JP2001295168A - Stretchable woven/knitted fabric and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stretchable woven/knitted fabric containing a polyurethane elastic yarn which is sufficiently stabilized to a discoloring deterioration by nitrogen oxides (NOx) not only in a grey fabric (before a secondary processing) but also after the secondary processing such as dyeing and finishing. SOLUTION: This woven/knitted fabric is obtained by compounding a hindered amine compound having a specific structure to the polyurethane elastic yarn used for the stretchable woven/knitted fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretchable woven or knitted fabric comprising non-stretchable fibers such as polyester fibers, polyamide fibers and cellulosic fibers, and polyurethane elastic yarns. More specifically, the present invention relates to the above-mentioned stretchable woven or knitted fabric which is stable to discoloration and deterioration even after being exposed to an atmosphere in the presence of a nitrogen compound (NOx) or undergoing a secondary processing step such as dyeing.

[0002]

2. Description of the Related Art Woven and knitted fabrics made of non-stretchable fibers such as polyester fibers, polyamide fibers, and cellulosic fibers and polyurethane elastic yarns are excellent in stretch performance. Medical applications such as foundations and underwear such as girdle and body suits, sports clothing such as swimsuits and leotards, outer garments such as ski pants and stretch denim, stretch corsets, stretch tape base fabrics, supporters, etc. It is used for a wide variety of applications, such as base cloth for stretch boots.

[0003] In general, polyurethane elastic yarns used for the above-mentioned applications are often produced from polyisocyanates and polyfunctional active hydrogen compounds having a relatively low molecular weight.

[0004] Among them, 4,4 'as a polyisocyanate
Polyurethane elastic yarns obtained from aromatic isocyanates such as diphenylmethane diisocyanate are widely used because of their particularly excellent mechanical properties. However, polyurethane elastic yarns obtained from aromatic isocyanates have the disadvantage that discoloration due to nitrogen oxides (hereinafter abbreviated as NOx) is particularly remarkable, and the woven or knitted fabric containing the polyurethane elastic yarns is subjected to an NOx-existing atmosphere. When exposed, a phenomenon such as the yellowing of white fabric into a butter-like color occurred in a short time.

[0005] NOx is contained in combustion gas and exhaust gas, and even in a very small amount, causes marked discoloration of the polyurethane elastic yarn. For this reason, suppressing discoloration of the polyurethane elastic yarn due to NOx has been studied for a long time. For example, phosphite-based antioxidants and discoloration inhibitors such as aliphatic amine derivatives and hydrazine derivatives are known. Among them, phosphite antioxidants and hindered amine compounds as aliphatic amine derivatives are widely used because of their high stabilizing effect.

However, when a stretchable woven or knitted fabric mixed with a polyurethane elastic yarn containing a stabilizer such as a phosphite-based antioxidant or a hindered amine compound is dyed, the stabilizing effect may be significantly impaired. Often there was. Therefore, when a stretchable woven or knitted fabric containing these polyurethane elastic yarns or a final product thereof is exposed to an atmosphere containing nitrogen oxides (NOx), there is a high risk of causing problems such as yellowing and deterioration. .

[0007]

SUMMARY OF THE INVENTION The present invention has been intensively studied in view of such circumstances, and the presence of NOx has been observed even after post-processing such as dyeing of polyurethane elastic yarn used for stretchable woven or knitted fabric. It is an object of the present invention to provide a sufficiently stable performance against discoloration degradation even in an atmosphere in which the discoloration occurs.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a polyurethane elastic yarn used in a stretchable woven or knitted fabric contains a hindered amine compound, and a specific hindered amine compound is used as the hindered amine compound. It has been found that the stabilizing effect is enhanced even after post-processing such as dyeing processing by using.

Further, when a specific compound is used as a phenolic antioxidant and a phosphite-based antioxidant in addition to the hindered amine compound in the polyurethane elastic yarn, a higher stabilizing effect can be obtained and the polyurethane elastic yarn can be obtained. The inventor has found that the woven or knitted fabric in which the yarn is mixed is highly stabilized against discoloration and deterioration due to NOx even after post-processing, and the present invention has been completed.

That is, the present invention relates to a stretchable woven or knitted fabric composed of non-stretchable fibers such as polyester, nylon and cotton yarn and polyurethane elastic yarn, wherein the polyurethane elastic yarn is compounded with a hindered amine compound. , Is stable against discoloration deterioration due to nitrogen compounds (NOx), and even after secondary processing such as dyeing processing,
A stretchable woven or knitted fabric characterized by being stable, wherein a hindered amine compound blended in the polyurethane elastic yarn contains, in one molecule, a monovalent organic group represented by the following general formula (1):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]

The following general formula (2)

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or more monovalent and / or divalent organic groups (D) selected from the group consisting of divalent organic groups represented by
1) a hindered amine compound having at least one organic group (D) per 1 kg of the hindered amine compound.
1) A hindered amine compound having a number of 1.3 mol or more and a solubility in an acidic solution of 5.0 × 10 ⁻³ eq / l or less.

A preferred hindered amine compound is represented by the following general formula (3) in one molecule.

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]

A monovalent organic group represented by the following general formula (4):

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or two selected from the group consisting of divalent organic groups
One or more selected from the group consisting of at least one kind of monovalent and / or divalent organic groups (D2), a cycloalkyl group having 5 to 10 carbon atoms, and a cycloalkylene group having 5 to 10 carbon atoms.
A compound having at least one kind of a monovalent and / or divalent organic group (F1), wherein the weight fraction of the organic group (D2) in the molecule (W _D2 (%)) and the weight fraction of the (F1) (W _F1 (%))
Is a hindered amine compound satisfying the following mathematical expressions (5) and (6). 40 ≦ (W _D2 + W _F1) ≦ 70 Equation (5) 0.6 ≦ (W _D2 ÷ W _F1 ) ≦ 3 Equation (6) [In the above equation, W _D2 represents the weight% of the organic group (D2); W _F1 represents the weight% of the organic group (F1). ]

A preferred hindered amine compound is represented by the following general formula (5)

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom or a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 10 carbon atoms.
Represents any one of the above alkoxy groups. X ¹ represents a —O— group or a —NH— group. ]

A radically polymerizable hindered amine derivative monomer component (D3) of one kind or a mixture of two or more kinds selected from the group represented by the following general formula (6):

Embedded image[In the above general formula, R^FiveRepresents a hydrogen atom or a methyl group
Represent. R⁶Represents a cycloalkyl group having 5 to 10 carbon atoms.
You. Y¹Represents a -O- group or a -NH- group. ]
Of one or a mixture of two or more selected from the group consisting of
Radiopolymerizable monomer component (F2)
Hindered amine compound obtained by copolymerization
And the component (D3) of the hindered amine compound,
(F2) satisfies the following formulas (7) and (8).
Hindered amine compound. 80 ≦ (W_D3+ W_F2) ≦ 100 Equation (7) 0.5 ≦ (W_D3÷ W_F2) ≦ 2.3 Expression (8)_D3Is the weight fraction (%) of the component (D3),
W_F2Represents the weight fraction (%) of the component (F2)]  A preferred hindered amine compound has the following general formula:
(7)

