TWI629385B - Composite fiber and method for forming the same - Google Patents

Composite fiber and method for forming the same Download PDF

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TWI629385B
TWI629385B TW105144143A TW105144143A TWI629385B TW I629385 B TWI629385 B TW I629385B TW 105144143 A TW105144143 A TW 105144143A TW 105144143 A TW105144143 A TW 105144143A TW I629385 B TWI629385 B TW I629385B
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composite fiber
thermoplastic polymer
fiber according
triallyl
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TW105144143A
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TW201742959A (en
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馮學利
胡瑋
張峻綺
蕭凱仁
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財團法人工業技術研究院
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/082—Melt spinning methods of mixed yarn
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/36—Matrix structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/022—Moisture-responsive characteristics hydrophylic

Abstract

本揭露提供一種複合纖維，包括：一第一區域，此第一區域之成分包括一色料及一樹脂；以及一第二區域，此第二區域之成分包括交聯之一熱塑性聚合物，其中該交聯之熱塑性聚合物包括平均粒徑不大於1000nm之膠體粒子。本揭露亦提供一種複合纖維之製造方法。 The present disclosure provides a composite fiber comprising: a first region, the composition of the first region comprising a colorant and a resin; and a second region, the component of the second region comprising a crosslinked thermoplastic polymer, wherein the crosslinking The thermoplastic polymer is a colloidal particle having an average particle diameter of not more than 1000 nm. The present disclosure also provides a method of manufacturing a composite fiber.

Description

複合纖維及其製造方法 Composite fiber and manufacturing method thereof

本揭露係有關於一種複合纖維及其製造方法。 The present disclosure relates to a composite fiber and a method of manufacturing the same.

在紡織纖維產業中，聚醯胺(尼龍)、聚酯、與聚烯烴產品為數眾多，但由於此些材料為疏水性，故其纖維製品有不吸濕、不吸水等缺點。為了改善上述缺點，過去曾有將聚酯等疏水性聚合物與具有親水性的聚合物，像是乙烯-乙烯醇共聚物(Ethylene vinyl alcohol copolymer；EVOH)，進行複合紡絲形成芯鞘型複合纖維，以改善聚酯系纖維的親水性性能。 In the textile fiber industry, polyamine (nylon), polyester, and polyolefin products are numerous. However, since these materials are hydrophobic, the fiber products have disadvantages such as no moisture absorption and no water absorption. In order to improve the above disadvantages, in the past, a hydrophobic polymer such as polyester and a hydrophilic polymer such as an ethylene-vinyl alcohol copolymer (EVOH) were used for composite spinning to form a core-sheath type composite. Fiber to improve the hydrophilic properties of polyester fibers.

然而，親疏水性不同之材料進行複合紡絲後，兩材料間界面之接著性小，故常有分離現象，造成後加工過程中發生斷絲而影響作業或成品起毛有損外觀等問題產生。另外，聚酯和乙烯-乙烯醇共聚物形成的複合纖維在進行紡織品染色階段，纖維表層的乙烯-乙烯醇共聚物(EVOH)由於其熔點及軟化點低，因而常有膨潤、纖維間有溶黏現象發生，導致成品布手感不良之問題。 However, after the composite spinning of materials having different hydrophilicity and hydrophobicity, the interface between the two materials is small, so there is often a separation phenomenon, which causes problems such as breakage during post-processing and affecting the appearance of the work or the fluffing of the finished product. In addition, the composite fiber formed by the polyester and the ethylene-vinyl alcohol copolymer is in the stage of textile dyeing, and the ethylene-vinyl alcohol copolymer (EVOH) of the fiber surface layer is often swelled and dissolved between fibers due to its low melting point and softening point. The stickiness phenomenon occurs, resulting in a problem of poor hand feel of the finished fabric.

因此，目前亟需一種改良的複合纖維材料及其製程以解決上述問題。 Therefore, there is an urgent need for an improved composite fiber material and its process to solve the above problems.

根據一實施例，本揭露提供一種複合纖維，包括： 一第一區域，該第一區域之成分包括一樹脂；以及一第二區域，該第二區域之成分包括交聯之一熱塑性聚合物，其中該交聯之熱塑性聚合物包括平均粒徑不大於1000nm之膠體粒子。或根據另一實施例，該第一區域之成分更包括一色料。 According to an embodiment, the present disclosure provides a composite fiber comprising: a first region, the composition of the first region comprising a resin; and a second region, the component of the second region comprising a crosslinked thermoplastic polymer, wherein the crosslinked thermoplastic polymer comprises an average particle size of not more than 1000 nm colloidal particles. Or according to another embodiment, the composition of the first region further comprises a colorant.

