no particular limitations on the coagulation bath, and examples thereof include water, organic solvents such as methanol and acetone, aqueous solutions of organic substances and / or inorganic substances (including water dilutions of organic solvents), and the like. The coagulation bath is preferably water or an organic and / or inorganic aqueous solution, more preferably water or a water dilution of an organic solvent, and still more preferably water.

The melt spinning method is a method for producing a fiber by melting a thermoplastic polymer composition, discharging it from a die, and cooling (including cooling). The fiber obtained after cooling may be further stretched.

The fiber of the present invention is
(A) Fiber production by mixing compound (1), at least one compound selected from compound group S, a portion of the thermoplastic polymer to be used, and other additives as required. Prepare a masterbatch for
(B) preparing a thermoplastic polymer composition by mixing the masterbatch, the remaining thermoplastic polymer and optionally other additives;
(C) The thermoplastic polymer composition can also be produced by a method including discharging from the die.

The total amount of the compound (1) and at least one compound selected from the compound group S in the thermoplastic polymer composition used for producing the fiber is preferably 0.001 to 10 with respect to 100 parts by weight of the thermoplastic polymer. Parts by weight, more preferably 0.001 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, and particularly preferably 0.02 to 1 part by weight. The total amount of compound (1) and at least one compound selected from compound group S in the fiber production masterbatch is preferably 1 to 40 parts by weight, more preferably 100 parts by weight of the thermoplastic polymer. Is 5 to 35 parts by weight, more preferably 10 to 20 parts by weight. When the thermoplastic polymer composition is prepared by mixing the fiber production masterbatch and the remaining thermoplastic polymer, the amount of the fiber production masterbatch used is preferably 0.1 per 100 parts by weight of the remaining thermoplastic polymer. The amount is 1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, still more preferably 1 to 20 parts by weight.

The weight ratio of compound (1) to at least one compound selected from compound group S in the thermoplastic polymer composition (that is, compound (1): at least one compound selected from compound group S) is preferably 1000. : 1 to 1: 100, more preferably 1000: 1 to 1:10, particularly preferably 1000: 1 to 1: 1. The weight ratio in the fiber production masterbatch is also the same as in the above-mentioned thermoplastic polymer composition.

The fineness of the fiber of the present invention is not particularly limited, but is usually 0.01 to 1000 dtex, preferably 0.05 to 500 dtex, and more preferably 0.1 to 100 dtex.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples, and Reference Examples, but the present invention is not limited thereto. In the following, “parts” means “parts by weight” unless otherwise specified.

The following were used as compound (1).
Compound (1-a): 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 8,10-tetraoxaspiro [5.5] undecane (Sumitomo Chemical Co., Ltd., Sumilizer (registered trademark) GA-80)
Compound (1-b): Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid (manufactured by Cytec Industries, Syanox (registered trademark) CY-1790)
Compound (1-c): bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] (manufactured by BASF Japan, Irganox (registered trademark)) 245)
Compound (1-d): N, N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propanamide] (BASF Japan, Irganox (registered trademark) 1098 )

As the compounds included in the compound group S, the following were used.
Compound (Sa): myo-inositol Compound (Sb): Trehalose

The following were used as the thermoplastic polymer.
Thermoplastic polymer (Pa): Polyurethane resin (manufactured by Nippon Milactolan, trade name: KHT-302)
Thermoplastic polymer (Pb): Nylon 6 (manufactured by Ube Industries, trade name: UBE NYLON SF1018A, relative viscosity 3.2)
Thermoplastic polymer (Pc): Polyester resin (Bell Polyester Products, trade name: TK3, intrinsic viscosity 0.65)

Examples 1 to 3, Comparative Example 1 and Reference Example 1 (Production of polyurethane fiber)
(Manufacture of fibers)
After dry blending compound (1), compound group S and thermoplastic polymer with the composition shown in Table 1, a nozzle (hole diameter: 0.5 mm, number of holes: 60) was attached to a single screw extruder having a screw diameter of 40 mm. Using a spinning device, set temperature C1 (cylinder temperature): 190 ° C, C2 (cylinder temperature): 190 ° C, C3 (cylinder temperature): 190 ° C, AD (adapter temperature): 200 ° C, D (die temperature): Spinning at 205 ° C., cooling, and winding of spandex fibers (polyurethane elastic yarn) having a fineness of 100 dtex with a first roll speed of 48 m / min and a second roll speed of 50 m / min with a winder.

