JP2005105424A - Water-repellent and hygroscopic conjugated fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester conjugated fiber having hygroscopicity and water repellency which are functions of wool in combination. <P>SOLUTION: The polyester water-repellent and hygroscopic conjugated fiber is obtained by carrying out core-sheath conjugated spinning of a polymer of a core part and a polymer of a sheath part. The polymer of the core part is a polyester polymer containing a hygroscopic substance and the polymer of the sheath part is a polyester polymer containing a water-repellent substance. The weight ratio of the polymer of the sheath part to the polymer of the core part is within the range of (90:10) to (10:90). A metal organic sulfonate X represented by formula (I) (wherein, R<SB>1</SB>s are each an aromatic hydrocarbon group or the like; X<SB>1</SB>s are each an ester-forming functional group or the like; X<SB>2</SB>s are each an ester-forming functional group or the like; M is an alkali metal atom or the like; and i is 1 or 2 according to M) and a polyoxyalkylene glycol Y represented by HO-(R<SB>2</SB>-O)<SB>j</SB>-H (wherein, R<SB>2</SB>s are each a 2-3C straight chain or branched chain alkylene group; and j is an integer of 2-1,000) are contained within the range satisfying a specific relationship as the hygroscopic substance. A specified compound in an amount of 1-80 pts.wt. based on 100 pts.wt. of the polymer of the sheath part containing the water-repellent substance is contained as the water-repellent substance. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a composite fiber, and more specifically, to a polyester-based water-repellent / hygroscopic composite fiber having both good hygroscopicity and water repellency and having functionality similar to wool.

  Polyester, especially polyethylene terephthalate, is widely used for fibers, films, and other molded articles because of its excellent mechanical, physical and chemical performance.

  However, compared with natural fibers such as cotton, silk, and wool, and semi-synthetic fibers such as rayon and acetate, they have a drawback in terms of functionality such as low hygroscopicity. As an attempt to compensate for this, a method of adding various hygroscopic components to the polymer has been taken, but none of them has been excellent in terms of post-treatment and strength.

  For example, a composite fiber blended with polyoxyalkylene glycol (for example, see Patent Document 1), a hollow fiber made of a fiber-forming polymer having a groove penetrating from the fiber surface to the hollow portion (for example, see Patent Document 2), metal. A microporous fiber or the like (for example, see Patent Document 3) obtained by treating a polyester fiber containing a condensate of a sulfonate compound and a polyoxyalkylene glycol with an alkali has been proposed. Low and comparable to natural fibers are not available.

  Further, as a method for imparting hygroscopicity to synthetic fibers by post-processing, a method for improving hygroscopicity of synthetic fibers by graft polymerization of vinyl carboxylic acid using a radical initiator, an electron beam or the like is also known. (For example, refer to Patent Document 4). However, in this case, there are problems such as fiber strength reduction due to processing, texture hardening, and insufficient moisture absorption durability.

  Thus, it is very difficult to impart a sufficient level of hygroscopicity to synthetic fibers, and it is very difficult to obtain synthetic fibers having mutually contradicting functions such as hygroscopicity and water repellency, and are still practical. There are no examples.

  Moreover, a method for obtaining a synthetic fiber fabric having both hygroscopicity and water repellency is known (see, for example, Patent Document 5). This is a hygroscopic fiber fabric coated with a water-repellent resin on the fiber surface by a treatment such as padding or spraying, which impairs the fiber texture and is inferior in water-repellent washing durability. That is, imparting durable water repellency to the hygroscopic fibers has not been realized.

  On the other hand, wool, which is an example of natural fiber, has two contradictory functions of moisture absorption and water repellency, and is blended with synthetic fiber in order to impart the function and texture to the textile. However, in recent years, there has been a demand for development of recyclable products in response to increasing environmental awareness. In this respect, textiles in which wool is blended with polyester fibers have a problem that depolymerization is difficult.

Japanese Examined Patent Publication No. 39-5214 (Claims) Japanese Patent Publication No. 60-37203 (Claims) JP-A-60-167969 (Claims) JP-A-4-272272 (Claims) JP-A-9-31845 (Claims)

  An object of the present invention is to solve the problems of the prior art and to provide a polyester-based composite fiber that has both moisture absorption and water repellency, which are functions of wool.

That is, the present invention is a water repellent and hygroscopic composite fiber formed by core-sheath composite spinning of a core polymer and a sheath polymer,
(A) The core polymer is a polyester-based polymer containing a hygroscopic substance, the sheath polymer is a polyester-based polymer containing a water-repellent substance, and the weight ratio of the sheath polymer to the core polymer is 90:10. -10: 90,
(B) As the hygroscopic substance, the following formula (I)

［上記式中、Ｒ_１は芳香族炭化水素基又は脂肪族炭化水素基、Ｘ_１はエステル形成性官能基、Ｘ_２はエステル形成性官能基又は水素原子、Ｍはアルカリ金属原子又はアルカリ土類金属原子、ｉはＭがアルカリ金属原子のときには１、アルカリ土類金属原子のときには２である。］
で示される有機スルホン酸金属塩Ｘと、下記式（ＩＩ）

[In the above formula, R ₁ is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, X ₁ is an ester-forming functional group, X ₂ is an ester-forming functional group or a hydrogen atom, and M is an alkali metal atom or alkaline earth. The metal atom, i, is 1 when M is an alkali metal atom and is 2 when M is an alkaline earth metal atom. ]
An organic sulfonic acid metal salt X represented by formula (II):

