JP2003171857A - Elastic warp knitted fabric with excellent resistance to complex embrittlement - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane elastic yarn satisfying an acceptable quality level set based on an evaluation method for an elastic warp knit fabric using a polyurethane elastic yarn, prepared by assuming the use of a consumer such as repeating wearing, washing, drying in the sun and chlorine bleaching. <P>SOLUTION: The level acceptable by the consumer is set by providing the method for testing complex embrittlement by assuming the wearing, the washing, the drying in the sun, and the chlorine bleaching. (a) A phenol-based antioxidant, (b) a phosphite-based antioxidant and (c) a hindered amine compound having a specific structure are compounded with the polyurethane elastic yarn used in an elastic woven or knitted fabric to satisfy the level. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stretchable warp knitted fabric composed of non-stretchable fibers such as polyester fibers, polyamide fibers and cellulosic fibers and polyurethane elastic yarn. More specifically, the present invention relates to a stretchable warp knitted fabric which does not easily become brittle even after repeated washing, bleaching, sun-drying, and wearing when it is used as clothes and the like and which maintains a suitable kickback property for a long period of time.

[0002]

2. Description of the Related Art As an elastic warp knitted fabric composed of non-stretchable fibers such as polyester fibers, polyamide fibers, cellulosic fibers and polyurethane elastic fibers, a polyurethane elastic yarn having a relatively large fineness is knitted with an insertion structure. Russell knitted fabric and tricot fabric made by knitting polyurethane fibers with a relatively fineness in a knit structure have excellent stretchability, so they have foundations and underwear for bras, girdles, bodysuits, swimwear and leotards, It is used in a wide variety of applications such as sports clothing such as skiing and skating racing suits, stretch bandages, medical applications such as stretchable corsets and supporters, and stretch boot base fabrics.

Polyurethane elastic yarns generally used for the above-mentioned applications are often produced from polyisocyanates and polyfunctional active hydrogen compounds having a relatively low molecular weight. Among them, polyurethane elastic yarns obtained from aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate as polyisocyanates are widely used because they have particularly excellent mechanical properties. However, if warp knitted fabric is used with this composition, repeated stretching and washing /
Embrittlement may occur in which the yarn deteriorates due to sun drying and bleaching and the stretchability is impaired. It has been studied for a long time to add a stabilizer or an antioxidant to the yarn for the purpose of improving this phenomenon. For example, phosphite-based antioxidants, aliphatic amine derivatives and hydrazine derivatives are known. However, it is said that the stretchability of the product was impaired when it was repeatedly worn, washed, dried and dried, and repeatedly bleached despite using such polyurethane elastic yarn with stabilizers and antioxidants added. There have been occasional cases of consumer complaints.

[0004]

The present invention has been earnestly studied in view of such circumstances, and is intended for use in products using stretchable warp knitted fabric in which polyurethane elastic yarns are knitted, worn, washed, sun-dried and bleached. The object is to provide a polyurethane elastic yarn which can set an acceptable quality level even after repetition of the above and eliminate this.

[0005]

[Means for Solving the Problems] As a result of diligent studies, the present inventor has conducted a test and chlorine bleaching on a stretchable warp knitted fabric in which polyurethane elastic yarns have been knitted Drying in the sun: ・ Tests that assume expansion and contraction when worn are repeated, and it is found that if the stress retention rate after a certain cycle has a certain level, the demands of the majority of consumers can be tolerated. It has been found that the performance can be significantly improved by adding a specific compound to the polyurethane elastic yarn, and the present invention has been completed.

[0006] That is, the present invention is a stretchable warp knitted fabric composed of non-stretchable fibers and polyurethane elastic yarn, and stress retention after 50 cycles of a combined washing test assuming home washing, sun drying and wearing. A stretchable warp knitted fabric excellent in washing compound embrittlement characterized by having a rate of 60% or more and / or chlorine bleaching / sun-drying and chlorine compound embrittlement test assuming wearing and repeating 30 cycles. A stretchable warp knitted fabric excellent in chlorine compound embrittlement characterized by having a stress retention rate of 50% or more, wherein the polyurethane elastic yarn contained in the stretchable warp knitted fabric is a, phenol-based. The composition contains an antioxidant, b, a phosphite-based antioxidant, and c, a hindered amine compound.

The hindered amine compound blended in the polyurethane elastic yarn contains a monovalent organic group represented by the following general formula (1) in one molecule and

[Chemical 10] [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. ]

The following general formula (2)

[Chemical 11] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. ]
A hindered amine compound having at least one monovalent and / or two or more monovalent and / or divalent organic groups (D1) selected from the group consisting of divalent organic groups represented by: Is a hindered amine compound having a number of organic groups (D1) of 1.3 mol or more and a solubility in an acidic solution of 5.0 × 10 −3 eq / l or less.

Further, a preferable hindered amine compound is
Represented by the following general formula (3) in one molecule

[Chemical 12] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ² 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. ] Represented by a monovalent organic group and the following general formula (4),

[0010]

[Chemical 13] [In the above general formula, R represents an alkyl group having 1 to 3 carbon atoms. ] One or two selected from the group consisting of divalent organic groups
One or more monovalent and / or divalent organic group (D2), a saturated cycloalkyl group having 5 to 10 carbon atoms, and 5 carbon atoms
1 or 2 or more monovalent and / or divalent organic groups selected from the group consisting of 10 saturated cycloalkylene groups (F
A compound having 1), which is an organic compound (D2) in the molecule
And (F1) are hindered amine compounds satisfying the following numerical formulas (6) and (7). 40 ≦ (W _D2 + W _F1) ≦ 70 Formula (6) 0.6 ≦ (W _D2 ÷ W _F1 ) ≦ 3 Formula (7)

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

[Chemical 14] [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 of the alkoxy groups. X1 represents an -O- group or an -NH- group. ] The 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: and the following general formula (6)

[0012]

[Chemical 15] [In the above general formula, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a saturated cycloalkyl group having 5 to 10 carbon atoms. Y ¹ represents a -O- group or a -NH- group. ] A hindered amine compound obtained by radical copolymerization with a radically polymerizable monomer component (F2) of one kind or a mixture of two or more kinds selected from the group represented by: A hindered amine compound in which the weight fractions of the component (D3) and the component (F2) satisfy the following formulas (8) and (9) may be used. 80 ≦ (W _D3 + W _F2 ) ≦ 100 Formula (8) 0.5 ≦ (W _D3 ÷ W _F2 ) ≦ 2.3 Formula (9) [W _D3 is the weight% of the component (D3), W _F2 represents the weight% of the component (F2)]

[0013] Further more preferred hindered amine compound
May be a structure represented by the following general formula (7).

[Chemical 16] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ^{8 each} represent a hydrogen atom or a methyl group. R ⁹ represents any of 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- group or -NH- group. n and m represent positive numbers such that 0.35 ≦ (n / m) ≦ 1.75]

The phenolic antioxidant blended in the polyurethane elastic yarn is a phenolic antioxidant represented by the following general formula (8).

[Chemical 17] [In the above general formula, R10 represents a group selected from a t-butyl group, a sec-butyl group, and a neobentyl group. ]

The phosphite type antioxidant is
A hydrogenated bisphenol A / pentaerythritol phosphato polymer having a structure represented by the following formula (9).

