JP2000290835A - Elastic yarn - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastic yarn having flexibility, excellent in resistance to heat aging and water resistance, and useful for a covering yarn, or the like, by employing a thermoplastic polyester elastomer having a specific melting temperature above which all crystalline regions disappear, a specific Vicat softening temperature and a specific elongation at break. SOLUTION: This elastic yarn has a melting temperature above which all crystalline regions disappear, expressed by the formula y>=200+0.5x [wherein, (x) is the content (wt.%) of a hard segment-constituting structural unit; (y) is the melting temperature ( deg.C) measured by DSC at the warm-up speed of 20 deg.C/min from room temperature], a Vicat softening temperature expressed by the formula z>=50+1.5x [wherein, (z) is the Vicat softening temperature ( deg.C) measured according to ASTM D1525] and an elongation of >=100%. The thermoplastic polyester elastomer is constituted by repeating units of formulae I-IV [wherein, R is a 6-18C aromatic group; G is a polyoxyalkylene having a molecular weight of 400-6,000; D is a hydrogenated dimer diol, or the like; R' is a 1-25C alkylene; (a) is 30-95 wt.%; (b)/(b+c) is 0.01-0.99; (d) is 0-20 mol%] and has a reduced viscosity of 0.5-4.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an elastic yarn using a thermoplastic elastomer composition. More specifically, the present invention relates to an elastic yarn using a polyester elastomer having a specific structure excellent in heat aging resistance, water resistance and flexibility up to a high temperature region of 130 ° C. or more.

[0002]

2. Description of the Related Art Conventionally, spandex has been mainly used as an elastic yarn because of its extremely excellent elastic recovery performance. However, spandex has the drawbacks that it is difficult to dye a cross-knitted fabric with polyester fibers due to poor heat and moisture resistance, and that it is easily yellowed by light irradiation. Therefore, its use is currently limited.

[0003] For this reason, elastic yarns made of polyester elastomers, for example, polyetherester elastomers, have recently been proposed and are beginning to be used for some applications. However, while this elastic yarn is superior to spandex in terms of moisture and heat resistance, it is not yet sufficient. For example, in a process of dyeing a knitted and woven fabric with polyester fibers, a higher degree of hydrolysis resistance is required, and further improvement is desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an elastic yarn made of a polyester elastomer which is flexible and has good heat aging resistance and excellent water resistance up to a high temperature range of 130 ° C. or more. It is.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, by using a specific hard segment and a plurality of specific soft segments in a polyester elastomer, The inventors have found that the problem is solved, and have completed the present invention. That is, the present invention provides a thermoplastic polyester elastomer having a crystal melting point represented by the following formula (1) and a Vicat softening temperature represented by the following formula (2), and having an elongation at break of 100% or more. This is an elastic yarn using Crystal melting point: y ≧ 200 + 0.5x (1) Vicat softening temperature: z ≧ 50 + 1.5x (2) (where x is a weight% substantially constituting a hard segment with respect to the thermoplastic polyester elastomer of the composition) And y is the crystal melting point (° C.) measured by raising the temperature from room temperature by DSC at 20 ° C./min, and z is ASTM D1525.
Shows the Vicat softening temperature (° C.) measured based on The elongation at break is a value measured based on JIS K6251. As a preferred embodiment, the following general formulas (1) to (4)
And a reduced viscosity of 0.1.
It is an elastic yarn using a thermoplastic polyester elastomer of 5 to 4.0.