［上記式中、Ｒ_２は炭素数２〜３の直鎖状又は分岐鎖状のアルキレン基であり、ｊは２〜１０００の整数である。］
で示されるポリオキシアルキレングリコールＹが、当該芯部ポリマー中、下記数式（１）、（２）、（３）を満たす範囲で含有し、

[Wherein R ₂ is a linear or branched alkylene group having 2 to 3 carbon atoms, and j is an integer of 2 to 1000. ]
In the core polymer, the polyoxyalkylene glycol Y represented by the formula (1), (2), and (3) are contained in a range that satisfies the following:

［上記数式中、ｘとｙとは、それぞれ、吸湿性物質を含有するポリエステル系ポリマーの１００重量部に対して、有機スルホン酸金属塩Ｘが含有している重量部とポリオキシアルキレングリコールＹが含有している重量部を表す。］
（Ｃ）当該撥水性物質として、下記式（ＩＩＩ）で示されるエステル反応性シリコーン、下記式（ＩＶ）で示されるダイマー酸、下記式（Ｖ）で示されるダイマー酸、下記式（ＶＩ）で表されるダイマージオールおよび下記式（ＶＩＩ）で表されるダイマージオールからなる群のより少なくとも１種選ばれる化合物を、前記撥水性物質を含有する鞘部ポリマーの１００重量部に対し、１〜８０重量部含有する撥水吸湿複合繊維である。

[In the above formula, x and y are respectively the parts by weight of the organic sulfonic acid metal salt X and the polyoxyalkylene glycol Y with respect to 100 parts by weight of the polyester polymer containing the hygroscopic substance. Represents parts by weight. ]
(C) As the water-repellent substance, an ester-reactive silicone represented by the following formula (III), a dimer acid represented by the following formula (IV), a dimer acid represented by the following formula (V), and the following formula (VI) 1 to 80 of the compound selected from the group consisting of the dimer diol represented by the following formula (VII) and 1 part by weight of the sheath polymer containing the water-repellent substance. It is a water repellent and hygroscopic composite fiber containing parts by weight.

［上記式中、Ｍｅはメチル基を表し、ｎは１〜１００の整数である。］

[In the above formula, Me represents a methyl group, and n is an integer of 1 to 100. ]

[上記式中、Ｒ_３とＲ_４およびＲ_７とＲ_８は同一もしくは異なるアルキル基を、Ｒ_５とＲ_６およびＲ_９とＲ_１０は同一もしくは異なるアルキレン基であり、Ｒ_３〜Ｒ_６およびＲ_７〜Ｒ_１０の炭素数の合計は２４〜３６の範囲である。また式（Ｖ）中、六員環内の点線の円は六員環内に０〜３個の不飽和結合があることを表す。]

[In the above formula, R ₃ and R ₄ and R ₇ and R ₈ are the same or different alkyl groups, R ₅ and R ₆ and R ₉ and R ₁₀ are the same or different alkylene groups, and R _{3 to} R ₆ and The total number of carbon atoms of R _{7 to} R ₁₀ is in the range of 24 to 36. In the formula (V), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]

[上記式中、Ｒ_１１とＲ_１２およびＲ_１５とＲ_１６は同一もしくは異なるアルキル基を、Ｒ_１３とＲ_１４およびＲ_１７とＲ_１８は同一もしくは異なるアルキレン基であり、Ｒ_１１〜Ｒ_１４およびＲ_１５〜Ｒ_１８の炭素数の合計は２４〜３６の範囲である。また式（ＶＩＩ）中、六員環内の点線の円は六員環内に０〜３個の不飽和結合があることを表す。]

[In the above formula, R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ are the same or different alkyl groups, R ₁₃ and R ₁₄ and R ₁₇ and R ₁₈ are the same or different alkylene groups, and R _{11 to} R ₁₄ and The total number of carbon atoms of R _{15 to} R ₁₈ is in the range of 24 to 36. In the formula (VII), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]

  According to the present invention, it is possible to provide a polyester composite fiber having both durable hygroscopicity and water repellency. Therefore, it is possible to avoid problems such as fiber strength reduction, texture hardening, and inferior durability and hygroscopicity, which have been regarded as problems in the past.

  The moisture-absorbing and water-repellent composite fiber in the present invention uses a polyester polymer containing a hygroscopic substance as a core polymer (hereinafter referred to as polymer A), and a polyester polymer containing a water-repellent substance as a sheath polymer (hereinafter referred to as polymer B). The core-sheath composite spinning is performed in a weight ratio of the sheath polymer to the core polymer in the range of 90:10 to 10:90.

  This hygroscopic substance contains an organic sulfonic acid metal salt X represented by the above formula (I) and a polyoxyalkylene glycol Y represented by the above formula (II). The water-repellent substance is represented by the ester-reactive silicone represented by the formula (III), the dimer acid represented by the formula (IV), the dimer acid represented by the formula (V), and the formula (VI). 1 to 80 parts by weight of the compound selected from the group consisting of the dimer diol and the dimer diol represented by the above formula (VII) with respect to 100 parts by weight of the sheath polymer.

  When the weight ratio of the sheath polymer to the core polymer is larger than 90:10, the sheath polymer cracks and the water repellency disappears due to the hygroscopic swelling of the core polymer A. The functions of water repellency and moisture absorption cannot be expressed. On the other hand, when the ratio of the sheath polymer is smaller than 10:90, the improvement of the hygroscopic performance is hardly recognized and the hygroscopic water repellent fiber does not function. More preferably, the weight ratio is in the range of 70:30 to 30:70.