[Chemical 18] In the polyurethane elastic yarn, the compounding amount of the phenolic antioxidant with respect to (a) polyurethane is 0.1 to 2.
0% by weight, (b) the content of the phosphite antioxidant is 0.1 to 2% by weight, and (c) the content of the hindered amine compound is 0.5 to 5% by weight.

An elastic warp knitted fabric in which the polyurethane elastic yarn is knitted in the state of a bare yarn or a composite elastic yarn,
It is a Russell fabric knitted with an insertion structure or a tricot fabric knitted with a knit structure.

The stress retention rate is expressed by the following equation (equation (5)). Tn ÷ T0 × 100 (%) Formula (5) Here, T0 and Tn are widths of 2 with an Instron type tensile tester.
80% of the test piece set to 5 mm and the tension interval of 100 mm
The value of the extension stress at the third time when the extension three times repeated test is conducted. T0 is an untreated test piece, and Tn is a combined embrittlement test (washing, chlorine) after repeating the cycle for n cycles. It is a value.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the warp knitted fabric in which polyurethane elastic yarns are interwoven is suitable for sports clothing to expand and contract in accordance with the movement of the body, and for foundations, the body can be lightened with appropriate power. It retains a beautiful silhouette and holds the performance not seen in other materials. On the other hand, because it is a delicate material, the polyurethane elastic thread contained in the fabric gradually deteriorates due to the effects of sunlight (ultraviolet rays), moisture, and nitrogen oxide gas (NOx gas) during repeated washing and wearing It is also known that chlorine may deteriorate even at the disinfecting concentration contained in tap water.

In general, when a person sits on a chair or crouches down in daily life, the most stretched part is the buttocks, and it is said that the skin is stretched by about 40% by the above movement. It is said that more flexion or twisting is required during sports. Underwear and sports clothing worn in close contact with the skin are required to be stretched to some extent when worn, and to expand and contract following the movement of the skin. The present inventor has devised a test method in consideration of repeated expansion and contraction during wearing and exposure to ultraviolet light during washing and sun drying. That is, the following method was adopted as the laundry combined fragility test method in the present invention, which is assumed to be used for practical washing, sun drying, and stretching when worn.

(Washing test) A commercially available fully automatic washing machine (ES-S75 type fully automatic washing machine (spiral / instantaneous reversal method) manufactured by Sharp Corporation) is used. Connect the water supply hose to the water supply faucet that can switch between hot water and water. A high water level (52 liters) is filled with hot water at 50 ° C. to dissolve a commercially available neutral detergent powder at a rate of 1 gram / liter. A test piece is put into a commercially available washing net and washed with a strong water flow for 15 minutes. The test piece is fixed by sewing the four corners to the net. Drain after washing. Then three rinses are performed. 1
The first time was pool rinsing with warm water at the same temperature as when washing, rinsing with water after draining, and finally pool rinsing with water. When rinsing is complete, drain and drain (6 minutes).

(Experimental Drying Drying Test) Using a UV fade meter, keeping the temperature inside the apparatus at 63 ° C., the above washing test is completed, and a wet test piece is put in and a UV ray is used for 5 hours using a carbon arc as a light source. Irradiate. The surface to be irradiated at this time is a needle loop surface, and the portion that serves as a gripping margin of the chuck during the repeated expansion / contraction test and 80% elongation stress measurement test is shielded from the irradiation.

(Expansion / contraction test when worn) As described above, it is generally said that when a person sits on a chair or crouches, the skin grows by about 40%, and it is said that the skin further grows in sports and the like. Shorts sewn using a two-weight ricott with spandex knitted are worn with a stretch of about 30%,
If this is performed as described above, as a result, it is stretched from the state of the dough to about twice. The test piece is repeatedly stretched and contracted assuming that the shorts were worn for one day and spent daily life. 100% expansion and contraction is repeated 7500 times using a Soviet-type expansion and contraction tester for the test piece after the sun-drying test. At this time, the repetition rate of expansion and contraction is 20 per minute.
0 times. This washing test → sun drying test → stretch test
Repeat 1 cycle for 50 cycles.

As a chlorine compound test method assuming chlorine bleaching, a round meter washing tester (JIS L0
821-1983 (according to the attached document), a test solution prepared by dissolving sodium hypochlorite to have an effective chlorine concentration of 10 ppm and adjusting the pH to 7.0 ± 0.2 has a bath ratio of 1; 100 to the test piece. In a pot for exclusive use of a round meter tester, the temperature is kept at 50 ° C ± 2 ° C so that 60
Drive for minutes. At this time, do not use stainless steel balls. 6
After 0 minutes, the test piece is taken out of the pot and drained with filter paper.

[0024] After that, an assumed sun-drying test and an expansion-contraction test when worn are conducted under the same conditions as those carried out in the above-mentioned laundry complex embrittlement test. Chlorine dip test → Expected sun-dry test → Expected elastic wear test is repeated for 30 cycles.

The stress retention rate referred to in the present invention is measured and calculated by the following method. Using an Instron type tensile tester, 25 mm (25 mm in fabric wale direction), 100 mm pulling length (100 mm in fabric course direction), chuck grip length 25 m
m sample is prepared and extension / recovery test up to 80% is performed 3 times. Draw the elongation / recovery curve at this time on the chart 3
Read the 80% elongation stress for the second time. The 80% elongation stress of the third time in the sample collected from the cloth before being subjected to the laundry complex embrittlement test and the chlorine complex embrittlement test is taken as an untreated value and is T0. Then, the third 80% elongation stress of the sample taken from the dough after the respective composite embrittlement test is performed is read. 5,10,20,30,4 for washing embrittlement test
Samples were taken at the end of 0,50 cycles, and the values of 80% elongation stress at the third time were taken as T5, T10, T2.
0, T30, T40, T50. When subjected to the chlorine compound brittleness test, samples are taken at the end of 5, 10 and 20 cycles, and the values of the 80% elongation stress at the third time are designated as T5, T10 and T20.

The stress retention rate at the end of n cycles is calculated by the following equation.
Calculation is performed as in (Equation (5)). Tn ÷ T0 * 100 (%) Formula (5) Here, Tn is the third 80% of the sample after the end of n cycles.
Elongation stress T0 is 80% elongation stress for the 3rd time of untreated sample

The present inventor tried to set a level acceptable as a consumer by a questionnaire survey from the stress retention rate and the number of cycles thus obtained. 20
Twenty women in the age range of 50 to 50 were compared with the stress retention rate to find out where there was a difference in the feel of the tricot fabric and the Russell fabric mixed with spandex. As a result, when the stress retention rate is 50% or less, a difference of 90% or more is felt by the monitor and the stress retention rate is 60%.
However, it was the monitors of 30% or less that felt the difference.
Next, a product life questionnaire was conducted on shorts and girdles in which spandex was mixed with the monitor. Although there were some differences depending on the age, there were many people who wanted it to be worn for about two years. Generally, even underwear has seasonality of spring / summer products and autumn / winter products, and if the same product is worn once a week, it is repeatedly worn and washed 50 times. From this result, the present inventor has set the allowable level in the washing composite embrittlement test assuming washing, sun-drying and wearing to be a stress retention rate of 60% or more after 50 cycles.