(Measurement of elastic recovery after heat treatment)
Fibers of length L ₁ obtained was heat treated for 1 minute at 100 ° C.. Thereafter, the fiber was stretched by 200% using an autograph AGS-20KNG manufactured by Shimadzu Corporation and allowed to stand for 1 minute, then gradually weighted, and the length L ₂ of the fiber after standing for 3 minutes was measured. ) To calculate the elastic recovery rate. The results are shown in Table 1.
Elastic recovery rate (%) = 100 × (L ₁ −L ₂ ) / L ₁ (I)

Examples 4 and 5, Comparative Example 2 and Reference Example 2 (Production of nylon 6 fiber)
(Manufacture of fibers)
After dry blending compound (1), compound group S and thermoplastic polymer with the composition shown in Table 2, a nozzle (hole diameter: 0.5 mm, number of holes: 60) was attached to a single screw extruder having a screw diameter of 40 mm. Using a spinning device, spinning was performed at set temperatures C1: 270 ° C., C 2: 270 ° C., C 3: 270 ° C., AD: 27 ° C., D: 270 ° C. Stretching was performed at a rotational speed of 78 m / min for one roll and 21 m / min for a second roll, heat setting was performed at 125 ° C., and nylon 6 fiber having a fineness of 7.1 dtex was wound at 200 m / min.

(Measurement method of strength reduction rate)
The tensile strength S ₁ before heat treatment of the obtained fiber and the tensile strength S ₂ after heat treatment at 190 ° C. for 5 minutes in an air atmosphere were measured, and the strength reduction rate was calculated from the following formula (II). The tensile strength before and after the heat treatment was measured using an autograph AGS-20KNG manufactured by Shimadzu Corporation under the conditions of a grip interval of 25 cm and a pulling speed of 25 cm / min. The results are shown in Table 2.
Strength reduction rate (%) = 100 × (S ₁ −S ₂ ) / S ₁ (II)

Examples 6 to 9 and Reference Example 3 (Production of polyester fiber)
(Manufacture of fibers)
After dry blending compound (1), compound group S and thermoplastic polymer with the composition shown in Table 3, a nozzle (hole diameter: 0.5 mm, number of holes: 60) was attached to a single screw extruder having a screw diameter of 40 mm. Using a spinning device, spinning was performed at set temperatures C1: 285 ° C, C2: 285 ° C, C3: 285 ° C, AD: 290 ° C, D: 285 ° C, cooled, and the number of rotations of the first roll was 56 m / The polyester fiber having a fineness of 6.3 dtex was wound with a winder at a rotation speed of 205 m / min.

(Measurement of strength reduction rate)
A tensile strength S ₃ before hydrothermal treatment of the resulting fibers, and a 100 ° C. for 30 minutes a tensile strength S ₄ after the hot water treatment was measured to calculate the strength decrease rate from the following formula (III). The tensile strength before and after the hot water treatment was measured using an autograph AGS-20KNG manufactured by Shimadzu Corporation under the conditions of a grip interval of 25 cm and a pulling speed of 25 cm / min. The results are shown in Table 3.
Strength reduction rate (%) = 100 × (S ₃ −S ₄ ) / S ₃ (III)

Examples 10 to 17 (Production of fiber using a masterbatch for fiber production)
A masterbatch for fiber production is obtained by melt-kneading compound (1), compound group S and thermoplastic polymer with the composition shown in Table 4. A thermoplastic polymer composition can be obtained by dry blending 1 to 30 parts by weight of the masterbatch with 100 parts by weight of the same thermoplastic polymer contained in the masterbatch. The composition containing the thermoplastic polymer (P-a) is spun as in Examples 1 to 3, and the composition containing the thermoplastic polymer (Pb) is spun as in Examples 4 and 5. Accordingly, the composition containing the thermoplastic polymer (Pc) can be produced by spinning in the same manner as in Examples 6 to 9.