[0016]

Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ⁸ represent either a hydrogen atom or a methyl group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
X and Y represent either -O- groups or -NH- groups. n and m represent positive numbers such that 0.35 ≦ (n / m) ≦ 1.75] is obtained. In a more preferred embodiment, the polyurethane elastic yarn further contains a phenolic antioxidant and a phosphite-based antioxidant,

Further, the phenolic antioxidant compounded in the polyurethane elastic yarn is a phenolic antioxidant represented by the following general formula (8):

Embedded image [In the above formula, R ¹⁰ represents a group selected from a t-butyl group, a sec-butyl group, and a neobentyl group. ]

And a phosphite-based antioxidant,
Including the structure represented by the following formula (9)

Embedded image A hydrogenated bisphenol A pentaerythritol phosphite polymer, wherein the blending amount of the phenolic antioxidant with respect to (a) polyurethane is 0.1 to 2.0% by weight;
(B) The compounding amount of the phosphite-based antioxidant is 0.1
(C) 0.5 to 5% by weight of the hindered amine compound.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The polyurethane elastic yarn used in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of polyurethane.

Known polyurethanes such as polyether-based, polyester-based, and polycarbonate-based polyurethanes can be used. Such a polyurethane can be obtained by reacting a polyisocyanate, a polymer diol and, if desired, a low molecular weight polyfunctional active hydrogen compound. Examples of the polyisocyanate include 4,4'-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6
-One or a mixture of tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, xylylene diisocyanate and the like can be used. Among them, 4,4'-diphenylmethane diisocyanate is preferable. The polymer diol is a substantially linear polymer having a hydroxyl group at both terminals and a molecular weight of 600 to 7000, for example, a polyether such as polytetramethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol, polypentamethylene ether glycol. Polyol, copoly (tetramethylene neopentylene) ether diol, copoly (tetramethylene-2-methylbutylene) ether diol, copoly (tetramethylene
Copolyether polyols containing two or more alkylene groups having 6 or less carbon atoms, such as 2,3-dimethylbutylene) ether diol and copoly (tetramethylene / 2,2-dimethylbutylene) ether diol, adipic acid, sebacic acid, Maleic acid, itaconic acid, mazeleiic acid, malonic acid, succinic acid, glutaric acid, suberic acid, dodecanedicarboxylic acid, β-methyladipic acid, hexahydroterephthalic acid and other dibasic acids and / or a mixture of two or more dibasic acids It is obtained from one or a mixture of two or more glycols such as ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,4-dimethylolcyclohexane. Polyester polyol, polyether ester Diol, polylactone diol,
Any polyol such as polycarbonate diol can be used.

Examples of the low-molecular polyfunctional hydrogen compound include compounds having two or more active hydrogen groups capable of reacting with an isocyanate group in the molecule (chain extenders). Examples of the chain extender include one or two of water, hydrazine, ethylenediamine, propylenediamine, xylylenediamine, polyamines such as diethylenetriamine, polyols such as ethylene glycol and butanediol, polyhydrazide, polysemicarbazide, and polyhydroxylamine. Mixtures of more than one species.

As a compound having only one active hydrogen capable of reacting with an isocyanate group in the molecule as a terminal terminator together with a chain extender, one of dialkylamines such as ethylamine, dimethylamine and dibutylamine may be used. Alternatively, a mixture of two or more kinds can be used.

The polyurethane can be polymerized by a known method. For example, the polymerization can be carried out by any method such as solution polymerization and melt polymerization and a combination thereof.
Also, an arbitrary method such as a one-shot method in which the raw materials are mixed at once, or a prepolymer method in which a prepolymer is first formed and the chain is extended can be used.

The method of spinning the polymerized polyurethane composition to form elastic fibers is not particularly limited, but it is preferable to dry spin the polyurethane composition solution.

In the third aspect of the present invention, the monovalent and / or divalent organic group (D1) is a monovalent organic group represented by the above formula (1) and a monovalent organic group represented by the above formula (2). One or two or more selected from the group consisting of divalent organic groups
Is a divalent and / or divalent organic group. Organic group (D1) is 1
In the case of a valent organic group, it is preferable that the organic group is bonded to another site in the compound at the 4-position of the piperidine ring in the general formula (1). R in the above general formula (1)
¹ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and among them, a hydrogen atom or a methyl group is more preferable from the viewpoint of stabilizing effect. When the organic group (D1) is a divalent organic group,
It is preferable that the compound is bonded to another site in the compound at the 1-position and 4-position of the piperidine ring in the general formula (2). Preferred examples of the organic group (D1) include the following structural formulas (10) to (12);

[0026]

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[0027]

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[0028]

Embedded image And the group represented by These organic groups may be composed of only one type of organic group or may be composed of a mixture of two or more types of organic groups within the range defined as described above. Further, it may be composed of a mixture of a monovalent organic group and a divalent organic group. Among them, it is most preferable that the organic group (D1) comprises the organic group represented by the general formula (12). Hindered amine compound 1kg
It is necessary that the number of organic groups (D1) per unit is 1.3 mol or more. If the number of organic groups (D1) is smaller than this, the number of effective sites contributing to stabilization in the compound is reduced, so that the stabilizing effect is lost. Organic group (D
As the number of 1) decreases, the amount of the hindered amine compound must be increased in order to obtain the same effect, which is economically disadvantageous. Hindered amine compound 1k
2.0 mol as the number of organic groups (D1) per g
Above is more preferable in terms of stabilizing effect.

The solubility of the hindered amine compound in the present invention in an acidic solution is measured by the following method. (Measurement of Base Amount per kg of Hindered Amine Compound) 0.0200 g of the hindered amine compound is accurately weighed. When the hindered amine compound is in a solution state, the hindered amine compound may be once separated from the solution and then weighed, or the solution amount such that the weight of the hindered amine compound becomes a predetermined amount as the solution is weighed. Is also good. As a method for separating the hindered amine compound, any known method such as reprecipitation, recrystallization, and evaporation of the solvent can be used. The weighed hindered amine compound is dissolved in 100 ml of the solvent. It is desirable that the solvent used is one that dissolves the hindered amine compound well, does not exhibit basicity itself, and is miscible with water. Examples of such solvents include methanol, ethanol,
Examples thereof include lower alcohol solvents such as propanol, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and ether solvents such as tetrahydrofuran and dioxane. Among these solvents, those in which the hindered amine compound to be measured is soluble can be appropriately selected and used. The hindered amine compound solution was mixed with a glass electrode (GE-101 / Hiranuma Sangyo Co., Ltd.) and a reference electrode (R) using a 1 / 100N hydrochloric acid aqueous solution using a potentiometric titrator (COMMITE-980 / Hiranuma Sangyo Co., Ltd.).
E-101 / Hiranuma Sangyo Co., Ltd.). The end point in the titration curve is defined as the titer. The amount of the base per kg of the hindered amine compound is calculated by the following formula (9).
Can be determined by: B _A = V × F × 10 ^-2 ÷ 0.0200 Formula (9) [In the above formula, B _A represents the amount of base (eq / kg) per 1 kg of the hindered amine compound, and V represents the titer (ml).
And F represents a factor of a 1 / 100N hydrochloric acid aqueous solution. (Preparation of acidic solution) 1.200 g of acetic acid and 0.250 g of anhydrous sodium acetate are accurately weighed and dissolved in 1 liter of pure water using a volumetric flask. (Measurement of solubility of hindered amine compound in acidic solution)
From the amount of base per kg of the hindered amine compound, the weight of the sample for the solubility test was determined to be 5.0 × 10 ^{−5 in} total base amount.
It is determined by the following equation (10) so as to be mol. w _A = (5 × 10 ⁻² ) ÷ B _A Formula (10) [In the above formula, w _A is the weight (g) of the hindered amine compound, and B _A is the amount of base (eq / kg) per kg of the hindered amine compound. Respectively. ]

