JP2002004108A - Brassiere - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a brassiere fully stabilized against discoloration and deterioration caused by nitrogen oxides(NOx), and retaining it stabilizating effect even after to further processings such as dyeing or finishing. SOLUTION: This brassiere is such that a stretchable knitted fabric comprising inelastic fibers and polyurethane elastic yarns containing a hindered amine compound, it used as at least part thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bra using a stretchable knitted fabric comprising non-stretchable fibers such as polyester fibers, polyamide fibers and cellulosic fibers and polyurethane elastic yarn. More specifically, nitrogen compounds (NO
The present invention relates to a bra using a stretchable knitted fabric that is stable to discoloration and deterioration even when exposed to an atmosphere in the presence of x) or undergoes a secondary processing step such as dyeing processing.

[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 dyeing 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, the stabilizing effect may be significantly impaired. Often there was. For this reason, when exposed to an atmosphere in which nitrogen oxides (NOx) exist in a stretchable woven or knitted fabric or a final product in which these polyurethane elastic yarns are mixed, there is a great risk of causing problems such as yellowing and deterioration. .

[0007]

SUMMARY OF THE INVENTION The present invention has been intensively studied in view of the above circumstances. Discoloration / deterioration of polyurethane elastic yarns after post-processing such as dyeing, and even in an atmosphere where NOx is present. The object of the present invention is to solve the above-mentioned problem by providing a sufficiently stable performance and using a stretchable knitted fabric using the polyurethane elastic yarn for the construction of a bra.

[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 knitted fabric for a bra contains a hindered amine compound. It has been found that the use of a hindered amine compound enhances the stabilizing effect even after post-processing such as dyeing.

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 knitted fabric in which the yarn is mixed is highly stabilized against discoloration deterioration due to NOx even after post-processing, and the present invention has been completed.

That is, the present invention relates to a brassiere using a stretchable knitted fabric composed of non-stretchable fibers such as polyester, nylon and cotton yarn and polyurethane elastic yarn, wherein the polyurethane elastic yarn comprises a hindered amine compound. A stretchable woven or knitted fabric which is stable against discoloration deterioration due to a nitrogen compound (NOx) and is stable even after secondary processing such as dyeing. The hindered amine compound blended in the elastic yarn is selected from the group consisting of a monovalent organic group represented by the following general formula (1) and a divalent organic group represented by the following general formula (2) in one molecule. One or more of one
Amine compound having at least one divalent and / or divalent organic group (D1), wherein the number of organic groups (D1) per 1 kg of the hindered amine compound is 1.3 mol.
1 or more and the solubility in an acidic solution is 5.0 ×
10 ^-3 eq / l or less

[0011]

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[In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. R1 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. ]

[0013]

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[In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. ]

The preferred hindered amine compound is selected from the group consisting of a monovalent organic group represented by the following general formula (3) and a divalent organic group represented by the following general formula (4) in one molecule. Selected from the group consisting of one or more 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 one or more monovalent and / or divalent organic groups (F1), wherein the weight fraction of the organic groups (D2) in the molecule (WD2 (%)) and (F
The compound whose weight fraction (WF1 (%)) of 1) satisfies the following formulas (1) and (2). 40 ≦ (WD2 + WF1) ≦ 70 Equation (1) 0.6 ≦ (WD2 ÷ WF1) ≦ 3 Equation (2)

[0016]

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[In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. R2 represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ]

[0018]

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[In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. ]

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

[0021]

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[In the above general formula, R is a group having 1 to 4 carbon atoms.
Represents an alkyl group. R3 represents a hydrogen atom or a methyl group. R4 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. X1 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):

[0024]

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[In the above formula, R5 represents a hydrogen atom or a methyl group. R6 represents a cycloalkyl group having 5 to 10 carbon atoms. Y1 represents an -O- group or an -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: Component (D
3) and the weight fraction of component (F2) is expressed by the following formula (7):
It is a hindered amine compound satisfying (8). 80 ≦ (WD3 + WF2) ≦ 100 Equation (7) 0.5 ≦ (WD3 ÷ WF2) ≦ 2.3 Equation (8) [wherein WD3 is a weight fraction (%) of the component (D3);
WF2 represents a weight fraction (%) of the component (F2).] Further, a preferred hindered amine compound is represented by the following general formula (7)

[0026]

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[In the above formula, R represents an alkyl group having 1 to 4 carbon atoms. R7 and R8 represent either a hydrogen atom or a methyl group. R9 represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. X and Y represent either -O- groups or -NH- groups. n and m are 0.35 ≦ (n / m) ≦ 1.7
A positive number such that the number is 5). In a further preferred embodiment,
The polyurethane elastic yarn is further blended with a phenolic antioxidant and a phosphite antioxidant,
Further, the phenolic antioxidant compounded in the polyurethane elastic yarn is a phenolic antioxidant represented by the following general formula (8),

[0028]

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[In the above general formula, R10 is a t-butyl group, s
represents a group selected from an ec-butyl group and a neobentyl group. And a phosphite-based antioxidant represented by the following formula (9):
Including the structure represented by

[0030]

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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 amount of the phosphite ester antioxidant is 0.1 to 2% by weight, and (c) the amount of the hindered amine compound is 0.5 to 5% by weight.