[0006]

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[0007]

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[0008]

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[0009]

Embedded image Wherein R is an aromatic group having 6 to 18 carbon atoms, and G is a molecular weight of 40.
A polyoxyalkylene group having 0 to 6000, D represents a hydrogenated dimer diol and / or a derivative thereof, and R ′ represents an alkylene group having 1 to 25 carbon atoms. A, b, and c each represent the weight percent of each repeating unit in the entire polymer,
d represents mol% of the total polymer, a represents 30 to 95% by weight, and the ratio of b to the sum of b and c is 0.01 to 0.9.
9, d is 0 to 20 mol%. In addition, the relationship between the weight% constituting the hard segment and the crystal melting point is preferably y ≧ 200 + 0.55x, more preferably y ≧ 200 + 0.6x. The relationship between the weight percentage of the hard segment and the Vicat softening temperature is preferably z ≧ 50 + 1.7x, and more preferably z ≧ 70 + 1.7x. y,
When z does not satisfy the above formula, the heat resistance is not sufficient, and the difference in characteristics from the elastic yarn using the conventional polyetherester elastomer becomes unclear. Also, y and z
Are the crystal melting point and the Vicat softening temperature when a high polymer is formed only with the components constituting the hard segment. From the viewpoint of elastic properties, preferably, the upper limit of y is 300 and the upper limit of z is 250.

The Vicat softening temperature is ASTM D15
The measurement is performed according to 25. Depending on the shape of the sample, the sample is melt-molded to prepare and measure a measurement sample.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the thermoplastic elastomer used in the present invention, the acid component constituting the repeating unit represented by the general formulas (1) to (4) in order to satisfy the formulas (1) and (2) is an aromatic dicarboxylic acid. Mainly, specifically, it is preferable to use one or a combination of two or more selected from terephthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid, and particularly, terephthalic acid and naphthalenedicarboxylic acid It is preferable to use one or a combination of two selected from the above. The aromatic dicarboxylic acid is preferably at least 70 mol% of the total acid component, more preferably at least 80 mol%.
Mol% or more. As other acid components, alicyclic dicarboxylic acids and aliphatic dicarboxylic acids are used, and examples of the alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid, tetrahydrophthalic anhydride and the like. As aliphatic dicarboxylic acids, succinic acid, glutaric acid, adipic acid,
Azelaic acid, sebacic acid, dodecandioic acid, dimer acid, hydrogenated dimer acid and the like can be mentioned. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is preferably less than 30 mol% of the total acid component, more preferably 2 mol%.
Less than 0 mol%.

The glycol component constituting the repeating unit represented by the general formula (1) (hereinafter referred to as ester unit (1)) is cyclohexanedimethanol cyclohexanedimethanol. 1,4-cyclohexanedimethanol has two types of isomers, a cis form and a trans form, and it is preferable that the ratio of the trans form is large. The ester unit (1) is desirably 30 to 95% by weight, preferably 40 to 90% by weight, and particularly preferably 50 to 85% by weight in the whole polymer. The value is the value of x in the formula (1) and the value of a in the general formula (1). If it exceeds 95% by weight, it is inferior in flexibility because it is difficult to obtain an elastomer having elasticity, and if it is less than 30% by weight, the melting point is lowered and the heat resistance is deteriorated.

The glycol component constituting the repeating unit represented by the general formula (2) (hereinafter referred to as the ester unit (2)) is not particularly limited, but for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or a mixture thereof. A derivative at both ends ethylene oxide adduct is desirable. The molecular weight of the polyalkylene glycol is desirably 400 to 6,000, preferably 800 to 3,000, and particularly desirably 1,000 to 2,000. If the molecular weight is less than 400, the elastic performance is insufficient,
Further, the blockability of the obtained elastomer is reduced, that is, a segment having a length sufficient for the hard segment of the elastomer to exhibit crystallinity is not obtained, so that the melting point and the softening temperature of the polymer are lowered. Further, when the molecular weight exceeds 6,000, phase separation becomes easy, compatibility during polymerization with other copolymer components becomes poor, copolymerization becomes difficult, and this also causes insufficient elasticity. Absent.

The hydrogenated dimer diol which is a glycol component constituting the repeating unit represented by the general formula (3) (hereinafter referred to as the ester unit (3)) is not limited to its production method. A compound containing, as a main component (50% by weight or more), a compound represented by the following general formula (5) obtained by hydrogenating dimer acid which is a dimer of a saturated fatty acid (15 to 21 carbon atoms), or a compound represented by the following general formula: It is a mixture of a compound represented by (5) and a compound represented by the following general formula (6).