The hindered amine compound having the weight determined by the above equation (10) is accurately weighed and sealed in a glass ampoule together with 5 ml of the acidic solution prepared as described above. The ampoule is heat-treated at 100 ° C. for 1 hour and opened after cooling. Dissolve 3 ml of the ampoule in an ampoule filtered with a filter having a pore size of 0.45 μm and 1 ml of a 1 / 10N aqueous sodium hydroxide solution in 100 ml of a solvent. As the solvent to be used, the same solvent as that used in the above-mentioned measurement of the amount of base can be used. The mixed solution is subjected to neutralization titration with a 1 / 100N aqueous hydrochloric acid solution using a potentiometric titrator. As a blank, 3 ml of distilled water containing 3.6 × 10 ⁻³ g of acetic acid and 0.75 × 10 ⁻³ g of anhydrous sodium acetate, and 1 / 10N
1 ml of an aqueous sodium hydroxide solution is dissolved in 100 ml of a solvent, and titrated in the same manner. In the titration, the point at which all the bases (hindered amine compound, sodium acetate, and sodium hydroxide) in the liquid to be titrated are all determined as the end point, and the titer is determined. The solubility of the hindered amine compound in the acidic solution is determined from the titer of the sample solution and the blank solution as the amount of base dissolved per liter (1 liter) of the acidic solution by the following equation (11). S _A = (V _S −V _B ) ÷ 300 Equation (11) [where S _A is the solubility (eq / l) of the hindered amine compound in the acidic solution, and V _S is the sample solution 3
The ml of titer (ml), V _B is the titration of the blank solution 3ml (ml), B _A is the hindered amine compound 1k
The amount of base per gram (eq / kg) is shown. ]

In the hindered amine compound according to claim 3 of the present invention, the solubility in the acidic solution determined as described above must be 5.0 × 10 ⁻³ eq / l or less. The smaller the solubility, the better, but 2.5 ×
If it is 10 ^-3 eq / l or less, more preferable characteristics are exhibited.

The organic group (D2) of the hindered amine compound according to claim 4 of the present invention is a monovalent organic group represented by the general formula (3) and a divalent organic group represented by the general formula (4). One or more selected from the group consisting of
Is a divalent and / or divalent organic group. In the general formula (3), R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
Or an alkoxy group having 1 to 10 carbon atoms,
Among them, a hydrogen atom or a methyl group is more preferred from the viewpoint of a stabilizing effect. When the organic group (D2) is a divalent organic group, it is preferable that the organic group (D2) is bonded to other positions in the compound at the first and fourth positions of the piperidine ring in the general formula (4). Preferred examples of the organic group (D2) include groups represented by the above structural formulas (10) to (12). These organic groups may be composed of only one type of organic group or may be composed of a mixture of two or more types of organic groups within the range defined as described above. Further, it may be composed of a mixture of a monovalent organic group and a divalent organic group. Above all, it is most preferable that the organic group (D2) comprises only the organic group represented by the structural formula (12).

The organic group (F1) of the hindered amine compound according to claim 4 of the present invention is selected from the group consisting of a saturated cycloalkyl group having 5 to 10 carbon atoms and a saturated cycloalkylene group having 5 to 10 carbon atoms. One or more monovalent and / or divalent organic groups selected. When the carbon number of the organic group is small, the effect of each group is small, and when the carbon number is large, the number as the group is reduced, resulting in a small effect, and a sufficient stabilizing effect after processing cannot be obtained. As the organic group (F1), a saturated cycloalkyl group having 5 to 15 carbon atoms is particularly preferable. The cycloalkyl group in the present invention represents a group having at least one closed ring in which a plurality of carbon atoms are covalently bonded to each other. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. In the cycloalkyl group, the number of carbon atoms forming a ring may be three or more, but is more preferably five or six. The carbon atom forming the ring may have a linear or branched alkyl chain having 1 to 5 carbon atoms as a substituent. Although the number of alkyl groups as a substituent in the cycloalkyl group is not particularly limited, it is essential that the total number of carbon atoms be 5 to 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable from the viewpoint of the stabilizing effect that all cycloalkyl groups are constituted by covalent bonds and do not contain an unsaturated bond such as a double bond or a triple bond. The organic groups (F1) may all be the same group, or may be composed of two or more groups. The following general formulas (13) to (22) as examples of the organic group (F1);

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image [In the above general formulas (13) to (22), Z is any one of a hydrogen atom, a linear or branched saturated alkyl group having 1 to 5 carbon atoms, and a bonding site to another site in the hindered amine compound. Represents. However, the total number of carbon atoms in the formula does not exceed 10, and the number of bonding sites with other sites in the hindered amine compound in Z is 1 or 2. And the like. Among them, preferred are cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, bornyl group, isobornyl group, decahydronaphthyl group, and the most preferred are cyclohexyl group, isobornyl group. Group.

The hindered amine compound according to claim 4 of the present invention is a compound having one or more organic groups (D2) and (F1) in the molecule. Weight fraction of organic group (D2) and organic group (F1) in the hindered amine compound
Is required to be in the range of 40 to 70% by weight. If the amount is less than this, the stabilizing effect becomes small and a large amount of a stabilizer is required, which is economically disadvantageous. If the amount is larger than this, the stabilizing effect before various types of processing is relatively improved, but the stabilizing effect after various types of processing is lost. A more preferred range is from 50 to 60% by weight. In addition, the ratio of the weight fraction of the organic group (D2) to the weight fraction of the organic group (F1) is 0.6 to 3
Need to be between If it is smaller than 0.6, the stabilizing effect before processing becomes small, and if it is larger than 3, the stabilizing effect after various kinds of processing is lost. A more preferred range is from 1.0 to 2.5. The weight fraction of the organic groups (D2) and (F1) is expressed as a ratio of the total formula weight of each organic group to the molecular weight. When the hindered amine compound is a polymer compound having a repeating unit, the calculation can also be performed for the repeating unit.