[0028] Although it is overwhelming that the product in which spandex is mixed is pictographed to the effect that chlorine bleaching is not possible, consumer grievances of embrittlement presumed to be due to chlorine bleaching occur. In some cases. As a level that can withstand this, the present inventor has set that the stress retention rate after 20 cycles in the chlorine composite embrittlement test is 50% or more.
The reason for this is that when chlorine bleaching is performed about once in three times of normal wearing / washing, it is judged to be an acceptable level if it has about 80% of the level of the above-mentioned laundry embrittlement test.

The polyurethane elastic yarn used in the present invention is an elastic fiber obtained by spinning a polymer composition mainly composed of polyurethane. Polyurethane is polyether type,
Known polyurethanes such as polyester type and polycarbonate type can be used. Such a polyurethane can be obtained by reacting a polyisocyanate, a polymer diol, and optionally 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, 2,6-tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate,
1,4-cyclocyclohexane diisocyanate, 4,4
One type of'-dicyclohexylmethane diisocyanate, xylylene diisocyanate, or the like, or a mixture thereof can be used. Among them, 4,4'- is preferable.
It is diphenylmethane diisocyanate. Polymer diols have hydroxyl groups at both ends and have a molecular weight of 600.
To 7,000 substantially linear polymers such as polyether polyols such as polytetota ethylene ether glycol, polypropylene ether glycol, polyethylene ether glycol, polypentamethylene ether glycol, adipic acid, sebacic acid, maleic acid,
One or more mixtures of dibasic acids such as itaconic acid, mazelaic acid, malonic acid, succinic acid, glutaric acid, suberic acid, dodecanedicarboxylic acid, β-methyladipic acid and hexahydroterephthalic acid, and ethylene glycol, Polyester polydiol obtained from one or a mixture of two or more glycols such as 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 1,4-dimerolcyclohexane. Alternatively, any polyol such as polyether ester diol, polylactone diol, and 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 extender). As the chain extender, for example, water, hydrazine, ethylenediamine, propylenediamine, xylylenediamine, polyamines such as diethylenetriamine, polyols such as ethylene glycol and butanediol, polyhydrazide, polysemicarbazide, polyhydroxylamine, etc. A mixture may be mentioned.

As a compound having only one active hydrogen in the molecule which can react with an isocyanate group in the molecule together with a chain extender as a terminal hand terminator, one or two dialkylamines such as diethylamine, dimethylamine and dibutylamine. Mention may be made of mixtures of more than one species. Polyurethane can be polymerized by a known method. Polymerization can be carried out by any method such as solution polymerization and melt polymerization, and combinations thereof. Further, an arbitrary method such as a one-shot method in which the raw materials are collectively mixed or a prepolymer method in which a prepolymer is first formed and chain extension is performed can be employed.

There is no particular limitation on spinning the polymerized polyurethane composition into elastic fibers, but it is preferable to dry spin the polyurethane composition solution. Components other than polyurethane constituting the polyurethane composition is (a) a phenolic antioxidant, (b) a phosphite-based antioxidant,
(c) In addition to the hindered amine compound, a leveling agent, a stabilizer such as an ultraviolet absorber, a pigment, an antistatic agent, a surface treatment agent, a flame retardant, a reinforcing agent, and a chlorine deterioration inhibitor can be used.

As the phenolic antioxidant, any known phenolic antioxidant can be used. An appropriate compound can be selected in consideration of solubility in a solvent, compatibility with polyurethane and the like. 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-
t-butyl-4-hydroxybenzyl) -isocyanurate, 3,9-bis {2- [3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-
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-bul-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-t-butyl-4-hydroxyphenyl)
Propionyl] hydrazine, a polycondensation product of p-chloromethylstyrene and P-cresol, a polycondensation product of p-chloromethylstyrene and dinylbenzene, an isobutylene reaction product of a polycondensation product of p-cresol and divinylbenzene, and the like. 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-t-butyl-3-hydroxy-2,6
Most preferred is dimethyl) isocyanuric acid. The phenolic antioxidant can be used by blending it with polyurethane in an amount such that deterioration can be sufficiently suppressed in actual use. Also, two or more phenolic antioxidants may be used in combination. The blending amount of the phenolic antioxidant is preferably 0.1 to 2% by weight with respect to the polyurethane.

As the phosphite type antioxidant,
Any known compound can be used. A suitable 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'-biphenylene phosphonite, trisnoniphenyl phosphite, tris (2,4-diphenyl). -T-butylphenyl) phosphite,
Distearyl pentaerythritol diphosphite,
Di (2.4-di-t-butylphenyl) -pentaerythril diphosphite, di (2,6-di-t-butyl-
4-Methylphenyl) -pentaerythril diphosphite, triphenylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, 4,4'-butylidene-bis (3-methyl-6-t)
-Butylphenyl-ditodecyl) phosphite, cyclic neopentane tetrayl (octadecyl phosphite), tris (mono and / or dinonylphenyl) phosphite, diisodecyl pentaerythritose 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, tetraphenyl tetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4,4'-isopropylidene diphenyldiphosphite, Tetraphenyl
Examples include dipropylene glycol diphosphite. Among them, hydrogenated bisphenol A / pentaerythritol phosphite polymer and hydrogenated bisphenol A / phosphite polymer are preferable. The phosphite-based antioxidant can be used by blending with polyurethane in an amount such that deterioration can be sufficiently suppressed in actual use. Further, two or more kinds of phosphorous acid type antioxidants may be used in combination. The blending amount of phosphite antioxidant is
It is preferably between 0.1 and 2% by weight with respect to the polyurethane.

In the fourth aspect of the present invention, the monovalent and / or divalent organic group (D1) is represented by the monovalent organic group represented by the general formula (1) and the general formula (2). And a monovalent and / or divalent organic group selected from the group consisting of divalent organic groups. When the organic group (D1) is a monovalent organic group, it is preferably bonded to another site in the compound at the 4-position of the piperidine ring in the general formula (1). R1 in the general formula (1) is
Hydrogen atom, alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms
Any of the 10 alkoxy groups, and among them, a hydrogen atom or a methyl group is more preferable from the viewpoint of the stabilizing effect. Further, when the organic group (D1) is a divalent organic group, it is preferable that the organic group (D1) is bonded to other sites in the compound at the 1-position and 4-position of the piperidine ring in the general formula (2). As a preferable example of the organic group (D1), the following structural formula (10) to
(12);