根據另一實施例，本揭露提供一種複合纖維的製造方法，包括：混合96~99.79wt%之熱塑性聚合物、0.1~1.5wt%之交聯劑、0.1~1.5wt%之分散劑以形成一混合物；添加0.01~1wt%之交聯起始劑至混合物中並進行混練以形成一交聯之熱塑性聚合物；將交聯之熱塑性聚合物進行拉條及切粒以形成一交聯改質粒子；以及對交聯改質粒子與一樹脂進行複合熔融紡絲，其中該樹脂可含色料或不含色料。 According to another embodiment, the present disclosure provides a method for manufacturing a composite fiber, comprising: mixing 96-99.99% by weight of a thermoplastic polymer, 0.1 to 1.5% by weight of a crosslinking agent, and 0.1 to 1.5% by weight of a dispersing agent to form a composite fiber. Mixing; adding 0.01~1wt% of crosslinking initiator to the mixture and kneading to form a crosslinked thermoplastic polymer; crosslinking and granulating the crosslinked thermoplastic polymer to form a crosslinked modified particle And a composite melt spinning of the crosslinked modified particles with a resin, wherein the resin may or may not contain a colorant.

為讓本揭露之上述內容和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下： The above and other objects, features, and advantages of the present invention will become more apparent and understood.

A‧‧‧第一區域 A‧‧‧First area

B‧‧‧第二區域 B‧‧‧Second area

200‧‧‧方法 200‧‧‧ method

202-208‧‧‧步驟 202-208‧‧‧Steps

第1A~1E圖根據本揭露一些實施例顯示複合纖維之橫截面示意圖。 1A-1E are schematic cross-sectional views showing composite fibers in accordance with some embodiments of the present disclosure.

第2圖為根據本揭露一實施例顯示複合纖維之製造方法流程圖。 2 is a flow chart showing a method of manufacturing a composite fiber according to an embodiment of the present disclosure.

第3A、3B圖為根據本揭露一實施例顯示複合纖維之橫截面掃描式電子顯微影像圖(cross-section SEM Image)。 3A, 3B are cross-sectional SEM images showing cross-sections of composite fibers in accordance with an embodiment of the present disclosure.

第4A、4B圖為根據本揭露一實施例顯示複合纖維之橫截面掃描式電子顯微影像圖。 4A, 4B are cross-sectional scanning electron micrographs showing composite fibers in accordance with an embodiment of the present disclosure.

第5~9圖為根據本揭露一些實施例顯示複合纖維之橫截面掃描式電子顯微影像圖。 Figures 5-9 are cross-sectional scanning electron micrographs showing composite fibers in accordance with some embodiments of the present disclosure.

以下依本揭露之不同特徵舉出數個不同的實施例。本揭露中特定的元件及安排係為了簡化，但本揭露並不以這些實施例為限。舉例而言，於第二元件上形成第一元件的描述可包括第一元件與第二元件直接接觸的實施例，亦包括具有額外的元件形成在第一元件與第二元件之間、使得第一元件與第二元件並未直接接觸的實施例。此外，為簡明起見，本揭露在不同例子中以重複的元件符號及/或字母表示，但不代表所述各實施例及/或結構間具有特定的關係。 Several different embodiments are set forth below in light of the different features disclosed herein. The specific elements and arrangements in the disclosure are intended to be simplified, but the disclosure is not limited to the embodiments. For example, a description of forming a first element on a second element can include an embodiment in which the first element is in direct contact with the second element, and also includes having additional elements formed between the first element and the second element such that An embodiment in which one element is not in direct contact with the second element. In addition, for the sake of brevity, the disclosure is represented by repeated element symbols and/or letters in different examples, but does not represent a particular relationship between the various embodiments and/or structures.

本揭露實施例提供一種複合纖維，藉由使親水性熱塑性聚合物產生交聯改質，改善親疏水性材料間界面分離現象，以減緩纖維後加工發生斷絲、或成品起毛有損外觀的問題。透過本揭露實施例提供之複合纖維製造方法，亦可解決複合纖維在進行紡織品染色階段，因纖維表層的熱塑性聚合物如乙烯-乙烯醇共聚物(EVOH)產生膨潤、纖維間溶黏現象所導致成品布手感不良的問題。 The present disclosure provides a composite fiber which can improve cross-linking modification of a hydrophilic thermoplastic polymer, thereby improving the interfacial separation phenomenon between the hydrophilic and hydrophobic materials, thereby alleviating the problem that the fiber is broken after the fiber is processed, or the appearance of the finished product is damaged. Through the method for manufacturing the composite fiber provided by the disclosed embodiments, the composite fiber can be solved in the textile dyeing stage, and the thermoplastic polymer such as ethylene-vinyl alcohol copolymer (EVOH) of the fiber surface layer is swelled and interfiber viscous. The problem of the finished fabric is not good.