The hindered amine compound according to claim 5 of the present invention comprises one or more polymerizable hindered amine compound monomer components (D3) selected from the group represented by the above general formula (5), A hindered amine compound obtained by copolymerizing, as an essential component, one or more polymerizable monomer components (F2) selected from the group represented by the formula (6), and a component (D3) ) And the weight fraction of component (F2) are between 80 and 100% by weight, and the weight ratio of component (D) to weight fraction of component (F2)
It is necessary that the ratio of the weight fractions in 3) satisfies both that is between 0.5 and 2.3. The weight fraction of each component is represented by a ratio of the total weight derived from each component to the weight of the hindered amine compound. The weight of each component in the hindered amine compound can be determined by using any known method for analyzing a polymer.

Examples of quantification include, but are not limited to, quantification of each component by ¹ H-NMR, and quantification of a hindered amine component by neutralization titration. When it is difficult to determine the amount from the hindered amine compound, the weight% of the charged components can be used instead. If the sum of the weight fractions of the component (D3) and the component (F2) is less than 80% by weight, the stability before and after various types of processing cannot be well-balanced. More preferably, it is in the range of 95 to 100% by weight. The component (D) with respect to the weight fraction of the component (F2)
If the weight fraction ratio of 3) is less than 0.3, the stabilizing effect before processing becomes small, and if the stabilizing effect is to be sufficiently obtained, the compounding amount has to be increased, which is economical. Is also disadvantageous. On the other hand, if the ratio is larger than 2.3, the stabilizing effect before processing is sufficiently obtained, but the stabilizing effect after various types of processing is not obtained. Especially, it is especially preferable that it exists in the range of 1.0-1.6.

R ³ in the general formula (5) is a hydrogen atom or a methyl group, and more preferably a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 10 carbon atoms.
Of these, a hydrogen atom and a methyl group are more preferred, and a hydrogen atom is most preferred from the viewpoint of a stabilizing effect. X ¹ in the general formula (5) is -O-
Or an -NH- group, more preferably an -O- group. Polymerizable hindered amine compound monomer component (D
3) is 1 selected from the group represented by the general formula (5).
It is a kind or a mixture of two or more kinds, and each of R ³ , R ⁴ and X ¹ may be mixed with different groups, or each may be a single group. The most preferred combination is R
³ is a methyl group, R ⁴ is a hydrogen atom, and X ¹ is —O
-A group. Preferred examples of the polymerizable hindered amine compound monomer component (D3) include 2,2,6,
6-tetramethyl-4-piperidyl methacrylate,
2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, N- (2,2,
6,6-tetramethyl-4-piperidyl) -methacrylamide, N- (1,2,2,6,6-pentamethyl-4)
-Piperidyl) -methacrylamide, N- (2,2,
6,6-tetramethyl-4-piperidyl) -acrylamide, N- (1,2,2,6,6-pentamethyl-4-)
Piperidyl) -acrylamide. Among them, particularly preferred is 2,2,6,6-tetramethyl-4-
Piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6
6-pentamethyl-4-piperidyl methacrylate,
1,2,2,6,6-pentamethyl-4-piperidyl acrylate. Most preferred is 2,2,6,6
-Tetramethyl-4-piperidyl methacrylate. As the component (D3), compounds in the range of the compounds specified as described above can be mixed and used at an arbitrary composition ratio. Especially, it is preferable to use only 2,2,6,6-tetramethyl-4-piperidyl methacrylate.

R ⁵ in the general formula (6) is a hydrogen atom or a methyl group, and is more preferably a methyl group. R ⁶ is
One or more monovalent organic groups selected from the group consisting of saturated cycloalkyl groups having 5 to 10 carbon atoms and derivatives thereof. When the carbon number of the organic group is small, the effect of each group is small, and when the carbon number is large, the number as the group is reduced, resulting in a small effect, and a sufficient stabilizing effect after processing cannot be obtained. The cycloalkyl group in the present invention represents a group having at least one closed ring in which a plurality of carbon atoms are covalently bonded to each other. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. In R ⁶ , the number of carbon atoms forming a ring may be three or more, but is more preferably 5 or 6. The carbon atom forming the ring may have a linear or branched alkyl chain having 1 to 5 carbon atoms as a substituent. Although the number of alkyl groups as a substituent in the cycloalkyl group is not particularly limited, the total number of carbon atoms is 5 to 5.
It is essential that it be 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable from the viewpoint of the stabilizing effect that all cycloalkyl groups are constituted by covalent bonds and do not contain an unsaturated bond such as a double bond or a triple bond. The bonding site to X ² in R ⁶ may be either a carbon atom on the cycloalkyl group or an alkyl group present as a substituent of the cycloalkyl group. The general formula (13) described above as a specific example of R ⁶
To (22). Among them, preferred examples include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a decahydronaphthyl group, a norbornyl group, a bornyl group, and an isobornyl group. Most preferred are a cyclohexyl group and an isobornyl group. Y ¹ in the general formula (6) is a —O— group or a —NH— group, more preferably a —O— group. The polymerizable monomer component (F2) is one or a mixture of two or more selected from the group represented by the general formula (6), and each of R ⁵ , R ⁶ , and Y ¹ is different. The groups may be mixed or all may be a single group. The most preferred combination is where R ⁵ is a methyl group, R ⁶ is a cyclohexyl group, and Y ¹ is a —O— group.
Preferred examples of the polymerizable monomer component (F2) include:
Cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate, cyclononyl methacrylate, cyclodecyl methacrylate, decahydronaphthyl methacrylate, norbornyl methacrylate, bornyl methacrylate, isobornyl methacrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate , Cyclooctyl acrylate, cyclononyl acrylate, cyclodecyl acrylate, decahydronaphthyl acrylate, norbornyl acrylate, bornyl acrylate, isobornyl acrylate, N-cyclopentyl-methacrylamide,
N-cyclohexyl-methacrylamide, N-cycloheptyl-methacrylamide, N-cyclooctyl-methacrylamide, N-cyclononyl-methacrylamide,
N-cyclodecyl-methacrylamide, N-decahydronaphthyl-methacrylamide, N-norbornyl-methacrylamide, N-bornyl-methacrylamide, N-
Isobornyl-methacrylamide, N-cyclopentyl-acrylamide, N-cyclohexyl-acrylamide, N-cycloheptyl-acrylamide, N-cyclooctyl-acrylamide, norbornyl methacrylate, norbornyl acrylate, N-norbornyl-methacrylamide, N- Norbornyl-acrylamide,
N-cyclononyl-acrylamide, N-cyclodecyl-acrylamide, N-decahydronaphthyl-acrylamide, N-norbornyl-acrylamide, N-bornyl-acrylamide, N-isobornyl-acrylamide. Particularly preferred examples include cyclohexyl methacrylate, cyclohexyl acrylate,
Isobornyl methacrylate, isobornyl acrylate, and most preferred example is cyclohexyl methacrylate.