(About polyester polymers)
The polyester polymer used in the present invention comprises polyalkylene terephthalate having a terephthalic acid component as a main acid component and an alkylene glycol component as a main diol component. The term “main” means that a bifunctional carboxylic acid component other than alkylene terephthalate acid and a diol component other than alkylene glycol may be copolymerized within a range in which the effects of the present invention are not substantially impaired. To do. Specifically, it is preferable that 70 mol% or more of all repeating units is composed of alkylene terephthalate.

  Examples of the acid component other than the terephthalic acid component which is the main acid component include isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyloxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, and adipic acid. And aromatic and aliphatic dicarboxylic acid components such as sebacic acid and 1,4-cyclohexanedicarboxylic acid.

  Examples of alkylene glycol and / or other diol components as the main diol component include tetramethylene glycol, trimethylene glycol, ethylene glycol, cyclohexane-1,4-dimethanol, neopentyl glycol, bisphenol A, and bisphenol S. And aliphatic, alicyclic and aromatic diol compounds and polyoxyalkylene glycols.

  Furthermore, within the range in which the effects of the present invention are not substantially impaired, a tricarboxylic acid or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid, or a tricarboxylic acid such as glycerin, trimethylolpropane, or pentaerythritol. A functional or higher polyol may be used as a copolymerization component.

(About hygroscopic substances)
In the present invention, “containing a hygroscopic substance” includes not only containing the hygroscopic substance as a blend component but also including it in the polymer A by copolymerization. For example, when the organic sulfonic acid metal salt X represented by the above formula (I) is contained as a hygroscopic substance, the organic sulfonic acid metal salt represented by the above formula (I) is included in addition to including this compound as a blend component. It also means that the structural unit derived from X is contained in polymer A. Such a situation is the same for the polyoxyalkylene glycol Y represented by the formula (II).

Regarding the organic sulfonic acid metal salt X, R ₁ in the following formula (I) is an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

［上記式中、Ｒ_１は芳香族炭化水素基又は脂肪族炭化水素基、Ｘ_１はエステル形成性の官能基、Ｘ_２はエステル形成性官能基又は水素原子、Ｍはアルカリ金属原子又はアルカリ土類金属原子、ｉはＭがアルカリ金属原子のときには１、アルカリ土類金属原子のときには２である。］
Ｘ_１とＸ_２とについては、Ｘ_１はポリエステルに対して反応しエステルを形成しうるエステル形成性官能基、Ｘ_２はエステル形成性官能基又は水素原子である。エステル形成性官能基は、一般的にはヒドロキシル基、カルボキシル基またはそれらの低級エステルを表す。Ｍは、Ｎａ、Ｋ、Ｌｉなどのアルカリ金属原子、またはＭｇ、Ｃａなどのアルカリ土類金属原子であり、なかでもＮａ、Ｋであることが好ましい。ｉは、Ｍがアルカリ金属原子の時には１、アルカリ土類金属原子の時には２である。

[In the above formula, R ₁ is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, X ₁ is an ester-forming functional group, X ₂ is an ester-forming functional group or a hydrogen atom, and M is an alkali metal atom or an alkaline earth. A metal atom, i is 1 when M is an alkali metal atom, and 2 when M is an alkaline earth metal atom. ]
Regarding X ₁ and X ₂ , X ₁ is an ester-forming functional group capable of reacting with a polyester to form an ester, and X ₂ is an ester-forming functional group or a hydrogen atom. The ester-forming functional group generally represents a hydroxyl group, a carboxyl group or a lower ester thereof. M is an alkali metal atom such as Na, K, Li or the like, or an alkaline earth metal atom such as Mg, Ca. Among them, Na and K are preferable. i is 1 when M is an alkali metal atom, and 2 when M is an alkaline earth metal atom.

  Such organic sulfonic acid metal salt X can be used alone or as a mixture of two or more thereof. Preferred specific examples include dimethyl 5-sodium sulfoisophthalate, dimethyl 5-potassium sulfoisophthalate, and 5-lithium sulfoisophthalate. Dimethyl acid, 5-sodium sulfoisophthalic acid bis (p-hydroxyethyl) ester, 5-potassium sulfoisophthalic acid bis (p-hydroxyethyl) ester, 5-lithium sulfoisophthalic acid bis (p-hydroxyethyl) ester, etc. be able to.

For the polyoxyalkylene glycol Y, in the following formula (II), R ₂ is a linear or branched alkylene group having 2 to 3 carbon atoms, specifically an ethylene group or a 1,3-propylene group. 1,2-propylene group.

［上記式中、Ｒ_２は炭素数２〜３の直鎖状又は分岐鎖状のアルキレン基であり、ｊは２〜１０００の整数である。］
すなわちポリエチレングリコール、ポリプロピレングリコールを用いることが好ましい。ｊは２〜１０００の整数であり、ｊが１０００を超えると共重合し難く、吸湿の洗濯耐久性が低下することが多い。ｊは２〜５００の整数であることが好ましい。より好ましくはｊが１０〜３００の範囲であり、更に好ましくは２０〜１００の範囲である。

[Wherein R ₂ is a linear or branched alkylene group having 2 to 3 carbon atoms, and j is an integer of 2 to 1000. ]
That is, it is preferable to use polyethylene glycol or polypropylene glycol. j is an integer of 2 to 1000, and when j exceeds 1000, it is difficult to copolymerize and the hygroscopic washing durability often decreases. j is preferably an integer of 2 to 500. More preferably, j is in the range of 10 to 300, and more preferably in the range of 20 to 100.

  The organic sulfonic acid metal salt X and the polyoxyalkylene glycol Y are preferably copolymerized in the polymer A so that the hygroscopic washing durability does not deteriorate.