The polyurethane elastic yarn used in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of polyurethane.

As the polyurethane, known polyurethanes such as polyether type, polyester type and polycarbonate type can be mentioned. 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 weight 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 present invention, the monovalent and / or divalent organic group (D1) is a monovalent organic group represented by the general formula (1) and a divalent organic group represented by the general formula (2). And one or more monovalent and / or divalent organic groups selected from the group consisting of: When the organic group (D1) is a monovalent organic group, when the organic group (D1) has 4
It is preferable that the compound is bonded at the position to another site in the compound. R1 in the above general formula (1) is any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. More preferred. Further, when the organic group (D1) is a divalent organic group, it is preferable that the organic group (D1) is bonded to other positions 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 (10).
(12);

[0039]

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[0040]

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[0041]

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Examples of the group include: These organic groups are in the range defined as above,
It may consist of only one kind of organic group or may consist of a mixture of two or more kinds of organic groups. 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). The number of organic groups (D1) per kg of the hindered amine compound is 1.3 mol
1 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.
As the number of organic groups (D1) is smaller, the amount of the hindered amine compound must be increased to obtain the same effect, which is economically disadvantageous. As the number of organic groups (D1) per kg of the hindered amine compound,
2.0 mol or more is more preferable in terms of the 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: BA = V × F × 10−2 ÷ 0.0200 Formula (9) [In the above formula, BA is the amount of base (eq / kg) per kg of the hindered amine compound, and V is 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 l of pure water using a measuring 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. wA = (5 × 10−2) ÷ BA Equation (10) [wherein wA represents the weight (g) of the hindered amine compound, and BA represents the amount of base (eq / kg) per kg of the hindered amine compound. ]

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 the ampoule filtered with a 0.45 μm filter 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). SA = (VS−VB) ÷ 300 Equation (11) [wherein SA represents the solubility (eq / l) of the hindered amine compound in an acidic solution, and VS represents the sample solution 3
ml, titration (ml) of VB, titration (ml) of 3 ml of blank solution, BA: 1 k of hindered amine compound
The amount of base per gram (eq / kg) is shown. ]

In the hindered amine compound of the present invention, the solubility in the acidic solution determined as described above needs to be 5.0 × 10 ⁻³ eq / l or less. The smaller the solubility, the better, but 2.5 × 10 ^-3 e
If it is not more than q / l, more preferable characteristics are exhibited.

The organic group (D2) of the hindered amine compound in the present invention is a group consisting of a monovalent organic group represented by the general formula (3) and a divalent organic group represented by the general formula (4). One or more monovalent and / or divalent organic groups selected from the above. 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, and among them, a hydrogen atom or a methyl group is more preferable from the viewpoint of stabilizing effect. When the organic group (D2) 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 (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 in the present invention is one kind 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. Or two or more monovalent and / or divalent organic groups. 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 small, and as a result, the effect is small, 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. Organic group (F1)
May be the same group, or may consist of two or more groups. As an example of the organic group (F1), the following general formula (1)
3) to (22);

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[In the above general formulas (13) to (22), Z is a hydrogen atom, a linear or branched saturated alkyl group having 1 to 5 carbon atoms, or a bond to another site in the hindered amine compound. Represents any of the sites. 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 of the present invention is a compound having one or more organic groups (D2) and (F1) in the molecule. The sum of the weight fraction of the organic group (D2) and the weight fraction of the organic group (F1) in the hindered amine compound needs 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) needs to be between 0.6 and 3. If it is smaller than 0.6, the stabilizing effect before processing is small, and if it is larger than 3, the stabilizing effect after various processing is lost. More preferred ranges are:
The range is from 0 to 2.5. Organic groups (D2) and (F1)
Is expressed as a percentage of the total molecular weight of each organic group relative 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 in 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) and the above general formula (6) The polymerizable monomer component (F) of one or a mixture of two or more selected from the group represented by
2) is a hindered amine compound obtained by copolymerizing as an essential component, component (D3) and component (F2)
And the ratio of the weight fraction of component (D3) to the weight fraction of component (F2) is between 0.5 and 2.3. It is necessary to fulfill all of the things. 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 the quantification include, but are not limited to, quantification of each component by 1H-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. R4 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. X1 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 R3, R4 and X1 may be mixed with a different group, or each may be a single group. The most preferred combination is R
3 is a methyl group, R4 is a hydrogen atom, and X1 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.