In the claims of the present invention, the most preferable combination of the polymerizable hindered amine compound monomer component (D3) and the polymerizable monomer component (F2) is 2, 2 respectively.
2,6,6-tetramethyl-4-piperidyl methacrylate and cyclohexyl methacrylate.

The weight fraction of each component is represented by the ratio of the total weight derived from each component to the weight of the hindered amine compound. The weight of each component in the hindered amine compound can be determined by using any known method for analyzing a polymer. As an example of quantification,
Examples include, but are not limited to, quantification of each component by 1H-NMR, quantification of a hindered amine component by neutralization titration, and the like. When it is difficult to determine the amount from the hindered amine compound, the weight% of the charged components can be used instead.

The hindered amine compound of the present invention can be synthesized using the above compound as a raw material. Within the scope of the present invention, any known polymerizable monomer outside the scope of the present invention may be copolymerized at the same time as long as the effect is not impaired. In addition, a known chain regulator may be added as needed at the time of the polymerization reaction. The polymerization reaction can be carried out by any known method, but among them, a radical polymerization method is preferable.Moreover, since the reaction is simple and easy to control, the raw material is prepared in a solvent in the presence of a radical polymerization initiator. The solution polymerization method of reacting is preferred. The polymerization solvent used is, for example, toluene, benzene, xylene,
Hydrocarbon solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methanol, ethanol, isopropanol and n-butanol;
Amide solvents such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphonamide; ether solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; Any solvent can be used as long as it does not react with radicals and dissolves the polymerizable monomer and the copolymer.

As the polymerization initiator to be used, any known polymerization initiator can be used. Among them, 2,2′-azobis (2-diaminopropane) dihydrochloride, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4
-Dimethylvaleronitrile), 4,4′-azobis (4
-Cyanovaleric acid), dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis [2- (2-imidazoline-2)
-Yl) propane] dihydrochloride, 2,2'-azobis [2
-(2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-
Methyl-N- [1,1-bis (hydroxymethyl) -2
-Hydroxyethyl] propionamide {, 2,2'-
Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) methyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2 '-Azobisisobutylamide dihydrate, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 2,2'-azobis [N-
(2-propenyl) -2-methylpropionamide],
An azo polymerization initiator such as 2,2'-azobis (2,4,4-trimethylpentane) is preferable. The concentration of the polymerizable monomer at the time of polymerization preparation is not particularly limited.
Preferably it is between ７０70% by weight. A solvent can be added at any time as the reaction proceeds. The amount of the polymerization initiator to be added can be freely changed according to the desired degree of polymerization. Although not particularly limited, a range of 0.01 to 2% by weight based on the polymerizable monomer is appropriate. The polymerization initiator may be added to the system as it is, or may be added after being dissolved in a polymerization solvent. Further, it may be added at once or may be added in several times. If necessary, a known chain regulator may be added.

The reaction temperature is not particularly limited, but may be 50 to 1
00 ° C is preferred. The reaction time is not particularly limited,
Preferably, it is 24 hours. The amount of the unreacted polymerizable monomer in the polymer composition is not particularly limited, but is preferably 20% by weight or less based on the weight of the polymer. If the amount of the unreacted polymerizable monomer in the hindered amine compound is too large, the polymerizable monomer itself may cause deterioration and the stabilizing effect may be impaired. The obtained copolymer can be used as it is as a solution, or can be used after being purified by any method such as reprecipitation, evaporation of a solvent, and column chromatography. Although the molecular weight of the hindered amine compound in the present invention is not particularly limited, it is 1000 to 1000.
Preferably it is between 500,000. If it is smaller than 1,000, the mobility in the resin increases, and bleed out may occur. If it is larger than 500,000, the physical properties of the resin may be adversely affected, and the stabilizing effect may be inferior to the case where the molecular weight is small.
A more preferred molecular weight range is from 2000 to 20,000.
It is between 0. Those having an appropriate molecular weight can be used depending on the use and purpose. The molecular weight can be measured by a known method such as a gel permeation chromatography method, a light scattering method, and an osmotic pressure method.

The hindered amine compound in the present invention is a group in which all or a part of the hindered amino group comprises an organic carboxylic acid, carbon dioxide, a phosphoric acid compound, a phosphoric acid ester compound, a phosphorous acid compound, and a phosphorous acid ester compound. One or more compounds selected from the above may form a salt. All or part of the hindered amino group of the hindered amine compound, by forming a salt with the above compound, adjusts the basicity and solubility of the hindered amine compound without impairing the stabilizing effect inherent to the hindered amine compound. be able to.

The organic carboxylic acids include those having 1 to 10 carbon atoms.
Is preferred, and a saturated carboxylic acid is preferred. Further, monocarboxylic acids are preferable to polycarboxylic acids. Specific examples include formic acid, acetic acid,
Propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, acetoacetic acid, pyruvic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, naphthoacetic acid, phenyl Acetic acid and the like can be mentioned.

The phosphoric acid compound is phosphoric acid or a salt of phosphoric acid with a basic compound such as an amine or a metal ion. The phosphorous acid compound refers to phosphorous acid or a salt of phosphorous acid with a base compound such as an amine or a metal ion. The phosphate ester compound is preferably a phosphate monoester compound or diester compound, but may be a polymer compound having a phosphate monoester or diester structure partially. As the phosphite compound, a phosphite monoester compound or a diester compound is preferable, but a high molecular compound and a compound partially having a phosphite monoester or diester structure may be used. Good. The phosphate compound and the phosphite compound may be partially a salt with a base compound such as an amine or a metal ion.

The compounding time of the hindered amine compound of the present invention is not particularly limited as long as it is up to the spinning step. If it does not affect the polymerization reaction of the resin or the resin to be a fiber, it is added to the raw material. You can also.
It can also be blended after the polymerization of the resin or the resin to be a fiber is completed. It is preferable to mix the resin after the completion of the polymerization of the resin and before the molding. Antioxidants such as phenolic antioxidants, phosphite antioxidants, and thioether antioxidants; and ultraviolet light such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers Metal deactivators such as absorbents, dihydrazide derivative-based metal deactivators, oxalic acid derivative-based metal deactivators, magnesium stearate, higher fatty acid amides, higher fatty acid esters, polyorganosiloxanes, polytetrafluoro Anti-adhesives such as ethylene, inorganic fine particles such as titanium dioxide, magnesium oxide, zinc oxide, hydrotalcite, barium sulfate, magnesium silicate, calcium silicate, and other known additions such as flame retardants and fungicides It can also be mixed with an agent and added. In the case of spinning by a melting method when compounding the fibers, the hindered amine compound of the present invention can be compounded by melt-kneading the raw material resin.
In the case of spinning by a wet method or a dry method, the hindered amine compound of the present invention can be blended with the spinning dope by mixing the hindered amine compound alone or as a solution. The spinning device and spinning conditions used during spinning are not particularly limited,
Any known method can be selected depending on the composition, use, purpose, and thread properties of the resin. The hindered amine compounds of the present invention are particularly suitable as stabilizers for fibers, especially polyurethane fibers. Further, among polyurethane fibers, the polyurethane fiber is particularly suitable for a polyurethane fiber produced from a polyurethane solution by a dry spinning method or a wet spinning method.