  The ratio of the organic sulfonic acid metal salt X in the polymer A is preferably in the range of the following formula (1).

［上記数式中、ｘとｙとは、それぞれ、吸湿性物質を含有するポリエステル系ポリマーの１００重量部に対して、有機スルホン酸金属塩Ｘが含有している重量部とポリオキシアルキレングリコールＹが含有している重量部を表す。］
ｘ＞１５であるとポリマーの増粘が著しく、製糸に適切なポリマーが得られ難い。０≦ｘ≦１０であることがより好ましく、１≦ｘ≦８であることが更に好ましく、３≦ｘ≦５であることが更により好ましい。ポリマーＡ中におけるポリオキシアルキレングリコールＹの割合は、上記数式(２)の範囲にあることが好ましい。ｙ＞８０であると、ポリマーの溶融粘度が著しく下がり、形成に適したポリマーが得られ難い。２０≦ｙ≦７０であることが好ましく、５０≦ｙ≦６０あることが更に好ましい。

[In the above formula, x and y are respectively the parts by weight of the organic sulfonic acid metal salt X and the polyoxyalkylene glycol Y with respect to 100 parts by weight of the polyester polymer containing the hygroscopic substance. Represents parts by weight. ]
When x> 15, the viscosity of the polymer is remarkably increased, and it is difficult to obtain a polymer suitable for spinning. More preferably, 0 ≦ x ≦ 10, still more preferably 1 ≦ x ≦ 8, and still more preferably 3 ≦ x ≦ 5. The ratio of polyoxyalkylene glycol Y in polymer A is preferably in the range of the above formula (2). When y> 80, the melt viscosity of the polymer is remarkably lowered, and it is difficult to obtain a polymer suitable for formation. It is preferable that 20 ≦ y ≦ 70, and more preferably 50 ≦ y ≦ 60.

  The above x and y mean the weight part of the organic sulfonic acid metal salt X and the weight part of the polyoxyalkylene glycol Y with respect to 100 parts by weight of the polymer A, respectively. It is preferable that it exists in the range of 3). When 4x + y <10, sufficient hygroscopicity may not be exhibited, and when 150> 4x + y, the spinning condition is deteriorated, and a good fiber form may not be obtained. More preferably, the range is 15 ≦ 4x + y ≦ 120, and still more preferably the range is 20 ≦ 4x + y ≦ 100. Further, these x and y values are the values of the compounds as they are when they are included as simple blend components. Moreover, when it is contained as a copolymerization component, it is a value as a compound before copolymerization.

(About water-repellent substances)
In the present invention, “containing a water-repellent substance” includes not only containing a water-repellent substance as a blend component but also including by copolymerization. More specifically, for example, containing an ester-reactive silicone represented by the following formula (III) as a water-repellent substance includes not only this compound as a blending component but also both ends of the ester-reactive silicone. It also means that the structural unit from which hydrogen is removed is contained in the polymer B.

［上記式中、Ｍｅはメチル基を表し、ｎは１〜１００の整数である。］
このような事情は、上記式(ＩＶ)、（Ｖ）、（ＶＩ）、(ＶＩＩ)で表される化合物についても同様である。上記式（ＩＩＩ）で表されるエステル反応性シリコーンの具体例としては、市販されているチッソ社製サイラプレーン（商品名）等が挙げられる。

[In the above formula, Me represents a methyl group, and n is an integer of 1 to 100. ]
Such circumstances also apply to the compounds represented by the above formulas (IV), (V), (VI), and (VII). Specific examples of the ester-reactive silicone represented by the above formula (III) include commercially available Silaplane (trade name) manufactured by Chisso Corporation.

  The dimer acid and dimer diol used in the present invention are compounds represented by the following general formulas (IV) to (VII).

[上記式中、Ｒ_３とＲ_４およびＲ_７とＲ_８は同一もしくは異なるアルキル基を、Ｒ_５とＲ_６およびＲ_９とＲ_１０は同一もしくは異なるアルキレン基であり、Ｒ_３〜Ｒ_６およびＲ_７〜Ｒ_１０の炭素数の合計は２４〜３６の範囲である。また式（Ｖ）中、六員環内の点線の円は六員環内に０〜３個の不飽和結合があることを表す。]

[In the above formula, R ₃ and R ₄ and R ₇ and R ₈ are the same or different alkyl groups, R ₅ and R ₆ and R ₉ and R ₁₀ are the same or different alkylene groups, and R _{3 to} R ₆ and The total number of carbon atoms of R _{7 to} R ₁₀ is in the range of 24 to 36. In the formula (V), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]

[上記式中、Ｒ_１１とＲ_１２およびＲ_１５とＲ_１６は同一もしくは異なるアルキル基を、Ｒ_１３とＲ_１４およびＲ_１７とＲ_１８は同一もしくは異なるアルキレン基であり、Ｒ_１１〜Ｒ_１４およびＲ_１５〜Ｒ_１８の炭素数の合計は２４〜３６の範囲である。また式（ＶＩＩ）中、六員環内の点線の円は六員環内に０〜３個の不飽和結合があることを表す。]
上記式(ＩＶ)、（Ｖ）、（ＶＩ）、(ＶＩＩ)中のＲ_３〜Ｒ_６、Ｒ_７〜Ｒ_１０、Ｒ_１１〜Ｒ_１４、及びＲ_１５〜Ｒ_１８それぞれの官能基群について炭素数の合計は２４〜３６の範囲である。この範囲より小さいと十分な撥水性を発現しない場合があり、この範囲より大きいと共重合をしない、若しくはポリエステル系ポリマーとの相溶性が悪い場合がでてくる。六員環内には不飽和結合が０〜３個あるが、好ましくは０〜２個である。