[0015]

Embedded image(In the above formula, R¹, R^Two, R^Three, R^FourContains a substantially unsaturated group.
First, it is also substantially linear, of which R¹, R^TwoIs
Alkyl group, R^Three, R^FourIs an alkylene group; ¹~ R^Four
Are from 22 to 34. )

[0016]

Embedded image(In the above formula, R^Five, R⁶, R⁷, R⁸Contains a substantially unsaturated group.
First, it is also substantially linear, of which R^Five, R⁶Is
Alkyl group, R⁷, R⁸Is an alkylene group; ^Five~ R⁸
Is 25 to 37 in total. )

The hydrogenated dimer diol derivative is a diol compound substantially derived from hydrogenated dimer diol, and specific examples thereof include ethylene oxide and / or propylene oxide adducts of hydrogenated dimer diol. . The addition of the oxide compound may be at both ends or only one end of the hydrogenated dimer diol. The number of moles of the oxide compound to be added is preferably equimolar to 20 times the number of moles of the hydrogenated dimer diol.

As the glycol component constituting the repeating unit represented by the general formula (4) (hereinafter referred to as ester unit (4)), an alkylene glycol having 1 to 25 carbon atoms can be used. For example, ethylene glycol, diethylene glycol, propylene glycol,
1,3-butanediol, 1,4-butanediol,
1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, dimethylolheptane, dimethylolpentane, tricyclodecanedimethanol, ethylene oxide derivatives of bisphenol X (X is A, S, F).
These glycols are used in an appropriate combination depending on the balance of various properties. However, since it is premised that the crystallinity of the ester unit (1) composed of cyclohexanedimethanol and aromatic carboxylic acid is not hindered, these glycols are used in combination. The polymerization amount is desirably 20 mol% or less based on all glycol components.

The proportion of the ester unit (2) and the ester unit (3) is not particularly limited because it is used in an appropriate combination depending on various balances, but the weight sum of the ester unit (2) and the ester unit (3) is not limited. The ratio of the ester unit (2) is preferably 0.01 to 0.99, more preferably 0.05 to 0.95, and particularly preferably 0.1 to 0.9.
If it is less than 0.01, the elastic performance as an elastomer will be lacking, and if it is more than 0.99, compatibility with the hard segment will be lacking.

The thermoplastic polyester elastomer of the present invention may contain a trifunctional or higher polycarboxylic acid or polyol component in a small amount. For example, trimellitic anhydride, benzophenonetetracarboxylic acid, trimethylpropane, glycerin, pyromellitic anhydride, etc.
Mol% or less can be used.

Next, as a method for obtaining the thermoplastic polyester elastomer of the present invention, any known method can be adopted. For example, any of a melt polymerization method, a solution polymerization method, and a solid phase polymerization method may be appropriately used. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. It is, of course, desirable to carry out solid phase polymerization after melt polymerization in order to improve the viscosity of the resin. As a catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. Particularly, the titanium catalyst is preferably a tetraalkyl titanate such as tetrabutyl titanate or tetramethyl titanate, or a metal oxalate such as titanium potassium oxalate. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.

The obtained polyester elastomer may be a known antioxidant such as a hindered phenol type, sulfur type, phosphorus type or amine type, hindered amine type, triazole type, benzophenone type, benzoate type, nickel type, salicyl. -Based light stabilizers, antistatic agents, lubricants, molecular modifiers such as peroxides, compounds having reactive groups such as epoxy compounds, isocyanate compounds, carbodiimide compounds, metal deactivators, organic and inorganic compounds Nucleating agents, neutralizing agents, antacids, antibacterial agents, optical brighteners, glass fibers, carbon fibers, silica fibers, inorganic fibrous substances such as alumina fibers, carbon black, silica, quartz powder,
Glass beads, glass powder, calcium silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron oxide, titanium oxide, zinc oxide, alumina, calcium carbonate, barium carbonate Fillers such as metal carbonates and other various metal powders, mica, glass flakes, plate-like fillers such as various metal powders, flame retardants, flame retardant assistants, organic and inorganic pigments, etc. Can be added.