The hindered amine compound of the present invention can be added in such an amount as to exert a sufficient stabilizing action, depending on the type and use of the resin or fiber. Although not particularly limited, it is preferably 0.05 to 10% by weight based on the weight of the fiber. In the case of polyurethane fibers, it is particularly preferred that it is between 0.5 and 5% by weight.

The polyurethane elastic fiber preferably contains a phenolic antioxidant and a phosphite antioxidant in addition to the hindered amine compound of the present invention. When phenolic antioxidants are blended, light and spinning
The durability against heat during processing is improved. When a phosphite-based antioxidant is added, the NOx yellowing resistance can be further improved.

The constituents other than polyurethane constituting the polyurethane composition include (a) a phenolic antioxidant,
In addition to (b) phosphite ester antioxidants and (c) hindered amine compounds, stabilizers such as smoothing agents and ultraviolet absorbers, pigments, antistatic agents, surface treatment agents, flame retardants, reinforcing agents, and chlorine degradation And an inhibitor. Above all, in order to improve light resistance, it is preferable to blend an ultraviolet absorber such as a benzotriazole ultraviolet absorber or a triazine ultraviolet absorber. Any known compound can be used in a required amount as needed as the ultraviolet absorber.

As the phenolic antioxidant, any known phenolic antioxidant can be used. In consideration of solubility in solvents and compatibility with polyurethane,
Appropriate compounds can be selected. Examples of phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
t-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-t-butyl- 3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-tris (4-sec
-Butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1.3.5-tris (4-neopentyl-3)
-Hydroxy-2,6-dimethyl) isocyanuric acid,
2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-butylidenebis (4-methyl-6-t-butylphenol), 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, tris- (3,5-
Di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl｝ -2,4,8,1
0-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-t-
Butyl-4-hydroxyphenyl) propionate],
N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5-
Di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-
Butyl-4-hydroxybenzyl) -isocyanurate, isooctyl-3- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionate, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, polycondensate of p-chloromethylstyrene and P-cresol, p Polycondensates of chloromethylstyrene and divinylbenzene, and isobutylene reactants of p-cresol and polycondensates of divinylbenzene. Among them, 1,3,5-tris (4-t
-Butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid, 1,3,5-tris (sec-butyl-3-
(Hydroxy-2,6-dimethyl) isocyanuric acid, 1,
3,5-tris (4-neopentyl-3-hydroxy-
2,6-dimethyl) isocyanuric acid is particularly preferred,
1,3,5-Tris (4-tert-butyl-3-hydroxy-2,6-dimethyl) isocyanuric acid is most preferred.

The phenolic antioxidant can be used in the polyurethane in such an amount that the deterioration can be sufficiently suppressed in actual use. Also, two or more phenolic antioxidants may be used in combination. The compounding amount of the phenolic antioxidant is 0.1 to 2 with respect to the polyurethane.
Preferably it is between wt.%.

The phosphite-based antioxidants include:
Any known compound can be used. An appropriate compound can be selected in consideration of solubility in a solvent, compatibility with polyurethane, and the like. Examples of the phosphite-based antioxidant include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenephosphonite, trisnoniphenylphosphite, and tris (2,4
-Di-t-butylphenyl) phosphite, distearylpentaerythryl diphosphite, di (2.4
-Di-t-butylphenyl) -pentaerythryl diphosphite, di (2,6-di-t-butyl-4-methylphenyl) -pentaerythryl diphosphite, triphenyl phosphite, diphenylisodecyl phosphite , Phenyldiisodecyl phosphite, 4,4
'-Butylidene-bis (3-methyl-6-t-butylphenyl-ditodecyl) phosphite, cyclic neopentanetetrayl (octadecyl phosphite), tris (mono and / or dinonyl phenyl) phosphite, diisodecyl pentaeryth Litose diphosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, hydrogenated Bisphenol A pentaerythritol phosphite polymer, hydrogenated bisphenol A phosphite polymer, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-iso Examples include propylidene diphenyl diphosphite and tetraphenyl dipropylene glycol diphosphite. Among them, hydrogenated bisphenol A pentaerythritol phosphite polymer and hydrogenated bisphenol A phosphite polymer are preferred.
The phosphite-based antioxidant can be used by mixing it with polyurethane in such an amount that the deterioration can be sufficiently suppressed in actual use.

Further, two or more phosphorous acid antioxidants may be used in combination. The compounding amount of the phosphite-based antioxidant is preferably between 0.1 and 2% by weight based on the polyurethane.

The polyester fiber used in the present invention is a polyester fiber known to those skilled in the art, and a typical example is polyethylene terephthalate.

The polyamide fibers used in the present invention include nylon 6, nylon 66, nylon 46, and their cationically dyeable denatured products and polyamide / ester composite fibers. Can be used.

The cellulosic fibers used in the present invention include cotton yarns, rayon, blended yarns of these with polyester fibers and the like, and composite yarns of nylon / ester long fibers, etc., and any fineness can be selected. .

There is no particular limitation on non-elastic yarns such as animal hair fibers such as wool, cashmere and alpaca, silk, acrylic fibers, and promix fibers.

The polyurethane elastic yarn used in the present invention is usually used in the form of a bare (bare) yarn or a composite elastic yarn such as a single covering yarn, a double covering yarn, a core spun yarn, and a pliers.

The stretchable woven or knitted fabric targeted in the present invention is a stretchable woven or knitted fabric comprising the polyurethane elastic yarn and the above-mentioned inelastic yarn such as the polyester-based fiber, polyamide-based fiber, and cellulosic fiber. Examples of the woven fabric include plain weave, twill weave, and satin weave used for warp and / or weft. In the case of knitting, circular knitting is a flat knit, double-sided knitting, rib knitting, pearl knitting or a change knitted fabric thereof, and warp knitting is a tricot knitted fabric or Russell knitted fabric, and is not particularly limited. Examples of the knitting structure include a half knit, a reverse half knit, a double denby knit, a double atlas knit, a power net, a half power net, a satin net, and a triconet in the case of a tricot knitted fabric.

[0071]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited by these examples. The evaluation method used in the present invention is shown below.

(Measurement of solubility of hindered amine compound in acidic solution) The hindered amine compound solution was dropped into pure water to reprecipitate the hindered amine compound. The precipitate was filtered and dried under vacuum at 80 ° C. for 12 hours to obtain a hindered amine compound. The solubility of each of the obtained hindered amine compounds in an acidic solution was measured according to the method described in the text. Methanol was used as the solvent for the titration.

