WO2019059328A1 - Copolymer, processing agent for fiber, method for processing fiber, method for producing fiber product, and textile product - Google Patents

Abstract

The purpose of the present invention is to provide a copolymer capable of exhibiting high washing resistance against bore fleece. In order to achieve the purpose, this copolymer can be obtained by copolymerizing monomers containing components (a)-(c): (a) at least one among an aromatic dicarboxylic acid and a derivative thereof, (b) a polyol, and (c) a compound represented by general formula (1), and is characterized in that the mass ratio of (a)/(c) is at least 1.7. (1) R1R2R3R4N+ X- (in general formula (1), R1, R2, R3 and R4 are each independently a C1-3 linear or branched alkyl group which may be interrupted by a linking group, a C2-30 linear or branched alkenyl group, -(AO)nH, -(AO)mCH3, or a benzyl group of which one or more hydrogen atoms may be unsubstituted or substituted with a substituent, at least two among R1, R2, R3 and R4 are -(AO)nH, A is one or two or more selected from among C1-4 linear or branched alkylene groups, m and n each represent the average addition molar number of (AO) and are 0.1-20, the sum of the respective n's in each of the -(AO)nH's in the molecule is 2-60, and X- is an anion.)

Description

Copolymer, processing agent for fiber, method for processing fiber, method for producing fiber product, and fiber product

The present invention relates to a copolymer, a processing agent for fibers, a method for processing fibers, a method for producing fiber products, and a fiber product.

Processing agents for fibers are used, for example, for the purpose of imparting various functions to fibers.

As a processing agent for fibers, for example, there is a durable antistatic agent using a polyester resin (Patent Document 1). Further, for example, there is also a processing agent for fibers (antistatic agent) using a polyester resin obtained by copolymerizing an amine derivative (Patent Document 2).

Japanese Patent Publication No. 38-11298 Japanese Patent Application Laid-Open No. 2003-073657

In processing chemicals for textiles, it is important to be able to maintain the function imparted to the fibers even after laundering, and to be durable in washing (washing resistance).

Due to recent trends in textile products, processing agents for textiles are required to have high wash resistance. For example, it is required to exhibit high washing resistance even to clothing (bore fleece) having a distinctive shape with high designability in recent years.

Therefore, the present invention provides a copolymer capable of exhibiting high washing resistance to bore fleece, a processing agent for fibers, a method for processing fibers, a method for producing fiber products, and a fiber product. To aim.

In order to achieve the above object, the copolymer of the present invention is obtained by copolymerizing monomers containing the following components (a) to (c), and the mass ratio of (a) / (c) is 1 .7 or more.

(A) at least one aromatic dicarboxylic acid and derivatives thereof (b) a polyol compound (c) represented by the following general formula ^{(1) R 1 R 2 R} 3 R 4 N + X - ··· (1)

In the general formula (1),
R ¹ , R ² , R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms which may be separated by a linking group, or a linear or branched alkenyl having 2 to 30 carbon atoms And-(AO) _n H,-(AO) _m CH ₃ , or a benzyl group, and at least one hydrogen atom of the benzyl group may be substituted or not substituted with a substituent,
At least two of R ¹ , R ² , R ³ and R ⁴ are — (AO) _n H,
A is one or more selected from linear or branched alkylene groups having 1 to 4 carbon atoms,
m and n respectively represent the average addition mole number of (AO), and are 0.1 to 20, and the sum of n of each-(AO) _n H in the molecule is 2 to 60,
X ^- is an anion.

The processing agent for fibers of the present invention is characterized by containing the copolymer of the present invention.

The fiber processing method of the present invention is characterized by including an immersing step of immersing the fiber in the liquid containing the processing agent for fibers of the present invention, and a drying step of drying the fiber immersed in the liquid. I assume.

The method for producing a fiber product of the present invention is characterized by including the step of processing the fiber by the processing method of the present invention.

The fiber product of the present invention is characterized by being produced by the method for producing a fiber product of the present invention.

According to the present invention, it is possible to provide a copolymer capable of exhibiting high washing resistance to bore fleece, a processing agent for fibers, a method for processing fibers, a method for producing fiber products, and a fiber product. it can.

Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited by the following description.

In the copolymer of the present invention, for example, the mass ratio of (b) / {(a) + (c)} in the components (a) to (c) may be 0.5 or more.

[1. Copolymer]
The copolymer of the present invention is obtained by copolymerizing monomers containing the following components (a) to (c) as described above, and the mass ratio of (a) / (c) is 1.7 or more. It is characterized by

(A) at least one aromatic dicarboxylic acid and derivatives thereof (b) a polyol compound (c) represented by the following general formula ^{(1) R 1 R 2 R} 3 R 4 N + X - ··· (1)

In the general formula (1),
R ¹ , R ² , R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms which may be separated by a linking group, or a linear or branched alkenyl having 2 to 30 carbon atoms And-(AO) _n H,-(AO) _m CH ₃ , or a benzyl group, and at least one hydrogen atom of the benzyl group may be substituted or not substituted with a substituent,
At least two of R ¹ , R ² , R ³ and R ⁴ are — (AO) _n H,
A is one or more selected from linear or branched alkylene groups having 1 to 4 carbon atoms,
m and n respectively represent the average addition mole number of (AO), and are 0.1 to 20, and the sum of n of each-(AO) _n H in the molecule is 2 to 60,
X ^- is an anion.

(1) Component (a): At least one of aromatic dicarboxylic acid and derivatives thereof In the component (a), the aromatic dicarboxylic acid (divalent aromatic carboxylic acid) is not particularly limited. 8 to 20 aromatic dicarboxylic acids can be mentioned. Specific examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid. Moreover, as a derivative of aromatic dicarboxylic acid, for example, anhydride of aromatic dicarboxylic acid, lower alcohol ester, acid halide and the like can be mentioned. Examples of the lower alcohol ester include esters of lower alkyl alcohols, and more specifically, esters of linear or branched alkyl alcohols having 1 to 3 carbon atoms. Examples of lower alkyl esters of aromatic dicarboxylic acids include monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester and the like, and more specifically, for example, dimethyl isophthalate, dimethyl terephthalate and the like. Examples of acid halides of aromatic dicarboxylic acids include monochlorides, dichlorides, monobromides, dibromides and the like. Among the aromatic dicarboxylic acids and their derivatives, aromatic dicarboxylic acids and their methyl esters are preferred, and aromatic dicarboxylic acids having 8 to 12 carbon atoms and their methyl esters are more preferred, from the viewpoint of washing durability. Specific examples thereof include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, phthalic acid and dimethyl phthalate. Further, in the present invention, only one kind of aromatic dicarboxylic acid and its derivative may be used, or plural kinds thereof may be used in combination.

(2) Component (b): Polyol The polyol of the component (b) may be a compound having two hydroxyl groups in one molecule (diol) or a polyol having three or more hydroxyl groups in one molecule. Good.

Although it does not specifically limit as said diol, For example, aliphatic diol, alicyclic diol, aromatic diol, these alkylene oxide adducts, etc. are mention | raise | lifted. In the present invention, the diol may be a compound having two hydroxyl groups in one molecule, and the hydroxyl group may be either an alcoholic hydroxyl group or a phenolic hydroxyl group. Examples of the aliphatic diols include alkylene diols and polyalkylene diols derived from linear or branched alkylene groups. Specific examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, Examples include 6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene / polyoxypropylene block copolymer and the like. The molecular weight of the polyalkylene glycol (for example, polyethylene glycol) is not particularly limited, but may be, for example, 300 or more, 600 or more, or 1000 or more, and may be, for example, 10000 or less, 8000 or less, or 6000 or less. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol, hydrogenated bisphenol A and the like. Examples of the aromatic diol include bisphenol A, bisphenol S, hydroquinone and the like. Among these diols, diols having an oxyethylene group such as polyethylene glycol are preferable from the viewpoint of the affinity to water and the temporal stability of the processing agent for fibers. In addition, the diol may be used alone or in combination of two or more.