R5 in the general formula (6) is a hydrogen atom or a methyl group, and more preferably a methyl group. R6 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 small, and as a result, the effect is small, 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 R6, 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. The number of alkyl groups as a substituent in the cycloalkyl group is not particularly limited, but the total number of carbon atoms is 5
It is essential that the number be from 10 to 10. A cycloalkyl group is
It is preferable that it is 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 X2 in R6 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 R6
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. Y1 in the above general formula (6) is an -O- group or an -NH- group, and more preferably an -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 R5, R6, and Y1 is mixed with a different group. Or all may be a single group. The most preferred combination is where R5 is a methyl group, R6 is a cyclohexyl group, and Y1 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 present invention, the polymerizable hindered amine compound monomer component (D3) and the polymerizable monomer component (F
The most preferred combinations of 2) are 2, 2, respectively.
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 compounds as raw materials. 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 phosphite 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 Mix with 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 additives such as flame retardants and fungicides Can also be 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 for spinning are not particularly limited, and any known method can be selected depending on the resin composition, application, purpose, yarn properties, and the like. 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 blended in an amount sufficient to exert a 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 yarn 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 components other than the 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 typical examples thereof include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. I can do it.

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, 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. .

Further, there is no particular limitation as long as it is an inelastic yarn 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 a bare (bare) yarn, a single covering yarn, a double covering, an air covering yarn, a core spun yarn,
Used in the state of composite elastic yarn such as pliers.

The brassiere to be used in the present invention is a brassier made of a stretchable knitted fabric comprising the polyurethane elastic yarn and the inelastic fibers such as the polyester-based fibers, polyamide-based fibers, and cellulosic fibers. The knitting is a flat knit, a double-sided knit, a rib knit, a pearl knit or a change knitted fabric thereof, and the warp knitting is a tricot knitted fabric or a Russell knitted fabric, and is not particularly limited. As for the knitting structure, in case of tricot knitted fabric, half knitting, reverse half knitting, double denby knitting,
In double atlas knitting and Russell knitting, a power net, a half power net, a satin net, a triconet and the like can be exemplified.

[0087]

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 knitted fabric for evaluation was dried at 500 ml / dry air containing 200 ppm of NO2 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 1 min. After exposure, J
The buffered urea solution described in IS-L0855, followed by thorough washing with pure water, drying for 24 hours under a nitrogen stream, and color meter TC1500MC-88 (Tokyo Denshoku Co., Ltd.)
The b value in the Hunter Lab color system is measured for an eight-layer stretchable knitted fabric for evaluation using 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 inlet 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 1H-NMR spectrum of the obtained hindered amine compound was measured using DMSO-d6
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.

(Production Example 1 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. To 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 defoamed, air heated to 230 ° C. was extruded from a die having a fine pore diameter into a spinning tube in which air was flown, and a polyurethane elastic yarn was obtained by so-called dry spinning into a fibrous form.

(Production Example 2 of Polyurethane Elastic Yarn) In the spinning solution obtained 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 for Production of Polyurethane Elastic Yarn) All of the above-mentioned examples were carried out except that the hindered amine compound obtained in the Comparative Synthesis Example was replaced with 13.42 parts of the hindered amine compound obtained in the Example Synthesis Example. 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 CORPORATION) was prepared by combining 310 dtex of polyurethane elastic yarn obtained in Example 1 described above with 78 dtex-24 filament of nylon 6.
/ 130 inch width / 28 gauge) using 6 courses /
The fabric of the power net organization was knitted. This fabric was subjected to a usual dyeing finish process known to those skilled in the art to obtain a fabric having a density of 53 courses / inch and a lateral density of 33 wales / inch. A brassiere was prepared using the cloth for the wing.

Example 2 A Russell knitting machine (RSE-4N, manufactured by KARL MAYER CO., LTD.) Was used by combining the 235 dtex yarn of polyurethane elastic yarn obtained in Example 1 and 55 dtex-12 filament of nylon 6.
/ 130 inch width / 28 gauge), and knitted a 6-course power net fabric. This fabric is dyed and finished with a warp density of 68 courses / inch and a lateral density of 40 wales
I got an inch of dough. In the same manner as in Example 1, a brassiere using the cloth for the wing was produced.