(NOx discoloration test) About 1 g of the stretchable woven or knitted fabric for evaluation was mixed with 500 ml of dry air containing 200 ppm of NO ₂ generated using a permeator PD-1-B (Gastec Co., Ltd.). Exposure for 1.5 hours in a closed container with continuous flow at a flow rate of / min. After exposure,
The buffer urea solution described in JIS-L0855, then thoroughly washed with pure water, dried under a nitrogen stream for 24 hours, and using a color meter TC1500MC-88 (Tokyo Denshoku Co., Ltd.), a Hunter Lab color system. B in
The value is measured for eight evaluation stretchable woven or knitted fabrics.
The discoloration property (△ b) was determined by the following equation (9). Δb = b value after NOx processing−b value before NOx processing (Equation 9) The smaller the value of b, the smaller the discoloration and the better.

(Synthesis Example) Synthesis of Hindered Amine Compound A 2,2,6,6-flask with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser was attached to a 500 cc branched flask.
60 parts of tetramethyl-4-piperidyl methacrylate (ADEKA STAB LA-87 / Asahi Denka Kogyo Co., Ltd.), 40 parts of cyclohexyl methacrylate, and 213 parts of N, N'-dimethylacetamide were taken and dissolved by stirring.
Place the flask in an oil bath while bubbling nitrogen through it.
Heat to 0 ° C. with stirring.

After reaching 60 ° C., 0.8 parts of 4,4-azoisobutyronitrile (AIBN) were added. The reaction was maintained at 60 ° C. while stirring as it was. Five hours after the initial addition of AIBN, an additional 0.2 parts of AIBN was added. The reaction was further continued at 60 ° C. for 15 hours, and then cooled to room temperature to obtain a hindered amine compound solution in which the reaction was completed. Using a rotor with a cone angle of 3 ° and a radius of 14 mm, 3
The solution viscosity measured with an E-type viscometer at 0 ° C. is 15 poise
Met. The unreacted polymerizable monomer in the solution was quantified by gas chromatography and found to be 4% by weight based on the weight of the charged polymerizable monomer. The number average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent and a refractometer as a detector was 2,700. The ¹ H-NMR spectrum of the obtained hindered amine compound was measured using DMSO-d ₆
When measured at 50 ° C. using a 1: 1 mixture of methane and CDCl ₃ as a solvent, the proton of the methine carbon of the piperidyl group and the proton of the methine carbon of the cyclohexyl group were 5.0, 4,. 6 ppm, integration ratio is 5
2:48. Since this integral ratio is considered to be the molar ratio of the unit derived from 2,2,6,6-tetramethyl-4-piperidyl methacrylate and the unit derived from cyclohexyl methacrylate in the hindered amine compound, The percentage was calculated to be 60,40% by weight, which was consistent with the value determined from the charge.

Table 1 shows the characteristic values of the hindered amine compound.

(Comparative Synthesis Example) As the polymerizable monomer,
80 parts of 2,6,6-tetramethyl-4-piperidyl methacrylate and cyclohexyl methacrylate 20
A hindered amine compound was obtained in the same manner as in the synthesis example except that part was used. Table 1 shows the characteristic values of the hindered amine compound.

(Example 1 of Production of Polyurethane Elastic Yarn) 175.37 parts of polytetramethylene ether glycol having a number average molecular weight of 1800 and 38.92 parts of 4,4-diphenylmethane diisocyanate were added at 80 ° C. under a stream of N ₂ at 3 ° C.
The reaction was carried out for an hour to obtain a prepolymer having both ends at isocyanate groups. After cooling the prepolymer to 40 ° C.,
308.36 parts of N'-dimethylacetamide was added and dissolved. It was further cooled to 10 ° C. Ethylenediamine3.
A solution prepared by dissolving 58 parts and 0.46 part of diethylamine in 146.86 parts of N, N'-dimethylacetamide was added to the prepolymer solution with high speed stirring at one time and mixed to complete the reaction. The viscosity of this solution at 30 ° C. is 20
It was 00poise. In this solution, 13.42 parts of the hindered amine solution obtained in the above synthesis example, and 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl isocyanurate) as an antioxidant were added. (Cyanox 1790 / Japan Cyanamid)
2.15 parts, as an ultraviolet absorber, 1.08 parts of 2- [2-hydroxy- (3,5-di-t-amyl) phenyl] benzotriazole (KEMISORB74 / Chemiplo Kasei Co., Ltd.), and as an antiadhesive 0.69 parts of magnesium stearate was added and mixed with stirring to obtain a polyurethane solution. After the polyurethane solution was de-processed, the polyurethane heated yarn was extruded from a die having a fine pore diameter into a spinning cylinder in which air heated to 230 ° C. was flown to obtain a fibrous so-called dry spinning to obtain a polyurethane elastic yarn.

(Production Example 2 of Polyurethane Elastic Yarn) In the spinning dope in Production Example 1 of polyurethane elastic yarn, hydrogenated bisphenol A pentaerythritol phosphite polymer (JPH) was used as a phosphite-based antioxidant.
(-3800 / Johoku Chemical Co., Ltd.) A polyurethane elastic yarn was obtained in the same manner as in Production Example 1, except that 2.15 parts was further added.

(Comparative Example of Production of Polyurethane Elastic Yarn) As the hindered amine compound, except that 13.42 parts of the hindered amine compound obtained in the practical synthesis example was used, the hindered amine compound obtained in the comparative synthesis example was used. Example of production of polyurethane elastic yarn
A polyurethane elastic yarn was obtained.

(Example 1) A Russell knitting machine (RSE-4N, manufactured by KARL MAYER CO., LTD.) Was combined with the polyurethane elastic yarn 310 dtex yarn obtained in the above-mentioned manufacturing example 1 and a nylon 6 55 dtex-17 filament.
/ 130 inch width / 28 gauge) using 6 courses /
The fabric of the power net organization was knitted. The fabric was subjected to a usual dyeing finish known to those skilled in the art to obtain a fabric having a warp density of 60 courses / inch and a lateral density of 40 wales / inch.

(Example 2) A tricot knitting machine (manufactured by KARL MAYER Co., Ltd.) obtained by combining the polyurethane elastic yarn 44 dtex yarn obtained in the above-mentioned production example 1 with the nylon 6 55 dtex-12 filament (@Bright) was used. HKS2 / 180 inch width / 28 gauge), and knitted a half-structure two-way tricot fabric. This fabric was dyed and finished to obtain a fabric having a warp density of 100 courses / inch and a lateral density of 60 wales / inch.

(Example 3) A single circular knitting machine (XL-) manufactured by Fukuhara Seiki Co., Ltd. was combined with 44 dtex of the polyurethane elastic yarn obtained in the above-mentioned Production Example 1 and 48 filaments of polyester 165 dtex.
Using a 3FA / pot diameter 38 inches / 28 gauge), a fabric having a bare sheeting structure was knitted. This fabric was dyed and finished to obtain a fabric of 65 courses / inch and 42 wales / inch.