The polyol having three or more hydroxyl groups in one molecule may be, for example, a triol, a tetraol, or a polyol having five or more hydroxyl groups. Examples of the polyol having three or more hydroxyl groups in one molecule include aliphatic polyols, alicyclic polyols, aromatic polyols, and alkylene oxide adducts thereof. In the polyol having three or more hydroxyl groups in one molecule, the hydroxyl group may be either an alcoholic hydroxyl group or a phenolic hydroxyl group. As said triol, glycerol, trimethylol propane, and these alkylene oxide adducts etc. are mention | raise | lifted, for example. Examples of the tetraol include pentaerythritol and adducts of these alkylene oxides. Examples of the polyol having 5 or more hydroxyl groups in one molecule include sorbitol, and alkylene oxide adducts thereof and the like. Further, the polyol having three or more hydroxyl groups in one molecule may be used alone or in combination.

(3) Component (c): Compound Represented by the General Formula (1) The component (c) is a compound represented by the general formula (1). The general formula (1) is listed again below.

^{R 1 R 2 R 3 R 4} N + X - ··· (1)

In the above general formula (1), as described above, R ¹ , R ² , R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms which may be separated by a linking group A linear or branched alkenyl group having 2 to 30 carbon atoms,-(AO) _n H,-(AO) _m CH ₃ , or a benzyl group, and at least one hydrogen atom of the benzyl group is substituted by a substituent Optionally substituted, at least two of R ¹ , R ² , R ³ and R ⁴ are — (AO) _n H, and A is a C 1-4 linear chain Or one or more selected from branched alkylene groups.

In R ¹ , R ² , R ³ and R ⁴ , the carbon number of the linear or branched alkyl group is 1 to 30, as described above, and is, for example, 1 to 18, 3 to 16 or 4 to 12 May be The alkyl group is not particularly limited, and, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group, pentyl group, hexyl group, Examples include heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like. The carbon number of the linear or branched alkenyl group is, as described above, 2 to 30, and may be, for example, 2 to 12 or 2 to 8. The alkenyl group is not particularly limited, and examples thereof include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 3-methyl-2-butenyl and the like. Be Further, the connecting group is not particularly limited, and examples thereof include an ether bond, an ester bond, an amide bond and the like.

In A, examples of the linear or branched alkylene group having 1 to 4 carbon atoms include a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), and a trimethylene group (—CH ₂ CH ₂ CH ₂ -), A propylene group (-CHCH ₃ CH _2- ) and the like.

In the general formula (1), m and n each represent the average addition mole number of (AO) as described above, and are 0.1 to 20, for example, 0.5 to 15, 1 to 12 or It may be 2 to 10. The sum of n of each — (AO) _n H in the molecule is, as described above, 2 to 60, and may be, for example, 3 to 40, 5 to 30, or 10 to 20.

In the general formula (1), X ^- is an anion as described above. X ^- is any anion and is not particularly limited. Further, X ⁻ is not limited to monovalent anions, and may be anions of any valence such as divalent or trivalent. In the case where the charge of the anion is plural such as divalent or trivalent, for example, the number of molecules of ammonium (monovalent) in the general formula (1) is the number of molecules of anion × valence of anion (eg, When the anion is divalent, the number of molecules of ammonium (monovalent) is twice the number of molecules of the anion). Examples of X ^- include halogen ions (fluoride ions, chloride ions, bromide ions, iodide ions), acetate ions, nitrate ions, sulfate ions and the like.

(4) Ratio of Each Component, Optional Component, Etc. As described above, the copolymer of the present invention is obtained by copolymerizing a monomer containing the components (a) to (c), (a) / (c) The mass ratio of c) is 1.7 or more. Other than this, in the copolymer of the present invention, the ratio of the mass and the substance mass (number of moles) of the components (a) to (c) is not particularly limited, and is, for example, as follows.

The mass of the component (a) may be, for example, 5 to 50%, 15 to 45%, or 30 to 40% of the total mass of the components (a) to (c). Further, the amount of substance (number of moles) of the component (a) is, for example, 20 to 95%, 30 to 93%, or the total of the amount of substance (number of moles) of the components (a) to (c) It may be 40 to 90%.

The mass of the component (b) may be, for example, 30 to 90%, 35 to 80%, or 40 to 70% of the total mass of the components (a) to (c). Further, the amount of substance (number of moles) of the component (b) is, for example, 1 to 70%, 2 to 60%, or the total of the amount of substance (number of moles) of the components (a) to (c) It may be 3 to 50%.