(Comparative Examples 1-2) Knitting was carried out using the same yarn combination, knitting machine and knitting structure as in Examples 1-2 except that the polyurethane elastic yarn obtained in the above Comparative Production Example was used. Fabrics obtained by dyeing and finishing with the same properties as Examples 1 and 2 are Comparative Examples 1 and 2. In the same manner as in Example 1, a brassiere using the cloth for the wing was produced. The NOx discoloration test described above was performed on the wing portions of the brassiere of Examples 1 and 2 and Comparative Examples 1 and 2, b values before and after NOx treatment were measured, and discoloration Δb values were compared. Table 2 shows the results. Regardless of the organization,
The value is smaller than the Δb value of the comparative example, and it is hard to change color and is stable.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

The brassiere according to the present invention has a nitrogen oxide (N
It is sufficiently stabilized against discoloration deterioration due to Ox), and a good stabilizing effect is maintained even after secondary processing such as dyeing finish processing.

Continued on the front page F-term (reference) 3B029 HA02 HB00 4L002 AA01 AA06 AA07 AC01 CA01 EA05 FA03 4L035 EE07 GG03 JJ16 JJ21 JJ25

Claims (10)

[Claims] 1. A bra comprising at least a part of a stretchable knitted fabric comprising a polyurethane elastic yarn containing a non-stretchable fiber and a hindered amine compound. 2. The brassiere according to claim 1, wherein the non-stretchable fibers are at least one fiber selected from polyester fibers, polyamide fibers and cellulosic fibers. 3. The hindered amine compound is selected from the group consisting of a monovalent organic group represented by the following general formula (1) and a divalent organic group represented by the following general formula (2) in one molecule. One or more monovalent and / or divalent organic groups (D
1) a hindered amine compound having at least one organic group (D) per 1 kg of the hindered amine compound.
3. The brassiere according to claim 1, wherein the number 1) is 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. 4. Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R1 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. ] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. ] 4. The hindered amine compound is selected from the group consisting of a monovalent organic group represented by the following general formula (3) and a divalent organic group represented by the following general formula (4) in one molecule. One or more monovalent and / or divalent organic groups (D
2) and one or more monovalent and / or divalent organic groups (F) selected from the group consisting of cycloalkyl groups having 5 to 10 carbon atoms and cycloalkylene groups having 5 to 10 carbon atoms
1) a compound having the organic group (D2)
Weight fraction (WD2 (%)) and (F1) weight fraction (W
The brassiere according to any one of claims 1 to 3, wherein F1 (%) is a compound satisfying the following formulas (1) and (2). 40 ≦ (WD2 + WF1) ≦ 70 Equation (1) 0.6 ≦ (WD2 ÷ WF1) ≦ 3 Equation (2) [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R2 represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. ] 5. A radically polymerizable hindered amine derivative monomer component (D3) comprising one or a mixture of two or more hindered amine compounds selected from the group represented by the following general formula (5): A hindered amine compound obtained by radical copolymerization of one or more mixtures of radically polymerizable monomer components (F2) selected from the group represented by the following formula, and a component of the hindered amine compound: The brassiere according to any one of claims 1 to 4, wherein the weight fraction of (D3) and the component (F2) is a compound satisfying the following formulas (3) and (4). Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R3 represents a hydrogen atom or a methyl group. R4 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. X1 represents a -O- group or a -NH- group. ] [In the above general formula, R5 represents a hydrogen atom or a methyl group. R6 represents a cycloalkyl group having 5 to 10 carbon atoms. Y1 represents an -O- group or an -NH- group. 80 ≦ (WD3 + WF2) ≦ 100 Equation (3) 0.5 ≦ (WD3 ÷ WF2) ≦ 2.3 Equation (4) [wherein WD3 is the weight fraction (%) of the component (D3);
WF2 represents the weight fraction (%) of the component (F2)] 6. The hindered amine compound has a structure represented by the following general formula (7).
A brassiere according to any one of claims 1 to 5. Embedded image [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R7 and R8 represent either a hydrogen atom or a methyl group. R9 represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 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 brassiere according to claim 1, wherein the polyurethane elastic yarn contains a phenolic antioxidant and a phosphite ester antioxidant. 8. The phenolic antioxidant is a phenolic antioxidant represented by the following general formula (8), and the phosphite ester antioxidant is represented by the following formula (9). The brassiere according to claim 7, which is a hydrogenated bisphenol A pentaerythritol phosphite polymer having a structure. Embedded image [In the above general formula, R10 represents a group selected from a t-butyl group, a sec-butyl group, and a neobentyl group. ] 9. The polyurethane elastic yarn according to claim 1, wherein the blending amount of the phenolic antioxidant with respect to (a) polyurethane is 0.1 to 10%.
2.0% by weight, (b) the amount of the phosphite ester antioxidant is 0.1 to 2% by weight, and the amount of the hindered amine compound is 0.5 to 5% by weight. The brassiere according to claim 7 or 8. 10. The brassiere according to claim 1, wherein the polyurethane elastic yarn is knitted as a bare (naked) yarn or a composite elastic yarn thereof.