Example 4 As a polyurethane elastic yarn,
A cloth having a warp density of 60 courses / inch and a lateral density of 40 wales / inch was obtained in the same manner as in Example 1 except that the polyurethane elastic yarn obtained in Example 2 was used.

(Example 5) As a polyurethane elastic yarn,
Except for using the polyurethane elastic yarn obtained in Example 2, the same procedure as in Example 2 was carried out, and the density was 100 courses /
A fabric having an inch and a lateral density of 60 wales / inch was obtained.

(Example 6) As a polyurethane elastic yarn,
Except for using the polyurethane elastic yarn obtained in Example 2, all courses were 65 courses / inch as in Example 3.
A 42 wale / inch fabric was obtained.

(Comparative Examples 1 to 3) Knitting was performed using the same yarn combination, knitting machine, and knitting structure as in Examples 1 to 3, except that the polyurethane elastic yarns obtained in the above Comparative Production Examples were used. Fabrics obtained by dyeing and finishing with the same amount as in Examples 1 to 3 are Comparative Examples 1 to 3. For the fabrics of Examples 1 to 6 and Comparative Examples 1 to 3, the above-described NOx discoloration test was performed on the dough before and after the dyeing finish processing, and the b value before and after the NOx treatment was measured. The b values were compared. Table 2 shows the results. Regardless of the structure, the △ b value of the example is smaller than the △ b value of the comparative example, and it is hard to discolor and stable.

[0088]

[Table 1]

[0089]

[Table 2]

The stretchable woven or knitted fabric of the present invention is sufficiently stabilized against discoloration and deterioration due to nitrogen oxide (NOx), and has good stability even after secondary processing such as dyeing finishing. Effect is maintained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) D01F 6/70 D01F 6/70 Z F-term (Reference) 4L002 AA00 AA05 AA06 AA07 AC01 BA01 CA01 EA00 EA06 FA01 4L035 BB02 BB11 EE20 FF10 GG04 JJ16 JJ19 JJ25 KK05 MH02 MH09 MH13 4L048 AA26 AC12 DA01

Claims (11)

[Claims] 1. A stretchable woven or knitted fabric comprising a non-stretchable fiber and a polyurethane elastic yarn, wherein the polyurethane elastic yarn comprises a composition comprising a hindered amine compound. 2. The stretchable woven or knitted fabric according to claim 1, wherein the non-stretchable fibers are at least one fiber selected from polyester fibers, polyamide fibers, and cellulosic fibers. 3. A hindered amine compound blended in the polyurethane elastic yarn comprises a monovalent organic group represented by the following general formula (1) in one molecule: [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ¹ represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ] The following general formula (2) [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or more monovalent and / or divalent organic groups (D) selected from the group consisting of divalent organic groups represented by
1) a hindered amine compound having at least one organic group (D) per 1 kg of the hindered amine compound.
3) The hindered amine compound having a number of 1) of 1.3 mol or more and a solubility in an acidic solution of 5.0 × 10 ⁻³ eq / l or less, the stretchability according to claim 1 or 2, wherein Weaving and knitting. 4. The hindered amine compound is represented by the following general formula (3) in one molecule. [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² represents any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. A monovalent organic group represented by the following general formula (4): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. One or two selected from the group consisting of divalent organic groups
One or more selected from the group consisting of at least one kind of monovalent and / or divalent organic groups (D2), a cycloalkyl group having 5 to 10 carbon atoms, and a cycloalkylene group having 5 to 10 carbon atoms.
Compounds having at least one kind of monovalent and / or divalent organic groups (F1), wherein the weight fraction of organic groups (D2) in the molecule (W _D2 (%)) and the weight fraction of (F1) (W _F1 (%))
Is a hindered amine compound satisfying the following formulas (1) and (2): 40 ≦ ( _WD2 + _WF1) ≦ 70 Formula (1) 0.6 ≦ ( _WD2 ÷ _WF1 ) ≦ 3 Formula (2) The stretchable woven or knitted fabric according to any one of claims 1 to 3. 5. The hindered amine compound blended in the polyurethane elastic yarn is represented by the following general formula (5): [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ³ represents a hydrogen atom or a methyl group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 10 carbon atoms.
Represents any one of the above alkoxy groups. X ¹ represents a —O— group or a —NH— group. A radically polymerizable hindered amine derivative monomer component (D3) of one or a mixture of two or more selected from the group represented by the following general formula (6): [In the above general formula, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a cycloalkyl group having 5 to 10 carbon atoms. Y ¹ represents a —O— group or a —NH— group. A radically polymerizable monomer component (F2) of one or a mixture of two or more selected from the group represented by the following formula: The stretchable woven or knitted fabric according to any one of claims 1 to 4, wherein a weight fraction of the component (D3) and the component (F2) is a hindered amine compound satisfying the following formulas (3) and (4). . 80 ≦ (W _D3 + W _F2 ) ≦ 100 Equation (3) 0.5 ≦ (W _D3 ÷ W _F2 ) ≦ 2.3 Equation (4) [In the above equation, W _D3 is the weight fraction of the component (D3) ( %),
_WF2 represents the weight fraction (%) of the component (F2)] 6. The stretchable woven or knitted fabric according to claim 1, wherein the hindered amine compound blended in the polyurethane elastic yarn has a structure represented by the following general formula (7). Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ⁸ represent either a hydrogen atom or a methyl group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
X and Y represent either -O- groups or -NH- groups. n and m represent positive numbers such that 0.35 ≦ (n / m) ≦ 1.75] 7. The stretchable woven or knitted fabric according to claim 1, wherein the polyurethane elastic yarn contains a phenolic antioxidant and a phosphite ester antioxidant. 8. The phenolic antioxidant compounded in the polyurethane elastic yarn is a phenolic antioxidant represented by the following general formula (8): [In the above formula, R ¹⁰ represents a group selected from a t-butyl group, a sec-butyl group, and a neobentyl group. And a phosphite-based antioxidant having a structure represented by the following formula (9): The stretchable woven or knitted fabric according to any one of claims 1 to 7, which is a hydrogenated bisphenol A pentaerythritol phosphite polymer. 9. The polyurethane elastic yarn according to claim 1, wherein the blending amount of the phenolic antioxidant with respect to the polyurethane (a) is 0.1 to 2.0% by weight, and the blending amount of the phosphite ester antioxidant is (b). The stretchable woven or knitted fabric according to claim 7 or 8, wherein the amount of the hindered amine compound is 0.1 to 2% by weight and the amount of the hindered amine compound is 0.5 to 5% by weight. 10. The stretchable woven or knitted fabric according to claim 1, wherein the polyurethane elastic yarn of the stretchable woven or knitted fabric is obtained by cross-weaving or knitting as a bare (naked) yarn or a composite elastic yarn thereof. . 11. A method for producing a stretchable woven or knitted fabric produced from non-stretchable fibers and polyurethane elastic yarns, wherein the polyurethane elastic yarns comprise a composition containing a hindered amine compound. 10. The method for producing a stretchable woven or knitted fabric according to any one of 10 above.