These additives can be compounded using a kneader such as a heating roll, an extruder, or a Banbury mixer. Further, it can be added and mixed into the oligomer before the transesterification reaction or before the polycondensation reaction when producing the thermoplastic polyester elastomer resin composition.

The reduced viscosity of the thermoplastic polyester elastomer used in the present invention is preferably 0.5 to 4.0,
More preferably, it is 0.5 to 3.0. The reduced viscosity is 0.
If it is less than 5, mechanical properties are inferior, and if it exceeds 4.0, moldability is inferior. The lower limit of the melting point of the thermoplastic polyester elastomer composition of the present invention is not particularly limited, but is generally preferably 150 ° C. or higher. 200 ° C. or higher is preferred for applications requiring heat resistance, but 230 ° C. or higher is particularly preferred for applications requiring heat resistance. By the way, Adv. Chem. . Ser. , 176, 12
9 (1979). According to this publication, it is described that in a polyester elastomer composed of only polycyclohexane dimethylene terephthalate and polytetramethylene glycol, when polycyclohexane dimethylene terephthalate is contained in an amount of 50% by weight or more, phase separation occurs, and no elastic performance as an elastomer is exhibited. However, surprisingly, in the present invention, by changing the soft segment from polyalkylene glycol alone to a combined system of polyalkylene glycol and hydrogenated dimer diol and / or a derivative thereof, the amount of hard segment can be increased to 50% by weight or more. It has been found by the present inventor and others that sufficient elasticity is exhibited. The reason for this is not clear, but since the hydrogenated dimer diol having a cyclohexane skeleton and / or a derivative thereof functions as a compatibilizer between polycyclohexane dimethylene terephthalate and polyalkylene glycol, the compatibility between both is improved. It is estimated to be.

In the present invention, the polyetherester elastomer thus obtained is spun into fibers.
Although this spinning method is not particularly limited, a melt spinning method is usually employed in terms of simplicity. On this occasion,
If the ratio between the take-up speed and the discharge speed is changed, the properties of the fiber change depending on the take-up conditions, such as the elongation of the obtained fiber changing. Therefore, it is necessary to appropriately set the properties according to the purpose. If the spinning temperature is too high, thermal aging proceeds during spinning, which causes a deterioration in elastic performance. Therefore, a temperature higher by 10 to 20 ° C. than the melting point is preferable.

The spun fiber can be used as it is, but may be subjected to further stretching or heat treatment as needed. The temperature of the heat treatment is usually 130 to 180 ° C., and the stretching is usually room temperature to 70 ° C. or less, and the stretching ratio is 3 to 6.
Done in times.

The elastic yarn thus obtained is heated at 150 ° C. for 1 hour.
Even if heat treatment is performed for 0 minutes, it is necessary that they do not fuse with each other. In the case where the yarns are fused at 150 ° C., a problem occurs that the yarns are likely to adhere to each other in a spinning step, a post-processing step, or the like.

The elastic yarn of the present invention may be used in the form of a bare yarn as it is, or may be used in the form of a covering yarn obtained by covering other fibers such as nylon and polyester.

[0029]

The present invention will be specifically described below with reference to examples. In addition, in these Examples, each measurement item followed the following method. The weight% of polycyclohexane dimethylene terephthalate, polytetramethylene glycol and the like in the obtained polymer is a value measured by proton NMR. Reduced viscosity: 0.05 g of polymer in 25 ml of a mixed solvent (phenol / tetrachloroethane = 60/40 (wt.
/ Wt)) and 3 using an Ostwald viscometer.
It was measured at 0 ° C. Crystal melting point: The crystal melting point was measured by DSC at a rate of 20 ° C./min from room temperature. Vicat softening temperature: measured according to ASTM D1525. Tensile strength, elongation at break: Measured according to JIS K6251. Water resistance: immersed in boiling water at 100 ° C for one week,
The elongation retention at break was measured according to IS K6251. Heat aging resistance: Heat treatment is performed for one week with a gear type aging tester at 130 ° C., and after performing an aging test, JIS K62.
The elongation retention at break was measured according to No. 51. Fusing property: After performing heat treatment for 1 hour using a gear type aging tester at 150 ° C., the fusing property was evaluated.