[In the above formula, R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ are the same or different alkyl groups, R ₁₃ and R ₁₄ and R ₁₇ and R ₁₈ are the same or different alkylene groups, and R _{11 to} R ₁₄ and The total number of carbon atoms of R _{15 to} R ₁₈ is in the range of 24 to 36. In the formula (VII), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]
Carbon for each functional group of R _{3 to} R ₆ , R _{7 to} R ₁₀ , R _{11 to} R ₁₄ , and R _{15 to} R _{18 in the} above formulas (IV), (V), (VI), and (VII) The sum of the numbers is in the range of 24-36. If it is smaller than this range, sufficient water repellency may not be exhibited, and if it is larger than this range, copolymerization may not occur or compatibility with the polyester polymer may be poor. There are 0 to 3 unsaturated bonds in the 6-membered ring, preferably 0 to 2.

  The dimer acid represented by the above formula (IV) or (V) can be obtained by dimerizing a carboxylic acid having 18 carbon atoms such as linoleic acid or linolenic acid or an alcohol ester thereof. . Specific examples of dimer acid include commercially available Enpol (trade name) manufactured by Cognis. The dimer diol represented by the above formula (VI) or (VII) is a dimer obtained after removing by-products such as trimer acid and monomer acid from a low polymer of unsaturated fatty acid by separation and hydrogenation. It is an aliphatic both terminal diol obtained by hydrogenating an acid. Specific examples of dimer-diol include commercially available Sobamol (trade name) manufactured by Cognis.

  These compounds are preferably contained in an amount of 1 to 80 parts by weight with respect to 100 parts by weight of the polymer B containing a water repellent substance. When the amount is less than 1 part by weight, sufficient water repellency is not exhibited. When the amount exceeds 80 parts by weight, the viscosity of the polymer is remarkably lowered and spinning becomes difficult in many cases. More preferably, it is 2-30 weight part, More preferably, it is 4-6 weight part.

  The compounds represented by the above formulas (III), (IV), (V), (VI), (VII) are copolymerized in the polymer B so that the durability does not decrease. This is preferable. In addition, the “parts by weight” of the compounds represented by the above formulas (III), (IV), (V), (VI), (VII) is a value as a compound as it is when included as a simple blend component. It is. Moreover, when it is contained as a copolymerization component, it is a value as a compound before copolymerization.

  The composition of polymer A and polymer B thus obtained preferably has an intrinsic viscosity of usually 0.4 to 1.5 dl / g. When the intrinsic viscosity is less than 0.4 dl / g, there are many cases where it is not preferable because there is a decrease in physical properties such as a decrease in impact strength and a decrease in stretch moldability. When the intrinsic viscosity exceeds 1.5 dl / g, productivity is deteriorated and stretch moldability is often lowered, which is not preferable.

(About polymer production method)
What is necessary is just to synthesize | combine the polymer A and polymer B in this invention by the arbitrary methods well-known as a manufacturing method of polyester. Usually, a method of directly esterifying terephthalic acid and alkylene glycol, a method of transesterifying a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and alkylene glycol, or a method of reacting terephthalic acid and alkylene oxide The first stage reaction is first performed to produce a glycol ester of terephthalic acid and / or a low polymer thereof. This first stage reaction may be carried out in the presence of a transesterification catalyst, if necessary. Subsequently, the first stage reaction product is heated under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a desired degree of polymerization is produced. At this time, the above-described hygroscopic substance and water-repellent substance may be supplied into the reaction system at an appropriate stage before the completion of production. This appropriate stage can easily be found by trial and error.

  The reaction temperature during the first stage reaction (transesterification reaction) is usually 180 to 230 ° C., and the reaction pressure is normal pressure to 0.3 MPa. The reaction temperature during the second stage reaction (polycondensation reaction) is usually 200 to 260 ° C., and the reaction pressure is usually 60 to 0.1 kPa. Such a transesterification reaction and polycondensation reaction may be performed in one step or in multiple steps.

  As the transesterification catalyst used in these reaction steps, alkali metal salts such as sodium, alkaline earth metal salts such as magnesium and calcium, and metal compounds such as titanium, zinc and manganese are preferably used. As the polycondensation catalyst, it is preferable to use a germanium compound, an antimony compound, a titanium compound, a cobalt compound, or a tin compound. The amount of the catalyst used is not particularly limited as long as it is a necessary amount for proceeding the transesterification reaction and polycondensation reaction, and a plurality of catalysts can be used in combination.

  It is also preferable to add a stabilizer in any of the first stage reaction, the second stage reaction, or after the completion of the reaction. As the stabilizer, phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, or triphenyl phosphate, phosphites such as triphenyl phosphite or trisdodecyl phosphite, methyl acid phosphate, dibutyl phosphate, monobutyl Phosphate acid phosphate ester, phosphoric acid, phosphorous acid, hypophosphorous acid, or phosphorous compounds such as polyphosphoric acid, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- A hindered phenol-based antioxidant such as butyl-4-hydroxybenzyl) benzene, a sulfur-based antioxidant, or an amine-based antioxidant is preferred.