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21] The group represented by can be mentioned. These organic groups may be composed of only one kind of organic group or a mixture of two or more kinds of organic groups as long as they are in the ranges defined 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) is an organic group represented by the general formula (12). Hindered amine compound 1kg
The number of organic groups (D1) per unit needs to be 1.3 mol or more. If the number of organic groups (D1) is smaller than this, the number of effective sites that contribute to stabilization in the compound decreases, and the stabilization effect is lost. Organic group (D
The smaller the number of 1), the larger the amount of the hindered amine compound added to obtain the same effect, which is economically disadvantageous. Hindered amine compound 1k
As the number of organic groups (D1) per g, 2.0 mol
The above 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 1 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, it may be weighed after separating the hindered amine compound from the solution once, or by weighing the solution amount such that the weight of the hindered amine compound becomes a predetermined amount as a solution. Good. As a method for separating the hindered amine compound, any known method such as reprecipitation, recrystallization, or evaporation of the solvent can be used. The weighed hindered amine compound is dissolved in 100 ml of the solvent. The solvent used is preferably one that dissolves the hindered amine compound well, does not exhibit basicity, 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 applied to a glass electrode (GE-101 / Hiranuma Sangyo Co., Ltd.) and a reference electrode (R) by using a potentiometric titration device (COMMITTE-980 / Hiranuma Sangyo Co., Ltd.) with a 1/100 N hydrochloric acid aqueous solution.
Neutralization titration using E-101 / Hiranuma Sangyo Co., Ltd.). The end point in the titration curve is the titer. The amount of base per 1 kg of the hindered amine compound is calculated by the following mathematical formula (1
0) can be obtained. BA = V × F × 10 −2 ÷ 0.0200 Formula (10) [In the above formula, B A is the base amount (eq / kg) per 1 kg of the hindered amine compound, and V is the titer (ml).
And F represents the factor of 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 base amount per 1 kg of the hindered amine compound, the total base amount is 5.0 × 10 -5 based on the sample weight for the solubility test.
It is calculated by the following mathematical expression (11) so that it becomes mol. wA = (5 × 10 −2) ÷ BA Equation (11) [In the above equation, wA represents the weight (g) of the hindered amine compound, and BA represents the amount of base (eq / kg) per 1 kg of the hindered amine compound. ]

The weight of the hindered amine compound determined by the above mathematical formula (11) 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, cooled, and then opened. 3 ml of the solution in the ampoule filtered with a filter having a pore size of 0.45 μm and 1 ml of a 1 / 10N sodium hydroxide aqueous solution are dissolved in 100 ml of a solvent. As the solvent to be used, the same solvent as used in the above-mentioned measurement of the amount of base can be used. The mixed solution is neutralized and titrated with a 1/100 N hydrochloric acid aqueous solution using a potentiometric titrator. As a blank, acetic acid 3.6.times.10@-3 g, anhydrous sodium acetate 0.
3 ml of distilled water containing 75 × 10 −3 g and 1 ml of a 1 / 10N sodium hydroxide aqueous solution are dissolved in 100 ml of a solvent, and titrated in the same manner. In the titration, the end point is the point where all the bases (hindered amine compound, sodium acetate, and sodium hydroxide) in the liquid to be titrated are all titrated.
Obtain the titer. The solubility of the hindered amine compound in the acidic solution is determined by the following numerical formula (12) from the titer of the sample solution and the blank solution as the amount of the base dissolved per 1 l (1 liter) of the acidic solution. SA = (VS-VB) / 300 Equation (12) [In the above equation, SA is the solubility (eq / l) of the hindered amine compound in an acidic solution, and VS is the sample solution 3).
ml titer (ml), VB the blank solution 3 ml titer (ml), BA hindered amine compound 1k
The amount of base per gram (eq / kg) is shown. ]

In the hindered amine compound according to the third aspect of the present invention, the solubility in the acidic solution obtained as described above needs to be 5.0 × 10 -3 eq / l or less. Lower solubility is preferable, but 2.5x
When it is 10 -3 eq / l or less, more preferable properties are exhibited.

The organic group (D2) of the hindered amine compound according to claim 5 of the present invention is a monovalent organic group represented by the general formula (3) or a divalent organic group represented by the general formula (4). 1 or 2 or more 1 selected from the group consisting of groups
It is a valent and / or divalent organic group. In the general formula (3), R2 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 preferable from the viewpoint of the stabilizing effect. Further, when the organic group (D2) is a divalent organic group, it is preferable that the organic group (D2) is bonded to other sites 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 structural formulas (10) to (12). These organic groups may be composed of only one kind of organic group or a mixture of two or more kinds of organic groups as long as they are in the ranges defined 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) consists only of the organic group represented by the structural formula (12).

The organic group (F1) of the hindered amine compound according to claim 5 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. It is one or more selected 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 of the groups is small, and as a result, the effect becomes 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 ring in which a plurality of carbon atoms are covalently bonded to each other and closed. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. Further, in the cycloalkyl group, the number of carbon atoms forming a ring may be 3 or more, but 5 or 6 is more preferable. 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 it is essential that the total number of carbon atoms is 5 to 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable that all the cycloalkyl groups are composed of covalent bonds and do not contain unsaturated bonds such as double bonds and triple bonds from the viewpoint of the stabilizing effect. The organic groups (F1) may be the same group or may be composed of two or more kinds of groups. As examples of the organic group (F1), the following general formulas (13) to (22);

[0044]

[Chemical formula 22]

[0045]

[Chemical formula 23]

[0046]

[Chemical formula 24]

[0047]

[Chemical 25]

[0048]

[Chemical formula 26]

[0049]

[Chemical 27]

[0050]

[Chemical 28]

[0051]

[Chemical 29]

[0052]

[Chemical 30]

[0053]

[Chemical 31] [In the 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 binding site with 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 binding sites with other sites in the hindered amine compound in Z is 1 or 2. ] The group etc. which are represented by these can be mentioned. 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 like, and most preferred are cyclohexyl group and isobornyl group. It is a base.

The hindered amine compound according to claim 5 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
It is necessary that the sum of the weight fractions of is in the range of 40 to 70% by weight. If it is less than the above range, the stabilizing effect becomes small and a large amount of stabilizer is required to be added, which is economically disadvantageous. If it is more than this, the stabilizing effect before various processing is relatively improved, but the stabilizing effect after various processing is lost. A more preferable range is 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 processing is lost. A more preferable range is 1.0 to 2.5. The weight fraction of the organic groups (D2) and (F1) is expressed as the 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 repeating unit can be calculated.

The hindered amine compound in claim 6 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), and the above general compound. A hindered amine compound obtained by copolymerizing, as an essential component, a polymerizable monomer component (F2) of one kind or a mixture of two or more kinds selected from the group represented by formula (6), and a component (D3 ) And the weight fraction of the component (F2) is between 80 and 100% by weight, and the component (D) relative to the weight fraction of the component (F2).
It is necessary that the ratio of the weight fractions of 3) is between 0.5 and 2.3. 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 polymers.

Examples of quantification include, but are not limited to, quantification of each component by 1 H-NMR, quantification of hindered amine component by neutralization titration, and the like. Further, when it is difficult to quantify from the hindered amine compound, the weight% of the charged various components may be used instead. When 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 processing cannot be well expressed in good balance. A more preferred range is 95 to 100% by weight. In addition, the component (D
If the ratio of the weight fraction of 3) is less than 0.3, the stabilizing effect before processing becomes small, and if the stabilizing effect is to be obtained sufficiently, the compounding amount must be increased, and economically. Is also a disadvantage. On the other hand, when it is more than 2.3, the stabilizing effect before processing is sufficiently obtained, but the stabilizing effect after various processing is not obtained. Especially, it is especially preferable that it is in the range of 1.0 to 1.6.