The mass of the component (c) may be, for example, 0.1 to 30%, 1 to 25%, or 5 to 20% of the total mass of the components (a) to (c). Further, the amount of substance (number of moles) of the component (c) is, for example, 1 to 50%, 2 to 40%, or the total of the amount of substance (number of moles) of the components (a) to (c) It may be 3 to 30%.

The mass ratio of (a) / (c) is 1.7 or more as described above, and may be, for example, 2.0 or more, 2.5 or more, 3.0 or more, or 4.0 or more, For example, it may be 20.0 or less, 19.0 or less, 9.0 or less, or 6.0 or less.

The mass ratio of (b) / {(a) + (c)} may be, for example, 0.5 or more, as described above, and for example, 0.7 or more, 1.0 or more, or 1 2 or more, for example, 3.6 or less, 2.7 or less, or 2.1 or less.

The copolymer of the present invention may or may not contain any component other than the components (a) to (c) as a monomer component. The optional component is not particularly limited. For example, aliphatic dicarboxylic acids or lower alkyl esters thereof (linear carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid or methyl esters thereof, methyl Examples thereof include dicarboxylic acids having a side chain such as malonic acid, methylsuccinic acid and methylglutaric acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid). When the copolymer of the present invention contains the optional component, the content of the optional component is, for example, 0.1 to 10%, or the total mass of the components (a) to (c), for example. It may be 1.0 to 3.0%.

(5) Structure of Copolymer The structure of the copolymer of the present invention can be represented, for example, by the following general formula (I), but is not limited thereto.

In the general formula (I), L is an atomic group derived from the component (b) and is, for example, a linear or branched alkylene group, an alicyclic group, an aromatic group or the like. Ar is an aromatic group derived from the component (a). A, R ³ , R ⁴ and X ⁻ are atomic groups derived from the component (c), and the structures are as described above. j, k, l and p are degrees of polymerization and are each a positive integer. Although j is not particularly limited, it may be, for example, 7 to 230, or 20 to 140. Although k is not particularly limited, it may be, for example, 1 to 350 or 10 to 30. Although l is not particularly limited, it may be, for example, 1 to 600, or 2 to 50. Although p is not particularly limited, it may be, for example, 1 to 50, or 10 to 30. The copolymer of the general formula (I) may be, for example, a random copolymer or a block copolymer.

When the component (a) is terephthalic acid and the component (b) is polyethylene glycol, the copolymer of the general formula (I) can be represented by the following general formula (II).

In the general formula (II), A, R ³ , R ⁴ , X ⁻ , j, k, l and p are the same as the general formula (I).

The weight average molecular weight of the copolymer of the present invention is not particularly limited, but may be, for example, 8000 or more, 10000 or more, 15000 or more, or 20000 or more, and 100000 or less, 75000 or less, 50000 or less, or 40000 It may be the following.

(6) Method for Producing Copolymer The method for producing the copolymer of the present invention is not particularly limited. For example, the copolymer may be produced by copolymerizing the components (a) to (c) as a monomer component. it can. In addition, as described above, as a monomer component, optional components other than the components (a) to (c) may or may not be copolymerized. Although the mass ratio or the substance mass ratio (molar ratio) of each monomer component is not particularly limited, for example, it is as described above.