The fiber of the present invention has a small decrease in mechanical properties (elastic recovery rate, tensile strength, etc.) after heat treatment.

Claims

(A) a thermoplastic polymer;
(B) Formula (1):

(In the formula, each R 1 independently represents a C 1-8 alkyl group, a C 6-12 aryl group, or a C 7-18 aralkyl group.
Each R 2 independently represents a hydrogen atom or a C 1-3 alkyl group.
L 1 represents an m-valent C 1-26 organic group.
k represents an integer of 0 to 4.
m represents an integer of 1 to 4. )
A compound represented by
(C) The following compound group S:
(I) glucose,
(Ii) fructose,
(Iii) trehalose,
(Iv) sucrose,
(V) lactose,
(Vi) maltose,
(Vii) meletitol,
(Viii) stachyose,
(Ix) card run,
(X) glycogen,
(Xi) Formula (S1):

(In the formula, n represents an integer of 2 or more.)
A compound represented by
(Xii) C p H p + 2 (OH) p (wherein p represents an integer of 4 or more) (S2), and (xiii) C r H 2r O r (wherein r is 3 And at least one hydroxy group of the compound (S3a) having one aldehyde group or ketone group and r-1 hydroxy group is represented by -OR S3 (wherein R S3 Represents a C 1-12 alkyl group) and is substituted with an alkoxy group (S3)
At least one compound selected from:
Containing fiber.
The compound represented by the formula (1) is 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2. , 4,8,10-tetraoxaspiro [5.5] undecane, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] and tris The fiber according to claim 1, which is at least one selected from the group consisting of (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid.
The compound represented by the formula (1) is represented by the formula (1-1):

(In the formula, each R 3 and each R 4 independently represent a hydrogen atom or a C 1-6 alkyl group.
L 2 represents an m-valent C 1-24 organic group.
m represents an integer of 1 to 4. )
The fiber according to claim 1, which is a compound represented by the formula:
The total amount of the compound represented by the formula (1) and at least one compound selected from the compound group S is 0.001 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic polymer. The fiber according to any one of the above.
The fiber according to any one of claims 1 to 4, wherein at least one compound selected from the compound group S is at least one selected from the group consisting of trehalose and a compound represented by the formula (S1).
The fiber according to any one of claims 1 to 5, wherein the thermoplastic polymer is at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyurethane resin, polyamide resin and polyester resin.
The fiber according to any one of claims 1 to 6, wherein n is 5.
(A) a thermoplastic polymer;
(B) Formula (1):

(In the formula, each R 1 independently represents a C 1-8 alkyl group, a C 6-12 aryl group, or a C 7-18 aralkyl group.
Each R 2 independently represents a hydrogen atom or a C 1-3 alkyl group.
L 1 represents an m-valent C 1-26 organic group.
k represents an integer of 0 to 4.
m represents an integer of 1 to 4. )
A compound represented by
(C) The following compound group S:
(I) glucose,
(Ii) fructose,
(Iii) trehalose,
(Iv) sucrose,
(V) lactose,
(Vi) maltose,
(Vii) meletitol,
(Viii) stachyose,
(Ix) card run,
(X) glycogen,
(Xi) Formula (S1):

(In the formula, n represents an integer of 2 or more.)
A compound represented by
(Xii) C p H p + 2 (OH) p (wherein p represents an integer of 4 or more) (S2), and (xiii) C r H 2r O r (wherein r is 3 And at least one hydroxy group of the compound (S3a) having one aldehyde group or ketone group and r-1 hydroxy group is represented by -OR S3 (wherein R S3 Represents a C 1-12 alkyl group) and is substituted with an alkoxy group (S3)
At least one compound selected from:
The manufacturing method of a fiber including discharging the thermoplastic polymer composition containing this from a nozzle | cap | die.