R3 in the above general formula (5) is a hydrogen atom or a methyl group, 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 alkoxy groups, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is the most preferable from the viewpoint of the stabilizing effect. X1 in the general formula (5) is -O-.
Group or -NH- group, more preferably -O- group. Polymerizable hindered amine compound monomer component (D
3) is 1 selected from the group represented by the above general formula (5).
It is a single kind or a mixture of two or more kinds, and R3, R4, and X1 may be mixed in different groups, or each may be a single group. The most preferable 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 within the range of the compounds defined as above can be mixed at an arbitrary composition ratio and used. Above all, 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, more preferably a methyl group. R6 is
It 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 of the groups is small, and as a result, the effect becomes 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 ring in which a plurality of carbon atoms are covalently bonded to each other and closed. In a cycloalkyl group, when two or more rings are present in the same group, each ring may share some carbon atoms. Further, in R6, the number of carbon atoms forming a ring may be 3 or more, but 5 or 6 is more preferable. 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 to
It is indispensable to be 10. The cycloalkyl group is preferably composed of only carbon atoms and hydrogen atoms. It is preferable that all the cycloalkyl groups are composed of covalent bonds and do not contain unsaturated bonds such as double bonds and triple bonds from the viewpoint of the stabilizing effect. The bonding site with X2 in R6 may be either a carbon atom on the cycloalkyl group or an alkyl group existing as a substituent of the cycloalkyl group. As a specific example of R6, the general formula (13) described above is used.
To groups (22) and the like can be mentioned. Among them, preferable groups 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 general formula (6) is a -O- group or a -NH- group, and a -O- group is more preferable. The polymerizable monomer component (F2) is one kind or a mixture of two or more kinds selected from the group represented by the above general formula (6), and each of R5, R6 and Y1 is mixed with different groups. Or all may be a single group. The most preferable combination is when R5 is a methyl group, R6 is a cyclohexyl group, and Y1 is an -O- group.
As a preferred example of the polymerizable monomer component (F2),
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,
Mention may be made of N-cyclononyl-acrylamide, N-cyclodecyl-acrylamide, N-decahydronaphthyl-acrylamide, N-norbornyl-acrylamide, N-bornyl-acrylamide, N-isobornyl-acrylamide. Particularly preferred examples are cyclohexyl methacrylate, cyclohexyl acrylate,
Examples include isobornyl methacrylate and isobornyl acrylate, and the 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, 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 polymers. As an example of quantification,
Examples include, but are not limited to, quantification of each component by 1H-NMR, quantification of hindered amine component by neutralization titration, and the like. Further, when it is difficult to quantify from the hindered amine compound, the weight% of the charged various components may be used instead.

The hindered amine compound of the present invention can be synthesized using the above-mentioned 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 within a range that does not impair the effect. Further, a known chain regulator may be added during the polymerization reaction, if necessary. The polymerization reaction can be carried out by any known method, but among them, the radical polymerization method is preferable, and moreover, since the reaction is simple and the reaction can be easily controlled, the raw material in a solvent in the presence of a radical polymerization initiator is used. A solution polymerization method of reacting is preferable. The polymerization solvent used is, for example, toluene, benzene, xylene,
Hydrocarbon solvents such as, ester 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, N,
N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, amide solvents such as hexamethylphosphonamide, diethyl ether, tetrahydrofuran, dioxane, ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and the like, Any solvent can be used as long as it is a solvent that does not react with radicals and dissolves the polymerizable monomer and the copolymer.

As the polymerization initiator to be used, those used as 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, 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 '-Azobisisobutyramide dihydrate, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 2,2'-azobis [N-
(2-Propenyl) -2-methylpropionamide],
Azo-based polymerization initiators such as 2,2'-azobis (2,4,4-trimethylpentane) are preferable. The concentration of the polymerizable monomer at the time of charging the polymerization is not particularly limited, but is 20
It is preferably between about 70% by weight. A solvent can be added at any time as the reaction progresses. The amount of the polymerization initiator 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 suitable. The polymerization initiator may be added to the system as it is, or may be dissolved in a polymerization solvent and added. Also, it may be added at once or divided into several times. If necessary, a known chain regulator may be added.

The reaction temperature is not particularly limited, but is 50 to 1
00 ° C is preferred. The reaction time is not particularly limited, but 1 to
It is preferably 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 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 a solution as it is, or can be used after being purified by an arbitrary method such as reprecipitation, evaporation of a solvent, or column chromatography. The molecular weight of the hindered amine compound in the present invention is not particularly limited, but it is 1000-
It is preferably between 500000. If it is less than 1000, the mobility in the resin is increased and bleeding out may occur. If it is larger than 500000, the physical properties of the resin may be adversely affected, and the stabilizing effect may be inferior as compared with the case where the molecular weight is small.
A more preferable molecular weight range is 2000 to 20000.
It is between 0. 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 part of the hindered amino group is composed of organic carboxylic acid, carbon dioxide gas, phosphoric acid compound, phosphoric acid ester compound, phosphorous acid compound, phosphorous acid ester compound. A salt may be formed with one or more compounds selected from the above. By forming a salt with all or part of the hindered amino groups of the hindered amine compound, the hindered amine compound can be adjusted in terms of basicity and solubility without impairing the inherent stabilizing effect of the hindered amine compound. be able to.

The organic carboxylic acid has 1 to 10 carbon atoms.
The organic carboxylic acid of 1 is preferable, and a saturated carboxylic acid is preferable. Also, 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 etc. can be mentioned.

The phosphoric acid compound means a phosphoric acid or a salt of phosphoric acid and a basic compound such as an amine or a metal ion. The phosphorous acid compound represents phosphorous acid or a salt of phosphorous acid and a basic compound such as an amine or a metal ion. The phosphoric acid ester compound is preferably a phosphoric acid monoester compound or a diester compound, but may be a polymer compound which is partially a phosphoric acid monoester or diester structure. As the phosphite compound, a phosphite monoester compound or a diester compound is preferable, but even a compound having a phosphite monoester or diester structure as a polymer compound Good. The phosphoric acid ester compound and the phosphorous acid ester compound may partially be a salt with a basic compound such as an amine or a metal ion.

The compounding timing 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 the fiber, it is compounded in the raw material. You can also
It can also be blended after the polymerization of the resin or the resin to be the fiber is completed. It is preferable to mix the resin after the completion of polymerization of the resin and before molding. Also, antioxidants such as phenol-based antioxidants, phosphite-based antioxidants, and thioether-based antioxidants, and UV rays such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers. Absorbents, metal deactivators such as 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-sticking agents such as ethylene, inorganic fine particles such as titanium dioxide, magnesium oxide, zinc oxide, hydrotalcite, barium sulfate, magnesium silicate, calcium silicate, etc., and known additives such as flame retardants and antifungal agents. It can also be added. When the fiber is blended with the fiber, when the fiber is spun by the melt method, the hindered amine compound of the present invention can be blended by melt-kneading the raw material resin. In the case of wet or dry spinning, the hindered amine compound of the present invention can be added as a single substance or as a solution to the stock solution for spinning. The spinning device and spinning conditions used during spinning are not particularly limited, and any known method can be selected depending on the resin composition, application, purpose, yarn physical properties and the like. The hindered amine compound of the present invention is particularly suitable as a stabilizer for fibers, especially polyurethane fibers. Further, among the polyurethane fibers, it is particularly suitable for polyurethane fibers 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 an amount sufficient to exhibit a stabilizing effect depending on the type and use of the resin or fiber. Although not particularly limited, it is preferably 0.05 to 10% by weight with respect to the fiber weight. In the case of polyurethane fiber,
In particular, it is particularly preferable that it is between 0.5 and 5% by weight.