(About composite fibers)
The water repellent and hygroscopic composite fiber according to the present invention can be produced by a method similar to the method applied to a commonly known polyester composite fiber. For example, a method of melt spinning at a speed of 500 m to 2500 m / min, stretching and heat treatment, a method of melt spinning at a speed of 1500 m to 5000 m / min, and performing stretching and false twisting simultaneously or subsequently, etc. It can preferably be employed. Here, the roller temperature of the heat setting in the stretching step is preferably 130 to 170 ° C. When the temperature is within this range, the heat setting property is sufficient and the fiber is not melt cut. The “core sheath” structure in the present invention may be a single core sheath or a multicore sheath. Here, “single core” means a structure having only one core in the sheath, and “multi-core” means a structure having a plurality of cores. In the latter case, a so-called sea-island structure may be used. The arrangement of the multicores in the fiber cross section may or may not be symmetric. In the case of a sea-island structure, the “island” portion corresponds to the “core”. The cross-sectional shape of the fiber is not particularly limited, and may be an elliptical cross section, a triangular cross section, or a star cross section in addition to a circular cross section.

  With respect to hygroscopicity, the hygroscopic water-repellent core-sheath composite fiber in the present invention has a moisture absorption rate by a saturated moisture absorption method in the case of a fabric of 35 ° C. and a saturated equilibrium moisture absorption rate of 1 to 50 after being held for 24 hours in a 95% Rh environment. % Range can be realized. Although it is possible to make the saturation equilibrium moisture absorption rate exceed 50%, it is not preferable because the moldability of the polymer and the fiber processing stability are remarkably lowered. From the point of practicality, the range of 2 to 30% is preferable.

  Regarding water repellency, the moisture-absorbing and water-repellent core-sheath composite fiber in the present invention may be a water-repellent and moisture-absorbing core-sheath fiber that has a water-repellent retention time of 15 minutes or more according to the water-drop-drop water-repellent evaluation method when used as a fabric. it can. With a water repellent holding time of less than 15 minutes, it is at the same level as ordinary polyester fibers, and although it is hydrophobic, it cannot be said that it exhibits a water repellent function. A moisture-absorbing and water-repellent fiber that exhibits a water-repellent retention time of 20 minutes or more is preferable, and a moisture-absorbing and water-repellent fiber that exhibits a water-repellent retention time of 30 minutes or more is more preferable. The water-repellent hygroscopic core-sheath fiber according to the present invention can realize such a level of water-repellent holding time.

  The yarn form of the composite fiber of the present invention thus obtained may be either a filament or a staple, and the total yarn fineness, single yarn fineness, number of twists, number of entanglements, etc. are appropriately set according to the intended use of the fiber can do.

  The fiber of the present invention can also be used for spun yarn. The fabric is a woven fabric, a knitted fabric, or a nonwoven fabric mainly composed of the composite fiber obtained as described above. The filaments, staples, spun yarns, woven fabrics, knitted fabrics, and nonwoven fabrics mentioned here can be prepared by almost the same method as that produced using ordinary polyester fibers. In addition, this fiber / fabric may use 100% of the above-mentioned composite fiber, but may be a fiber, mixed fiber, mixed fiber, or knitted fiber with other fibers. Here, when used in combination with other fibers, when used as a composite yarn, it may be a mixed fiber, a composite false twisted yarn, such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, etc. Polyester fibers, nylon fibers such as nylon 6 and nylon 66, polyolefin fibers such as polyethylene and polypropylene, acrylic fibers, fibers such as para-type or meta-type aramid, and modified and / or composite fibers thereof, further natural fibers, It can be freely selected from recycled fiber, semi-synthetic fiber and the like. At this time, the production method of the spun yarn, the woven fabric, the knitted fabric and the nonwoven fabric can be produced under the same conditions as those for a normal polyester fiber. Even if it is slightly different from the normal conditions, those skilled in the art can easily find the optimum production conditions by trial and error. The conditions for blending with other fibers, blending, knitting, and knitting can also be manufactured under the same conditions as those used for ordinary polyester fibers.

  However, the present invention provides a polyester fiber with an excellent function of water repellency and moisture absorption similar to natural fibers / wool, and preferably, as a substitute for polyester / wool blending, blending, blending, Textiles, knitting, etc. are preferred. In this way, the present invention is useful as it can avoid the problems associated with separating wool in the chemical recycling process by depolymerization and can provide a desirable form as an easily recycled fiber product.

Hereinafter, the present invention will be described in more detail with reference to examples. Each value in the examples was determined according to the following method.
(A) Saturated moisture absorption The sample tubular knitted fabric was dried at 105 ° C. for 2 hours and then left in a desiccator maintained at 35 ° C. and 95% RH for 24 hours. It calculated | required according to following Numerical formula (4) from the weight of the cylinder knitted fabric before and behind leaving.

（イ）撥水評価方法
サンプル筒編地を二重にし、１００ｍｌのビーカーに輪ゴムでたるみのない様に固定した後、０．５ｍｌの純水を滴下ロートを用いて、静かに繊維表面に滴下した。繊維表面の水分が布帛へ染み込み、水滴のふくらみがなくなった状態までの時間を撥水保持時間として測定した。この方法を水滴滴下撥水評価方法という。
（ウ）ポリマーの固有粘度
３５℃のオルソクロロフェノール溶液で測定した値から求めた。
（エ）ポリマー組成分析評価
ポリマーサンプルを重水素化トリフルオロ酢酸／重水素化クロロホルム＝１／1混合溶媒に溶解後、日本電子(株)製ＪＥＯＬ Ａ−６００ 超伝導ＦＴ−ＮＭＲを用いて核磁気共鳴スペクトル（¹Ｈ−ＮＭＲ）を測定して、そのスペクトルパターンから常法に従って、有機スルホン酸金属塩、ポリオキシアルキレングリコール、エステル反応性シリコーンダイマー酸、ダイマージオールの成分含有量を定量した。