Polyester Synthesis Example 1 460 parts by weight of dimethyl terephthalate, 460 parts by weight of cyclohexanedimethanol, 50 parts by weight of hydrogenated dimer diol (HP1000, manufactured by Toagosei Co., Ltd.), 300 parts by weight of polytetramethylene glycol (molecular weight: 1000), Irganox -1330 (manufactured by Nippon Ciba Geigy) 2 parts by weight and tetrabutyl titanate 0.9 part by weight were charged,
The temperature was raised from room temperature to 260 ° C. over 2 hours, and then 26
The mixture was heated at 0 ° C. for 1 hour to perform a transesterification reaction. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was performed at 75 ° C. and 1 torr or less. Further, a polymerization reaction was carried out at 275 ° C. and 1 torr or less for 4 hours, and the polymer was taken out in the form of pellets to obtain polymer A. The reduced viscosity of the obtained polymer is 1.04, and a polycyclohexane dimethylene terephthalate component, a polytetramethylene glycol component,
The weight percent of the hydrogenated dimer diol component is 65%,
30% and 5%.

Polyester Synthesis Example 2 530 parts by weight of dimethyl terephthalate, 750 parts by weight of cyclohexanedimethanol, 50 parts by weight of hydrogenated dimer diol (HP1000, manufactured by Toagosei Co., Ltd.), 200 parts by weight of polytetramethylene glycol (molecular weight 1000), Irganox -1330 (manufactured by Nippon Ciba Geigy) 2 parts by weight and tetrabutyl titanate 0.9 part by weight were charged,
The temperature was raised from room temperature to 260 ° C. over 2 hours, and then 26
The mixture was heated at 0 ° C. for 1 hour to perform a transesterification reaction. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was performed at 75 ° C. and 1 torr or less. Further, the polymerization reaction was carried out at 275 ° C. and 1 torr or less for 4 hours, and the polymer was taken out in the form of pellets to obtain polymer B. The reduced viscosity of the obtained polymer is 1.10, and a polycyclohexane dimethylene terephthalate component, a polytetramethylene glycol component in the polymer,
The weight% of the hydrogenated dimer diol component is 75%,
20% and 5%.

Polyester Synthesis Example 3 590 parts by weight of dimethylnaphthalate, 400 parts by weight of 1,4-butanediol, 350 parts by weight of polytetramethylene glycol (molecular weight 1000), Irganox-1
330 parts (manufactured by Nippon Ciba Geigy) and 0.9 parts by weight of tetrabutyl titanate are charged, and room temperature to 220 ° C.
And then heated at 220 ° C. for 1 hour to carry out a transesterification reaction. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was carried out at r or less. Further 250
The polymerization reaction was carried out at a temperature of 1 ° C. or lower at 3 ° C. for 3 hours. The reduced viscosity of the obtained polymer was 1.78, and the weight percents of the polybutylene naphthalate component and the polytetramethylene glycol component in the polymer were 65% and 35%, respectively.

Polyester Synthesis Example 4 570 parts by weight of dimethyl terephthalate, 580 parts by weight of 1,4-butanediol, 350 parts by weight of polytetramethylene glycol (molecular weight: 1000), Irganox-1
330 parts (manufactured by Nippon Ciba Geigy Co., Ltd.) and 0.9 parts by weight of tetrabutyl titanate were charged, and room temperature to 200 ° C.
And then heated at 200 ° C. for 1 hour to perform a transesterification reaction. Then, the pressure inside the can was gradually reduced and the temperature was raised.
The initial polycondensation reaction was carried out at r or less. Further 245
The polymerization reaction was carried out at a temperature of 1 ° C. or lower at 3 ° C. for 3 hours. The reduced viscosity of the obtained polymer was 1.94, and the weight percentages of the polybutylene terephthalate component and the polytetramethylene glycol component in the polymer were 65% and 35%, respectively.