In addition to the hindered amine compound of the present invention, it is preferable to blend a phenolic antioxidant and a phosphite antioxidant in the polyurethane elastic yarn. If a phenolic antioxidant is added, light and spinning
The durability against heat during processing is improved. Addition of a phosphite antioxidant can further improve NOx yellowing resistance.

The constituents other than polyurethane constituting the polyurethane composition are (a) a phenolic antioxidant,
In addition to (b) phosphite-based 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 deterioration. Examples thereof include inhibitors. Above all, in order to improve the light resistance, it is preferable to add an ultraviolet absorber such as a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber. As the ultraviolet absorber, any known compound can be used in a necessary amount according to need.

The polyester fiber used in the present invention is a polyester fiber known to those skilled in the art, and polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, etc. are known as typical examples. . Any shape, fineness and cross-sectional shape of filament, spun yarn, false twisted yarn and the like can be selected.

The polyamide fiber used in the present invention is a polyamide fiber known to those skilled in the art. Nylon 6, nylon 11, nylon 46, nylon 66
The following are typical examples, but these cationic dyeable knitted fabrics and polyamide / ester composite fibers may be used, and any shape, fineness, and cross section can be selected.

Further, the cellulosic fiber used in the present invention is cotton, rayon, hemp, or a mixed spun yarn of these with a polyester fiber, a composite yarn of nylon long fiber or ester long fiber, and any fineness can be selected. it can.

There is no limitation as long as it is a non-stretchable fiber such as animal hair fiber such as wool, cashmere and alpaca, silk, acrylic fiber, promix fiber and the like.

The polyurethane elastic yarn used in the present invention is usually in the form of bare yarn (bare yarn), or the polyurethane elastic yarn is used as a core yarn, and a non-stretchable fiber such as polyamide fiber or cotton yarn is wound around it in a single or double layer. Single-covered yarn or double-covered yarn that has been spun, air-covered yarn made by aligning polyurethane elastic yarn and non-stretchable yarn and entangled with high-pressure air, and core-spun yarn that combines polyurethane elastic yarn and roving yarn in the spinning process of spinning. Alternatively, it is used in the form of a composite elastic yarn such as plyarn in which a polyurethane elastic yarn is used as a core yarn and a spun yarn is double-twisted with a twisted yarn.

The stretchable warp knitted fabric referred to in the present invention means that at least two reeds are used, at least one reed is provided with the polyurethane elastic yarn, and at least one other reed is provided with the non-stretchable fiber. In a Russell knitted fabric, which is a warp knitted fabric arranged and knitted, in the case of a Russell knitted fabric, a power net structure, half power net structure, tulle net structure, satin net structure, tricho A net organization and these change organizations can be illustrated.

In the tricot knitted fabric, a half structure in which the polyurethane elastic yarn is knitted in a knit structure, an inverse half structure, a double Denby structure, a double atlas structure and a modified structure thereof can be exemplified.

EXAMPLES The present invention will be specifically described below with reference to examples. Of course, the present invention is not limited to these examples. The evaluation methods and test methods used in the present invention are 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 vacuum dried 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 titration.

(Home washing assumption test) Stretchable warp knitted fabric using polyurethane elastic yarn in wale direction (width direction)
A strip of dough with a length of 50 mm and a length of 200 mm in the course direction (length direction) is sampled. 50 mm above and below the strip of fabric
Tokuseki Kikai Kogyo Co., Ltd. K mark pen (E
Type) (yellow) and draw a marking line. The dough sample is placed in a commercial laundry net. At this time in the net
The four corners of the cloth are sewn and fixed to the laundry net using Tegs so that the cloth sample is spread. A commercially available fully automatic electric washing machine (ES-S75 type fully automatic electric washing machine manufactured by Sharp Corporation; spiral / instantaneous reversal method) is used to wash at a high water level (52 liters) and strong water flow. Install a water supply device that can switch between hot water and water.
As a detergent, a commercially available household neutral detergent (Kao High Top manufactured by Kao Corporation) is dissolved at a rate of 1 g / liter. Drain after washing for the set time (15 minutes). Then rinse 3 times. First rinse with warm water (50 ° C) similar to washing, after draining, second rinse with water, then drain, then third rinse with water, then drain and drain for 6 minutes. To do.

(Experimental Test for Drying in the Sun) A fabric sample that has undergone the above-mentioned washing test is taken out and 50 mm above and below so that only the marked 100 mm center portion is exposed.
Shield and stick on a white mount. At this time, make sure that the needle loop surface of the dough faces up. The fabric sample is irradiated with arc light using carbon as a light source using a long life ultraviolet ray fade meter manufactured by Suga Test Instruments Co., Ltd. (Keep the temperature inside the device at 63 ° C and perform irradiation for 5 hours.

(Expansion / contraction test of cloth assumed to be worn) The cloth sample which has been subjected to the above-mentioned dry-drying assumption test is taken out from the device, and after slowly cooling, a Soviet-type expansion / contraction tester having a chuck having a chuck width of 50 mm (expansion test of Asano Oni Kikai Seisakusho) Machine (machine) and a chuck distance of 100 mm (marked reference line), and stretched 7500 times repeatedly at a speed of 200 times per minute.

(Dip test in chlorine water assuming chlorine bleaching)
From the elastic warp knitted fabric using polyurethane elastic yarn, a strip-shaped fabric having a width of 50 mm in the wale direction (width direction) and a length of 200 mm in the course direction (length direction) is sampled. Using a round meter washing tester (see the attached material to JIS L0821-1983), a solution prepared by adjusting the effective chlorine concentration to 10 ppm with sodium hypochlorite is added to the dough sample and the bath ratio is 1; 100. Put the dough sample into this pot and put it in the pot
Operate at 60 ° C for 60 minutes. At this time, do not use stainless steel balls. When the operation for 60 minutes is completed, remove the test piece from the pot and drain with a filter paper.

(Experimental Drying Expected Test, Expansive Expansion Test When Wearing) The above-mentioned sundry drying expected test at the time of the composite laundry embrittlement test and the elastic expansion test when wearing are followed.

(Number of repetitions) Home laundry presumed test (or chlorine bleaching presumed test) → sun-drying presumed test → 1 cycle is assumed to be stretchable when worn and 50 cycles in the case of washing complex embrittlement test, and chlorine complex weakness test In this case, repeat test of 30 cycles is performed.

(Measurement of 80% elongation recovery stress and calculation of stress retention rate after n cycles) The test piece was adjusted to have a width of 25 mm and a chuck distance of 100 mm, and a tensile tester manufactured by Orientec Co., Ltd. was used. The 80% elongation is repeated three times and the third 80% elongation stress is read. n
The stress retention rate after the cycle is calculated by the following formula (Formula 5). The measurement is repeated twice and the average value is taken as the elongation stress at that time. Tn ÷ T0 * 100 (%) (Equation 5) At this time, the third 80% elongation stress when T0 is untreated. The third 80% elongation stress after the Tn n cycle embrittlement test was performed.

(Synthesis Example): Synthesis of hindered amine compound 2,2,6,6-in a 500 cc side-armed flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a reflux condenser.
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.
While bubbling nitrogen through the flask in the oil bath, 6
Heat to 0 ° C. with stirring.