(A) Water repellency evaluation method Double the sample tube knitted fabric and fix it in a 100 ml beaker with rubber band so that there is no slack, then gently drop 0.5 ml of pure water onto the fiber surface using a dropping funnel. did. The time until the moisture on the fiber surface soaked into the fabric and the swell of water droplets disappeared was measured as the water repellent retention time. This method is referred to as a water drop dropping water repellency evaluation method.
(C) It was determined from the value measured with an orthochlorophenol solution having an intrinsic viscosity of 35 ° C. of the polymer.
(D) Polymer composition analysis evaluation After dissolving a polymer sample in deuterated trifluoroacetic acid / deuterated chloroform = 1/1 mixed solvent, JEOL A-600 superconducting FT-NMR manufactured by JEOL Ltd. was used as a nucleus. The magnetic resonance spectrum ( ¹ H-NMR) was measured, and the component contents of the organic sulfonic acid metal salt, polyoxyalkylene glycol, ester-reactive silicone dimer acid, and dimer diol were quantified from the spectrum pattern according to a conventional method.

  Furthermore, for organic sulfonic acid metal salts and ester-reactive silicones, polymer samples were heated and melted on an aluminum plate, and then a test molded body having a flat surface was prepared with a compression press machine. Quantification was also performed by measuring the content of sulfur and silicon elements using a 3270E type manufactured by company. Whether the copolymer is copolymerized or contained was evaluated from the temperature showing an endothermic peak by DSC measurement.

[Reference Example 1] (Production of polymer A 1)
100 parts by weight of dimethyl terephthalate, 64 parts by weight of tetramethylene glycol, 10 parts by weight of ethylene glycol, 10 parts by weight of sodium dimethyl-5-sulfoisophthalate as organic sulfonic acid metal salt X, and polyethylene as polyoxyalkylene glycol Y While charging 100 parts by weight of glycol (number average molecular weight 4000) into a reactor, adding tetrabutyl titanate and sodium acetate trihydrate as a transesterification catalyst, and distilling off by-produced methanol out of the system, A transesterification reaction was carried out to complete the transesterification reaction.

  Subsequently, the temperature was raised to 250 ° C., and the reaction product was subjected to a polycondensation reaction under high temperature and high vacuum to obtain a polymer having an intrinsic viscosity of 0.82 dl / g. As a result of analysis, 4 parts by weight of sodium dimethyl-5-sulfoisophthalate is copolymerized with respect to 100 parts by weight of polymer A, and 50 parts by weight of polyethylene glycol (number average molecular weight 4000) is also contained in the form of copolymerization. It was.

[Reference Example 2] (Production of polymer A 2)
In Reference Example 1, a polymer is produced in the same manner except that the amount of polyethylene glycol is changed so that 30 parts by weight of polyethylene glycol (number average molecular weight 4000) is contained in the form of copolymer with respect to 100 parts by weight of polymer A. As a result, a polymer having an intrinsic viscosity of 0.85 dl / g was obtained.

[Reference Example 3] (Production of polymer B 1)
100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol and 0.031 parts of manganese acetate tetrahydrate are charged into a reactor, and the temperature is raised from 140 ° C. to 240 ° C. over 3 hours in a nitrogen gas atmosphere. The transesterification was carried out while distilling methanol out of the system. After completion of the transesterification reaction, 0.024 part of phosphoric acid as stabilizer and 0.04 part of antimony trioxide as a polycondensation reaction catalyst were added, and further ester reactive silicone (molecular weight 1000, Silaplane FM manufactured by Chisso Corporation). -4411 (trade name)) 5 parts by weight were immediately added, the temperature was immediately raised to 285 ° C., and a polycondensation reaction was performed under reduced pressure to obtain a copolymer. As a result of analysis, 5 parts by weight of the ester-reactive silicone was contained in the form of copolymer with respect to 100 parts by weight of the polymer B.

[Reference Example 4] (Production of polymer B 2)
In the same manner as in Reference Example 3, a copolymer was obtained using 3 parts by weight of the same type of ester reactive silicone instead of 5 parts by weight of ester reactive silicone. As a result of analysis, 3 parts by weight of the ester-reactive silicone was contained in the form of copolymer with respect to 100 parts by weight of the polymer B.

[Reference Example 5] (Production of polymer B 3)
In the same manner as in Reference Example 3, a copolymer was obtained using 5 parts by weight of dimer acid (Empol 1008 {trade name} manufactured by Cognis) instead of 5 parts by weight of ester-reactive silicone (Reference Example). 5). It was also confirmed that the functional group corresponding to R _{3 to} R ₆ and R _{7 to} R ₁₀ had a carbon number in the range of 24 to 36. As a result of analyzing the obtained polymer, 5 parts by weight of dimer acid was contained in the form of copolymer with respect to 100 parts by weight of polymer B.

[Reference Example 6] (Production of polymer B 4)
Further, in the same manner as in Reference Example 3, a copolymer was obtained using 5 parts by weight of dimer diol (Sobamol 650NS {trade name} manufactured by Cognis) instead of 5 parts by weight of the ester-reactive silicone. It was also confirmed that the functional groups corresponding to R _{11 to} R ₁₄ and R _{15 to} R ₁₈ had a carbon number in the range of 24 to 36. As a result of analyzing the obtained polymer, 5 parts by weight of dimer-diol was contained in the form of copolymer with respect to 100 parts by weight of polymer B.

[Reference Example 7] (Production of polymer B 5)
A polyester containing no hygroscopic substance and no water-repellent substance was produced in the same manner as in Reference Example 3 except that no ester-reactive silicone was added.