Example 1 The polymer obtained in Polyester Synthesis Example 1 was discharged from a die having 12 holes at 275 ° C., and was wound at 400 m / min to obtain an elastic yarn.

Example 2 The polymer obtained in Polyester Synthesis Example 2 was discharged from a die having 12 holes at 285 ° C., and was wound at 400 m / min to obtain an elastic yarn.

Comparative Example 1 The polymer obtained in Polyester Synthesis Example 3 was discharged at 235 ° C. from a die having 12 holes, and wound at 400 m / min to obtain an elastic yarn.

Comparative Example 2 The polymer obtained in Polyester Synthesis Example 4 was discharged at 220 ° C. from a die having 12 holes and wound at 400 m / min to obtain an elastic yarn.

X in Table 1 is the weight% of the component substantially constituting the hard segment of the polyester elastomer.

[Table 1]

[0039]

As is clear from Table 1, Comparative Examples 1 and 2 using the conventional polyetherester elastomers are inferior in water resistance, heat aging resistance and fusibility. The elastic yarn of the present invention having the above-described structure can provide an elastic yarn having excellent heat aging resistance, water resistance, and flexibility up to a high temperature region of 130 ° C. or more, which greatly contributes to the industry. It is.

Continuing from the front page (72) Inventor Seiji Nakayama 2-1-1 Katata, Otsu-shi, Shiga F-term in Toyobo Co., Ltd. General Research Laboratory 4J002 CF101 GK01 4J029 AA03 AB07 AC03 AD01 AD05 AD06 AE02 BA02 BA03 BA05 BA07 BA08 BA09 BA10 BC09 BD06A BD07A BF09 BF25 BF26 CA02 CA04 CA05 CA06 CB05A CB06A CB07A CB10A CC05A CD03 CD04 CH02 DB02 JE182 KB02 4L035 AA09 EE01 EE20 HH10 4L036 MA05 MA37 UA06 UA08 UA30

Claims (4)

[Claims] 1. A thermoplastic polyester elastomer having a crystal melting point represented by the following formula (1) and a Vicat softening temperature represented by the following formula (2), and having an elongation at break of 100% or more: Elastic yarn using. Crystal melting point: y ≧ 200 + 0.5x (1) Vicat softening temperature: z ≧ 50 + 1.5x (2) (where x is the weight of a component substantially constituting a hard segment with respect to the thermoplastic polyester elastomer of the composition) %, Y is the crystal melting point (° C.) measured by raising the temperature from room temperature by DSC at 20 ° C./min, and z is ASTM D1.
525 shows the Vicat softening temperature (° C.) measured based on 525. The elongation at break is a value measured based on JIS K6251. ) 2. The elastic yarn using the thermoplastic polyester elastomer according to claim 1, wherein x, which is the weight% of the component substantially constituting the hard segment in the thermoplastic polyester elastomer, is 30 to 95. 3. The elastic yarn using the thermoplastic polyester elastomer according to claim 1, wherein a substantial hard segment in the thermoplastic polyester elastomer is composed of a repeating unit represented by the following general formula (1). 4. An elastic yarn comprising a thermoplastic polyester elastomer comprising a repeating unit represented by the following general formulas (1) to (4) and having a reduced viscosity of 0.5 to 4.0. Embedded image Embedded image Embedded image Embedded image Wherein R is an aromatic group having 6 to 18 carbon atoms, and G is a molecular weight of 40.
A polyoxyalkylene group having 0 to 6000, D represents a hydrogenated dimer diol and / or a derivative thereof, and R ′ represents an alkylene group having 1 to 25 carbon atoms. A, b, and c each represent the weight percent of each repeating unit in the entire polymer,
d represents mol% of the total polymer, a represents 30 to 95% by weight, and the ratio of b to the sum of b and c is 0.01 to 0.9.
9, d is 0 to 20 mol%. )