After reaching 60 ° C., 0.8 parts of 4,4-azoisobutyronitrile (AIBN) was added. While stirring as it was, the temperature was maintained at 60 ° C. for reaction. Five hours after the first addition of AIBN, 0.2 parts of AIBN was further 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. When the unreacted polymerizable monomer in the solution was quantified by gas chromatography, it was 4% by weight based on the weight of the charged polymerizable monomer. The polystyrene-reduced number average molecular weight 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 hindered amine compound thus obtained was measured with DMSO-d6.
When a 1: 1 mixture of benzene and CDCl3 was used as a solvent at 50 ° C., the protons of the methine carbon of the piperidyl group and the protons of the methine carbon of the cyclohexyl group were 5.0, 4. Detected at 6ppm, integration ratio is 5
It was 2:48. Since this integral ratio is considered to be the mol ratio of the units derived from 2,2,6,6-tetramethyl-4-piperidyl methacrylate and the units derived from cyclohexyl methacrylate in the hindered amine compound, the respective weight fractions The rate was calculated to be 60,40% by weight, which was in agreement with the value obtained from the charged amount.

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

(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 H anate were heated at 80 ° C. under N 2 gas flow. The reaction was carried out for 3 hours to obtain a prepolymer having isocyanate groups at both ends. After cooling the prepolymer to 40 ° C,
308.36 parts of N, N'-dimethylacetamide was added and dissolved. It was further cooled to 10 ° C. Add 3.58 parts of ethylenediamine and 0.46 parts of diethylamine to N, N'-
The solution dissolved in 146.86 parts of dimethylacetamide was added at once to the prepolymer solution which was being stirred at high speed, and mixed to complete the reaction. The viscosity of this solution at 30 ° C. was 2000 poise. 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-
2.15 parts of 3-hydroxy-2.6-dimethylbenzyl isocyanurate) (Cyanox 1790 / Nippon cyanamide), 2- [2-hydroxy- (3,5-di-t-amyl) phenyl as an ultraviolet absorber ] 1.08 parts of benzotriazole (KEMISORB74 / Kemipro Kasei Co., Ltd.) and 0.69 parts of magnesium stearate as an anti-adhesive agent were added and mixed with stirring to obtain a polyurethane solution. After defoaming the polyurethane solution, the polyurethane solution was extruded through a spinneret having a pore size into a spinning tube in which air heated to 230 ° C. was flowed to obtain a polyurethane elastic yarn by so-called dry spinning in a fibrous state.

(Production Example 2 of Polyurethane Elastic Thread) Implementation of Polyurethane Elastic Thread The spinning stock solution of Production Example 1 was prepared by adding hydrogenated bisphenol A pentaerythritol phosphite polymer (JPH) as a phosphite type antioxidant.
Polyurethane elastic yarn was obtained in the same manner as in Production Example 1, except that 2.15 parts by weight of -3800 / Johoku Chemical Industry Co., Ltd. was further added.

(Comparative Example of Production of Polyurethane Elastic Yarn) As the hindered amine compound, 13.42 parts of the hindered amine compound obtained in the practical synthesis example was used, except that the hindered amine compound obtained in the comparative synthesis example was used. The same procedure as in Production Example 1 of polyurethane elastic yarn
A polyurethane elastic yarn was obtained.

Example 1 Obtained by the above Production Example 1
Polyurethane elastic thread 310 decitex thread and nylon
56 decitex-17 filament of Ron 6 (Semida
Russell knitting machine (RS
6 using E-4N / 130 inch width, 28 gauge)
The cloth of the course power net organization was knitted. Hit the dough
Pre-wet, which is a normal dyeing finish process known to the trader
Method pretreatment, preset (185 ℃ * 40sec), dyeing
(Temperature rise 2 ℃ / min, keep 95 ℃ * 30min), Final
Set (170 ° C * 40sec) and perform density 189
Course / 2.54 cm, lateral density 40 wale / 2.54
cm, fabric weight 160g / m ²Got the dough.

(Example 2) Polyurethane elastic yarn obtained by the above Production Example 1 310 decitex yarn and polyethylene terephthalate 56 decitex 36
Russell knitting machine (RSE-4N / 130 inch width / 2 made by Karlmayer by combining filaments (semi-dal)
(8 gauge) was used to knit a 6-course power net fabric. A person skilled in the art knows the cloth by a pre-wetting pretreatment, which is a usual dyeing finish processing, and a preset (18
5 ℃ × 40sec), Dyeing (temperature rise 2 ℃ / min, 130 ℃ * 3)
0 minute keep), final set (170 ℃ × 40se)
c) The warp density is 189 courses / 2.54 cm, the lateral density is 40 wale / 2.54 cm, and the fabric weight is 160 g / m.
Got ² dough

Example 3 A tricot knitting machine (HKS2 / 180-inch width and 28-gauge) knitted half-structured fabric. A person skilled in the art knows the cloth, which is an ordinary dyeing finishing process. Pre-treatment of pre-wetting method, preset (185 ° C. × 40 sec), dyeing (temperature rise 2 ° C./min, 9
5 ℃ * 30 minutes keep), final set (170 ℃ ×
40 sec) and a density of 98 courses / 2.54c
m, lateral density 60 courses / 2.54 cm, fabric weight 212
A dough of g / m ² was obtained.

(Example 4) Polyurethane elastic yarn obtained by the above Production Example 1 was combined with 44 decitex yarn and polyethylene terephthalate 56 decitex 36 filament (semi-dal) in combination with Karlmayer tricot knitting machine (HKS2 / 180 inch width).・ 28
Gauge) was used to knit a half-tissue fabric. A person skilled in the art knows the fabric, which is an ordinary dyeing finishing process, a pre-wetting pretreatment, a preset (185 ° C. × 40 se).
c), dyeing (temperature rise 2 ° C./min, keep 130 ° C. × 30 min),
A final set (170 ° C. × 40 sec) was performed to obtain a dough having a warp density of 189 courses / 2.54 cm, a lateral density of 40 wale / 2.54 cm, and a dough weight of 212 g / m ² .

(Comparative Examples 1 to 4) Except for using the polyurethane elastic yarns obtained in the above Comparative Production Example, all were knitted with the same combination of yarns, knitting machine and knitting structure as in Examples 1 to 4. Comparative Examples 1 to 4 are fabrics obtained with the same properties as Examples 1 to 4 under the same dyeing and finishing conditions. Examples 1 to 4,
For the fabrics obtained in Comparative Examples 1 to 4, the above-described washing composite embrittlement test was performed for 5 cycles, 10 cycles, 20 cycles,
80% elongation stress was repeated 3 times after 30 cycles, 40 cycles and 50 cycles, and the stress retention rate in each cycle is shown in Table-1. Moreover, Example 1 to
4, the chlorine complex embrittlement test described above for the doughs obtained in Comparative Examples 1 to 4 was repeated 5 times, 10 cycles, 20 cycles and 30 cycles, and then repeated 80 times to measure 80% elongation stress and stress in each cycle. Retention rate is shown in Table-2
It was shown to. In all of the examples, the stress retention rate was higher than that of the comparative example, and the value was at a level at which there was no concern about consumer complaints. High pressure dyeing (1
In the case of 30 ° C. × 30 minutes), the comparative example breaks the yarn, but the example shows a high stress retention rate.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