The copolymerization method is also not particularly limited, but may be, for example, a known method or a modification thereof. Specifically, for example, the components (a) to (c) may be subjected to a polycondensation reaction under reduced pressure. Also, for example, when the component (a) is an ester of an aromatic dicarboxylic acid, transesterification may be performed in the presence of a suitable catalyst together with an alcohol solvent prior to the polycondensation reaction. The alcohol solvent is not particularly limited, and examples thereof include ethylene glycol and propylene glycol. The catalyst is also not particularly limited, and examples thereof include zinc oxide, zinc acetate, manganese acetate, antimony trioxide, tin acetate, dibutyltin oxide, tetrabutyl titanate, titanium isopropoxide and the like. The reaction time of the esterification reaction or transesterification reaction is also not particularly limited, and may be, for example, 0.3 hours or more, 0.5 hours or more, or 0.7 hours or more, 3 hours or less, 2 hours or less Or 1.5 hours or less. The reaction temperature is also not particularly limited, and may be, for example, 140 ° C. or more, 160 ° C. or more, or 170 ° C. or more, and may be 220 ° C. or less, 200 ° C. or less, or 190 ° C. or less. In the polycondensation reaction under reduced pressure of the components (a) to (c), the solvent is not particularly limited, but, for example, the same alcohol solvent as the transesterification reaction can be used. For example, the alcohol solvent used in the transesterification reaction may be used as it is as a solvent for the polycondensation reaction of the components (a) to (c) under reduced pressure. In the polycondensation reaction under reduced pressure, the reaction time is not particularly limited, but for example, it is preferably 1 hour or more, 1.5 hours or more, or 2 hours or more, and is 8 hours or less, 5 hours or less, Or preferably 4 hours or less. The reaction temperature is also not particularly limited, and may be, for example, 200 ° C. or more, or 220 ° C. or more, 280 ° C. or less, or 260 ° C. or less.

[2. Processing chemicals for textiles]
The processing agent for fibers of the present invention is characterized by containing the copolymer of the present invention as described above. The processing agent for fibers of the present invention may or may not contain any component other than the copolymer of the present invention. Examples of the optional components include organic solvents, water, and other optional components.

The processing agent for fibers of the present invention may be, for example, a processing agent for fibers in which the copolymer of the present invention is dissolved in the organic solvent. The organic solvent is not particularly limited, and examples thereof include ethers, esters, and the like. Examples of the ether include 1,4-dioxane and the like. Examples of the ester include ethyl acetate and the like. Further, for example, only one type of organic solvent may be used, or a plurality of types of organic solvents may be used in combination. The amount of the organic solvent used is not particularly limited, and may be, for example, 10 to 5000%, 30 to 4000%, or 100 to 3000% with respect to the mass of the copolymer of the present invention.

Furthermore, the processing agent for fibers of the present invention may be, for example, a processing agent for fibers obtained by dissolving the copolymer of the present invention in the organic solvent and further diluting with water. The water is not particularly limited, and may be, for example, tap water, distilled water, ion exchange water, or the like. From the viewpoint of cost, tap water etc. are preferable.

Moreover, in the processing agent for fibers of the present invention, the content rate of the water is not particularly limited, but for example, 200% by mass or more, 400% by mass or more, or 1000% by mass with respect to the mass of all components other than the water. It may be more than, 2500 mass% or less, 2000 mass% or less, or 1700 mass% or less. From the viewpoint of the performance of the processing agent for fibers, it is preferable that the water content is not too high. From the viewpoint of the stability of the processing agent for fibers, it is preferable that the water content is not too low.

Moreover, in the processing agent for fibers of the present invention, examples of optional components other than the organic solvent and water include aromatic sulfonates and the like. By including the aromatic sulfonate, for example, an effect of improving the antistatic performance immediately after the fiber processing (in a state without washing) can be obtained. The aromatic sulfonic acid salt is not particularly limited, and examples thereof include salts of sulfonic acids such as para-toluenesulfonic acid, meta-xylene sulfonic acid and cumene sulfonic acid. The aromatic sulfonate may be, for example, a salt of any metal, for example, a salt of an alkali metal (such as sodium or potassium), an alkaline earth metal (such as calcium or magnesium), or the like. The aromatic sulfonate is particularly preferably a sodium salt from the viewpoint of antistatic performance, and examples thereof include sodium paratoluenesulfonate, sodium metaxylenesulfonate, sodium cumenesulfonate and the like.

Moreover, in the processing agent for fibers of the present invention, the contents of the organic solvent and the optional components other than the water are not particularly limited. For example, when the aromatic sulfonate is added, the mass of the aromatic sulfonate may be, for example, 1 to 50% by mass with respect to the mass of all components other than the organic solvent and the water. . The mass of the aromatic sulfonate may be, for example, 0.1 to 10% by mass with respect to the total mass of the fiber processing agent of the present invention.