[Examples 1 to 5, 7 and Comparative Examples 1 to 3]
(Core-sheath composite spinning)
After the polymers A and B were dried, each was melted by a screw type extruder and supplied to a two-component composite spinning head via a gear pump. As the sheath polymer (polymer B) in Comparative Example 3, a polymer containing no water-repellent substance was used in place of the polymer.

  The supply amount of the core polymer (Polymer A) and the sheath polymer (Polymer B) was set so that the core / sheath weight ratio of the spun yarn would be the value shown in Table 1. Regarding the cross-sectional shape of the obtained fiber, it was a single-core core-sheath structure comprising a circular core part and a concentric sheath part.

  The melt polymer of the core part and the sheath part supplied at the same time was extruded at 285 ° C. using a composite spinneret having 24 circular composite spinning holes having a nozzle diameter of 0.3 mm, and then 1500 m / min through a goded roll. It was wound up at a speed of once. Subsequently, a 50 denier / 24 filament drawn yarn was obtained by drawing heat treatment with a heating roller at 90 ° C. and a drawing superheater at 170 ° C. at a draw ratio such that the obtained drawn yarn had an elongation of 35%.

(Fabric creation)
Fabric was made using a small cylinder knitting machine (CR-B type: needle 3.5 inches × 220 needles) manufactured by Koike Seisakusho.

  Table 1 shows the types and amounts of the hygroscopic substance and the water-repellent substance used in Examples and Comparative Examples, and Table 2 shows the evaluation results (water repellency retention time, saturated moisture absorption rate) of the fabric. In Table 1, the numbers of the core and the sheath mean parts by weight with respect to 100 parts by weight of the polymer A or the polymer B.

[Example 6]
In Example 1, a composite fiber and a fabric were prepared in the same manner except that spinning was performed using a spinneret having three cores, and a multicore core-sheath composite fiber and its fabric were obtained. It was. The obtained fabric was evaluated for water repellency retention time and saturated moisture absorption.

  According to the present invention, it is possible to provide a polyester composite fiber having both durable hygroscopicity and water repellency. Accordingly, problems such as a decrease in fiber strength, texture hardening, or inferior durability and hygroscopicity due to processing, which have been regarded as problems in the past, can be avoided. In addition, it is possible to provide fibers that have both moisture absorption and water repellency, which are the functions of wool, with polyester alone, so that it is possible to provide easily recyclable fiber products that have the functions of conventional polyester and wool blend fiber products. . In these respects, the industrial utility value of the present invention is extremely large.

Claims (4)

In the water-repellent and hygroscopic composite fiber formed by core-sheath composite spinning of the core polymer and the sheath polymer,
(A) The core polymer is a polyester-based polymer containing a hygroscopic substance, the sheath polymer is a polyester-based polymer containing a water-repellent substance, and the weight ratio of the sheath polymer to the core polymer is 90:10. -10: 90,
(B) As the hygroscopic substance, the following formula (I)

[In the above formula, R ₁ is an aromatic hydrocarbon group or an aliphatic hydrocarbon group, X ₁ is an ester-forming functional group, X ₂ is an ester-forming functional group or a hydrogen atom, and M is an alkali metal atom or alkaline earth. The metal atom, i, is 1 when M is an alkali metal atom and is 2 when M is an alkaline earth metal atom. ]
An organic sulfonic acid metal salt X represented by formula (II):

[Wherein R ₂ is a linear or branched alkylene group having 2 to 3 carbon atoms, and j is an integer of 2 to 1000. ]
In the core polymer, the polyoxyalkylene glycol Y represented by the formula (1), (2), and (3) are contained in a range that satisfies the following:

[In the above formula, x and y are respectively the parts by weight of the organic sulfonic acid metal salt X and the polyoxyalkylene glycol Y with respect to 100 parts by weight of the polyester polymer containing the hygroscopic substance. Represents parts by weight. ]
(C) As the water-repellent substance, an ester-reactive silicone represented by the following formula (III), a dimer acid represented by the following formula (IV), a dimer acid represented by the following formula (V), and the following formula (VI) 1 to 80 weights of the compound selected from the group consisting of the dimer diol represented by the dimer diol represented by the following formula (VII) and 100 parts by weight of the sheath polymer containing the water-repellent substance. Water repellent and hygroscopic composite fiber containing part.

[In the above formula, Me represents a methyl group, and n is an integer of 1 to 100. ]

[In the above formula, R ₃ and R ₄ and R ₇ and R ₈ are the same or different alkyl groups, R ₅ and R ₆ and R ₉ and R ₁₀ are the same or different alkylene groups, and R _{3 to} R ₆ and The total number of carbon atoms of R _{7 to} R ₁₀ is in the range of 24 to 36. In the formula (V), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]

[In the above formula, R ₁₁ and R ₁₂ and R ₁₅ and R ₁₆ are the same or different alkyl groups, R ₁₃ and R ₁₄ and R ₁₇ and R ₁₈ are the same or different alkylene groups, and R _{11 to} R ₁₄ and The total number of carbon atoms of R _{15 to} R ₁₈ is in the range of 24 to 36. In the formula (VII), a dotted circle in the six-membered ring indicates that there are 0 to 3 unsaturated bonds in the six-membered ring. ]   The water-repellent and hygroscopic composite fiber according to claim 1, wherein the core-sheath structure is a single-core core-sheath composite fiber.   The water-repellent and hygroscopic composite fiber according to claim 1, wherein the core-sheath structure is a multi-core core-sheath composite fiber.   The fabric using the water repellent and hygroscopic composite fiber according to any one of claims 1 to 3.