EFFECTS OF THE INVENTION A laundry complex embrittlement test and a chlorine complex embrittlement test were devised as evaluation methods assuming actual wearing and washing, and the elastic warp using the polyurethane elastic yarn obtained from the polyurethane composition of the present invention was used. The knitted fabric has a high stress retention rate in the composite embrittlement test. In particular, the performance of a knitted product with polyester, which has been subjected to high-pressure dyeing, is sufficiently recognized.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C08K 5/3492 C08K 5/3492 C08L 75/04 C08L 75/04 C09K 15/08 C09K 15/08 15/30 15/30 15/32 15/32 C // D01F 6/70 D01F 6/70 Z 6/94 6/94 A (C08L 75/04 C08L 33:14 33:14) 33:26 (C08L 75/04 C08L 85:02 33:26) (C08L 75/04 85:02) F term (reference) 4H025 AA15 AA53 AA62 AC05 AC07 4J002 BJ002 CK021 CQ013 EU136 FD033 FD036 FD042 GK01 4J100 AL08P AL08Q AM21P AM21Q BA03Q BC08Q BC07Q BC02Q BC02Q BC03Q BC04Q BC03Q BC02Q BC03Q FA03 FA19 JA11 4L002 AA05 AB02 AC00 AC01 CA01 EA06 FA01 FA09 4L035 BB03 BB14 EE07 EE08 EE20 JJ16 JJ19 JJ25

Claims (12)

[Claims] 1. A stretchable warp knitted fabric composed of non-stretchable fibers and polyurethane elastic yarn, which has a stress retention rate of 60 after 50 cycles of a combined washing test assuming home washing, sun drying and wearing. % Of elastic warp knitted fabric with excellent composite embrittlement characteristics. 2. A stretch warp knitted fabric composed of non-stretchable fibers and polyurethane elastic yarns, which has a stress retention rate after 20 cycles of chlorine bleaching and chlorine compound embrittlement test assuming that it is worn and dried. Stretchable warp knit fabric with excellent chlorine embrittlement, characterized by having a content of 50% or more. 3. A composition in which the polyurethane elastic yarn contained in the stretchable warp knitted fabric contains a, a phenol-based antioxidant, b, a phosphite-based antioxidant, and c, a hindered amine compound. The stretchable warp knitted fabric according to claim 1 and / or claim 2, which is a product. 4. A hindered amine compound contained in the polyurethane elastic yarn is a monovalent organic group represented by the following general formula (1) in one molecule and a compound represented by the following formula: [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. ] The following general formula (2) [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. ]
A hindered amine compound having at least one monovalent and / or two or more monovalent and / or divalent organic groups (D1) selected from the group consisting of divalent organic groups represented by: 1. The number of organic groups (D1) in (1) is 1.3 mol or more, and the solubility in an acidic solution is 5.0 × 10 −3 eq / l or less, which is a hindered amine compound. Item 3. The stretchable warp knitted fabric according to Item 2. 5. 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 one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. ] 1
Represented by a valent organic group and the following general formula (4): [In the above general formula, R represents an alkyl group having 1 to 3 carbon atoms. ] One or more monovalent and / or divalent organic groups (D2) selected from the group consisting of divalent organic groups, and 5 to 5 carbon atoms
A compound having one or more monovalent and / or divalent organic groups (F1) selected from the group consisting of a saturated cycloalkyl group having 10 and a saturated cycloalkylene group having 5 to 10 carbon atoms; And the weight fraction of organic compounds (D2) and (F1) in the molecule is a hindered amine compound satisfying the following formulas (1) and (2): 40 ≦ (W _D2 + W _F1) ≦ 70 Formula (1) 0.6 ≦ (W _D2 ÷ W _F1 ) ≦ 3 Formula (2) The stretchable warp knitted fabric according to claim 1 and / or 2. 6. A hindered amine compound compounded 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 of the alkoxy groups. X1 represents an -O- group or an -NH- group. ] The 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 formula and the following general formula (6): [In the above general formula, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ represents a saturated cycloalkyl group having 5 to 10 carbon atoms. Y ¹ represents a -O- group or a -NH- group. ] A hindered amine compound obtained by radical copolymerization with a radically polymerizable monomer component (F2) of one kind or a mixture of two or more kinds selected from the group represented by: The stretchable warp knitted fabric according to claim 1 or 2, wherein the weight fraction of the component (D3) and the component (F2) is a hindered amine compound satisfying the following formulas (3) and (4). Ground. 80 ≦ (W _D3 + W _F2 ) ≦ 100 Formula (3) 0.5 ≦ (W _D3 ÷ W _F2 ) ≦ 2.3 Formula (4) [W _D3 is the weight% of the component (D3), W _F2 represents the weight% of the component (F2)] 7. The hindered amine compound according to claim 3, wherein the hindered amine compound blended in the polyurethane elastic yarn has a structure represented by the following general formula (7): Alternatively, the stretchable warp knitted fabric according to claim 2. [Chemical 7] [In the above general formula, R represents an alkyl group having 1 to 4 carbon atoms. R ⁷ and R ^{8 each} represent a hydrogen atom or a methyl group. R ⁹ represents any of 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- group or -NH- group. n and m represent positive numbers such that 0.35 ≦ (n / m) ≦ 1.75] 8. A phenolic antioxidant blended in the polyurethane elastic yarn is a phenolic antioxidant represented by the following general formula (8): [In the above general formula, R10 represents a group selected from a t-butyl group, a sec-butyl group, and a neobentyl group. ] Further, the phosphorous acid ester-based antioxidant is represented by the following formula (9)
Including the structure represented by The stretchable warp knitted fabric according to any one of claims 3 to 7, which is a hydrogenated bisphenol A / pentaerythritol phosphato polymer. 9. In the polyurethane elastic yarn, (a) the compounding amount of the phenolic antioxidant with respect to the polyurethane is 0.1 to 2.0% by weight, and (b) the compounding amount of the phosphite antioxidant is The elastic warp knitted fabric according to claim 1, wherein the content of the hindered amine compound is 0.1 to 2% by weight, and the content of the hindered amine compound is 0.5 to 5% by weight. 10. A stretchable woven or knitted warp knitted fabric according to any one of claims 1 to 9, wherein the polyurethane elastic yarn is obtained by interlacing bare polyurethane yarn or a composite elastic yarn thereof. Warp knitted fabric. 11. The stretchable warp knitted fabric is a Russell fabric obtained by interlacing the polyurethane elastic yarn according to any one of claims 3 to 10 with an insertion structure, and / or 2. Elastic warp knitted fabric described in. 12. The stretchable warp knitted fabric is a tricot fabric obtained by interwoven with the polyurethane elastic yarn according to any one of claims 3 to 10 in a knit structure, and / or 2. Elastic warp knitted fabric described in. The stress retention rate is expressed by the following formula (Formula (5)). Tn ÷ T0 × 100 (%) Formula (5) Here, T0 and Tn are widths of 2 with an Instron type tensile tester.
80% of the test piece set to 5 mm and the tension interval of 100 mm
It is the value of the third extension stress when the extension three times repeated test is performed. T0 is the untreated test piece, and Tn is the composite embrittlement test (washing, chlorine) after the test cycle is repeated for n cycles. value.