Although the manufacturing method of the processing agent for textiles of this invention is not specifically limited, either, for example, you may only mix said each component. For example, as described above, the copolymer of the present invention may be dissolved in the organic solvent, or it may be further diluted with water.

[3. Applications of processing chemicals for textiles, methods of processing textiles, methods of manufacturing textiles, textiles]
The use of the fiber processing agent of the present invention is not particularly limited, and is optional, but can be used as a finishing agent, for example, for the purpose of imparting various functions to fiber products. Specifically, it can be used, for example, as a fiber durable antistatic agent, a water absorbing agent, and the like.

The processing agent for fibers of the present invention includes, for example, a polyester skeleton having durability against washing, an amine derivative having an antistatic property (tertiary amine or quaternary ammonium salt), and a polyol. By being a ternary copolymer with a skeleton, it is possible to achieve both high washing durability (washing resistance) and antistatic performance at a high level.

Although the use of the processing agent for fibers of the present invention is not particularly limited as described above, for example, it can be used for the method for processing fibers of the present invention or the method for producing the fiber products of the present invention using the same. The processing method of the fiber of the present invention includes, as described above, an immersing step of immersing the fiber in a containing liquid containing a processing agent for processing fiber, and a drying step of drying the fiber immersed in the containing liquid. Moreover, the manufacturing method of the textiles of the said invention includes the process of processing the said fiber by the processing method of the textiles of the said invention as mentioned above. Other than these, the method for processing the fiber of the present invention and the method for producing the fiber product of the present invention are not particularly limited. For example, the fibers may be squeezed as needed after immersion and before drying, or may be heated to about 40 to 100 ° C. during immersion. By processing the fibers in this manner, it is possible to appropriately impart a function (for example, antistatic performance) to the fibers. The type of the fiber is not particularly limited, but may be a natural fiber or an artificial fiber, and examples thereof include polyester fibers, and blended products of polyester fibers and other fibers. The fiber may be, for example, any fiber product, and it may be processed (finished) by the fiber processing method of the present invention to form the fiber product of the present invention. Although the kind of said textiles is not specifically limited, either, For example, cloth, clothes, a carpet, a nonwoven fabric etc. are mention | raise | lifted. The processing agent for textiles of the present invention may contain water as described above, but may be used as a diluted water solution diluted with water at the time of use. The mass of the copolymer of the present invention in the water dilution liquid is, for example, 0.01 mass% or more, 0.1 mass% or more, 1 mass% or more, 2 mass% or more with respect to the water dilution liquid. Or 3 mass% or more may be sufficient, 20 mass% or less, 15 mass% or less, or 10 mass% or less may be sufficient.

The processing agent for fibers of the present invention can be used for processing any fiber or fiber product as described above, but for example, it can be used for napped fabrics such as bores, flannel, fleece, felt, velvet, fake fur, etc. In particular, it is suitable for processing of bore fleece. In the present invention, the "bore fleece" refers to a fiber product having a long haired leg (for example, a cloth product etc.). The length of the haired foot is not particularly limited, but may be, for example, 0.1 mm or more, 0.5 mm or more, or 1.0 mm or more, and may be 30 mm or less, 20 mm or less, or 10 mm or less .

According to the processing agent for fibers of the present invention, for example, the resistance to washing can be exhibited even to a bore fleece in which it is difficult to exhibit the resistance to washing (resistance to washing) with conventional processing agents for fibers. For example, by processing a bore fleece using the processing agent for fibers of the present invention, the bore fleece can be provided with functions such as antistatic performance, and can be made into a bore fleece which is a fiber product of the present invention. The bore fleece is easy to be charged due to the long haired foot, but it is also possible to impart excellent antistatic performance to the bore fleece, for example, by processing it with the processing agent for fibers of the present invention. Moreover, the processing agent for fibers, the method for processing fibers, and the method for producing fiber products according to the present invention are not limited to the bore fleece as described above, and can be used for processing any fiber products. That is, the fiber product of the present invention is not limited to the bore fleece, but may be any fiber product.

Below, the Example of this invention is described. However, the present invention is not limited to the following examples.

[1. Production of copolymer]
First, the copolymers of Examples 1 to 3 and Comparative Examples 1 to 3 were produced as follows.

Example 1
105 g of dimethyl terephthalate (component (a)), 160 g of ethylene glycol, and 0.5 g of zinc acetate as a catalyst were placed in a reaction vessel, and transesterification was performed at 180 ° C. for 1 hour. At that time, methanol flowed out at around 140 ° C. Thereafter, 170 g of polyethylene glycol (Mw 3000, component (b)), 24 g of polyoxyethylene palm alkylmethyl ammonium chloride (component (c), manufactured by Lion Specialty Chemicals, Inc., trade name "Liposocard C / 25"), antioxidant The temperature was increased by adding 2.7 g of Adekastab AO-330 (ADEKA Co., Ltd.) as an agent, and the pressure was reduced after reaching 180.degree. Further, the temperature was raised and the pressure was reduced continuously, and the condensation reaction was carried out at 240 to 250 ° C. and 10 torr (about 1.3 kPa) or less for 3 hours to obtain an objective copolymer (polyester resin). In addition, "Mw" represents a weight average molecular weight. The same applies to the following.

Example 2
A copolymer (polyester resin) was obtained in the same manner as in Example 1 except that the amounts of components (b) and (c) were changed. More specifically, the example is used except that 147 g of polyethylene glycol (Mw 3000) and 48 g of polyoxyethylene co-alkyl methyl ammonium chloride are used instead of 170 g of polyethylene glycol (Mw 3000) and 24 g of polyoxyethylene co-alkylmethyl ammonium chloride. The condensation reaction was carried out in the same manner as 1 to obtain a target copolymer (polyester resin).

[Example 3]
A copolymer (polyester resin) was obtained in the same manner as in Example 1 except that the amounts of components (b) and (c) were changed. More specifically, it is an example except using 133 g of polyethylene glycol (Mw 3000) and 62 g of polyoxyethylene coc alkylmethyl ammonium chloride in place of 170 g of polyethylene glycol (Mw 3000) and 24 g of polyoxyethylene coc alkylmethyl ammonium chloride. The condensation reaction was carried out in the same manner as 1 to obtain a target copolymer (polyester resin).

Comparative Example 1
The same as Example 1 except using only 194 g of polyethylene glycol (Mw 3000) instead of 170 g of polyethylene glycol (Mw 3000) and 24 g of polyoxyethylene coc alkylmethyl ammonium chloride and not using polyoxyethylene cocylalkyl methyl ammonium chloride Condensation reaction to obtain a target copolymer (polyester resin).

Comparative Example 2
A copolymer (polyester resin) was obtained in the same manner as in Example 1 except that the amounts of components (b) and (c) were changed. More specifically, the example is used except that 123 g of polyethylene glycol (Mw 3000) and 72 g of polyoxyethylene co-alkylmethyl ammonium chloride are used instead of 170 g of polyethylene glycol (Mw 3000) and 24 g of polyoxyethylene co-alkylmethyl ammonium chloride. The condensation reaction was carried out in the same manner as 1 to obtain a target copolymer (polyester resin).

Comparative Example 3
Similar to Example 1 except that only 194 g of polyoxyethylene co-alkylmethyl ammonium chloride was used instead of 170 g of polyethylene glycol (Mw 3000) and 24 g of polyoxyethylene co-alkylmethyl ammonium chloride and no polyethylene glycol (Mw 3000) was used. Condensation reaction to obtain a target copolymer (polyester resin).

[2. Processing of fibers (production of fiber products) and performance evaluation]
A processing agent for fibers is manufactured using each of the copolymers (polyester resins) of Examples 1 to 3 and Comparative Examples 1 to 3 as follows, and a fiber product (bore fleece) is processed using the same. Thereby producing processed fiber products. Furthermore, the performance of the processing agent for fibers was evaluated by conducting tests on the manufactured fiber products.

[Production of processing chemicals for fibers (durable antistatic agent)]
After dissolving 2.0 g of each of the copolymers (polyester resins) of Examples 1 to 3 and Comparative Examples 1 to 3 in 58 g of 1,4-dioxane, respectively, 440 g of water is added to make a processing agent for fibers (Durable antistatic agent) was adjusted (manufactured). The fiber processing agent (durable anti-static agent) was used as a processing bath, and a fiber product (bore fleece) was processed as follows.

[Fiber processing]
A polyester bore fleece was used as a processing fiber (fiber product). This polyester bore fleece was immersed in the treatment bath for the above-mentioned processing agent for fibers (durable antistatic agent), squeezed with a mangle at a throttling rate of 70%, and dried with a tenter at 130 ° C. for 4 minutes. Thus, the polyester bore fleece was processed to produce a processed bore fleece. According to calculation results from the amount used, concentration and throttling rate of the processing bath, the processed bore fleece is 0.28% owf, ie, 100 g of bore fleece, the copolymer (polyester resin About 0.28 g).

[Washing resistance test]
The processed bore fleece was subjected to the washing resistance test according to JIS L 0217 103 using the following washing machine and detergent.

Washing machine: Fully automatic washing machine Detergent: Brand name "No phosphorus top" (Lion Corporation)

[Antistatic performance evaluation]
With respect to the processed bore fleece, the antistatic performance was evaluated by the friction voltage measurement method and the half life measurement method in accordance with the JIS L 1094 chargeability test method. The smaller the frictional charge voltage or the shorter the half life, the better the antistatic performance is. The evaluation of the antistatic performance was performed before and after the washing resistance test.

In Table 1 below, the compositions of the copolymers (polyester resins) of Examples 1 to 3 and Comparative Examples 1 to 3 and the results of the evaluation of the antistatic performance of the above-mentioned bore fleeces performed using each of them are shown together. . The results of the antistatic performance evaluation of the (untreated) bore fleece before processing are also shown in Table 1 below.

As shown in Table 1, all of the bore fleeces processed with the processing agent for fibers using the copolymer (polyester resin) of Examples 1 to 3 exhibited high antistatic performance. In addition, since they maintained high antistatic performance even after 5 times of washing, they were shown to have high washing resistance (washing resistance). On the other hand, Comparative Example 1 in which the component (c) was not used in the production of the copolymer (polyester resin), the mass ratio of the components (a) / (c) was 1.5 and 0.5 (both less than 1.7) In Comparative Examples 2 and 3 in which the above were both), the antistatic performance was significantly deteriorated after 5 times of washing, and thus it was shown that the washing resistance (washing durability) was low. In addition, in Comparative Examples 1 to 3, the antistatic performance before washing (0 times) was also inferior to that of Examples.

This application claims priority based on Japanese Patent Application No. 2017-182005 filed on Sep. 22, 2017, the entire disclosure of which is incorporated herein.

Claims (6)

A copolymer obtained by copolymerizing monomers containing the following components (a) to (c) and having a mass ratio of (a) / (c) of 1.7 or more.

(A) at least one aromatic dicarboxylic acid and derivatives thereof (b) a polyol compound (c) represented by the following general formula ^{(1) R 1 R 2 R} 3 R 4 N + X - ··· (1)

In the general formula (1),
R ¹ , R ² , R ³ and R ⁴ are each independently a linear or branched alkyl group having 1 to 30 carbon atoms which may be separated by a linking group, or a linear or branched alkenyl having 2 to 30 carbon atoms And-(AO) _n H,-(AO) _m CH ₃ , or a benzyl group, and at least one hydrogen atom of the benzyl group may be substituted or not substituted with a substituent,
At least two of R ¹ , R ² , R ³ and R ⁴ are — (AO) _n H,
A is one or more selected from linear or branched alkylene groups having 1 to 4 carbon atoms,
m and n respectively represent the average addition mole number of (AO), and are 0.1 to 20, and the sum of n of each-(AO) _n H in the molecule is 2 to 60,
X ^- is an anion. The copolymer according to claim 1, wherein a mass ratio of (b) / {(a) + (c)} in the components (a) to (c) is 0.5 or more. A processing agent for fibers, comprising the copolymer according to claim 1 or 2. An immersion step of immersing the fiber in a liquid containing the processing agent for processing a fiber according to claim 3;
A drying step of drying the fiber immersed in the containing liquid;
A method of processing fibers, comprising: A method of producing a fiber product, comprising the step of processing the fiber according to the processing method according to claim 4. A fiber product produced by the method according to claim 5.