本揭露實施例利用三官能基交聯劑對具有親水性的熱塑性聚合物進行交聯改質，再將經交聯的親水性熱塑性聚合物與疏水性樹脂進行複合紡絲，透過親水性熱塑性聚合物的交聯改質，可改善兩材料間界面的分離現象。此外，本揭露實施例之疏水性樹脂可先與色料混合後，再與經改質的親水性熱塑性聚合物進行複合紡絲，形成有色的複合纖維。本揭露實施 例中之色料亦可於複合紡絲的步驟中才與樹脂混和。 The disclosed embodiments use a trifunctional crosslinking agent to crosslink and modify a hydrophilic thermoplastic polymer, and then cross-link the crosslinked hydrophilic thermoplastic polymer with a hydrophobic resin to pass through a hydrophilic thermoplastic polymerization. The cross-linking modification of the material can improve the separation of the interface between the two materials. Further, the hydrophobic resin of the present embodiment may be first mixed with a colorant and then composite-spun with a modified hydrophilic thermoplastic polymer to form a colored composite fiber. Implementation of the disclosure The colorant in the example can also be mixed with the resin in the step of composite spinning.

在本揭露一實施例中，提供一種複合纖維。此複合纖維包括第一區域A以及第二區域B。 In an embodiment of the present disclosure, a composite fiber is provided. The composite fiber includes a first region A and a second region B.

在本揭露一實施例中，第一區域A之成分包括一樹脂。在本揭露另一實施例中，區域A之成分並包括一色料，且前述色料在第一區域A之成分中的重量百分比12wt%。前述色料可包括：有機染料(dye)、無機顏料(pigment)、有機顏料、特種顏料像是金屬碎片、螢光顏料、及珠光(pearlescent)顏料等、或是前述之組合。在一實施例中，前述色料在第一區域A之成分中的重量百分比8wt%。前述樹脂可為一疏水性樹脂，例如包括：聚酯樹脂(polyester resin)、聚醯胺樹脂(polyamide resin)、聚烯烴樹脂(polyolefin resin)、或前述各類樹脂之共聚物。在一實施例中，前述聚酯樹脂可包括聚對苯二甲酸乙二醇酯(polyethylene terephthalate；PET)、聚對苯二甲酸丁二醇酯(polybutylene terephthalate；PBT)、或前述之組合。 In an embodiment of the present disclosure, the composition of the first region A includes a resin. In another embodiment of the present disclosure, the composition of the region A includes a colorant, and the weight percentage of the foregoing colorant in the composition of the first region A 12wt%. The foregoing colorant may include: an organic dye (dye), an inorganic pigment, an organic pigment, a special pigment such as a metal fragment, a fluorescent pigment, a pearlescent pigment, or the like, or a combination thereof. In one embodiment, the weight percentage of the foregoing colorant in the composition of the first region A 8wt%. The foregoing resin may be a hydrophobic resin, and includes, for example, a polyester resin, a polyamide resin, a polyolefin resin, or a copolymer of the foregoing various types of resins. In an embodiment, the polyester resin may include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), or a combination thereof.

在本揭露一實施例中，第二區域B之成分包括交聯之一熱塑性聚合物。前述之熱塑性聚合物可為一親水性熱塑性聚合物，例如：乙烯-乙烯醇共聚物(EVOH)。在一些實施例中，乙烯-乙烯醇共聚物(EVOH)的乙烯莫耳百分比可為25~50%；在一些實施例中，乙烯-乙烯醇共聚物的乙烯莫耳百分比可為35~45%。此處需說明的是，若於交聯反應後所產生之無法溶解的膠體粒子的平均粒徑過大，會導致纖維的成型加工受到阻礙，然而，在本揭露實施例中，於第二區域B之成分內所產生的膠體粒子的平均粒徑可為1000nm，達到目前商業化纖維可 紡絲的標準；即，於第二區域B中該交聯之熱塑性聚合物包括平均粒徑不大於1000nm之膠體粒子。在一些實施例中，於第二區域B之成分內所產生的膠體粒子的平均粒徑可為500nm；在一實施例中，於第二區域B之成分內所產生的膠體粒子的平均粒徑可為350nm；在一實施例中，於第二區域B之成分內所產生的膠體粒子的平均粒徑可為200nm。 In an embodiment of the present disclosure, the composition of the second region B comprises crosslinking one of the thermoplastic polymers. The aforementioned thermoplastic polymer may be a hydrophilic thermoplastic polymer such as ethylene-vinyl alcohol copolymer (EVOH). In some embodiments, the ethylene-vinyl alcohol copolymer (EVOH) may have a vinyl mole percentage of from 25 to 50%; in some embodiments, the ethylene-vinyl alcohol copolymer may have a vinyl mole percentage of from 35 to 45%. . It should be noted here that if the average particle size of the insoluble colloidal particles produced after the crosslinking reaction is too large, the molding process of the fibers may be hindered. However, in the disclosed embodiment, in the second region B The average particle size of the colloidal particles produced in the composition may be 1000 nm, up to the current commercial fiber spinnable standard; that is, the crosslinked thermoplastic polymer in the second region B comprises colloidal particles having an average particle diameter of not more than 1000 nm. In some embodiments, the average particle size of the colloidal particles produced within the composition of the second region B can be 500 nm; in one embodiment, the average particle size of the colloidal particles produced in the composition of the second region B may be 350 nm; in one embodiment, the average particle size of the colloidal particles produced in the composition of the second region B may be 200nm.

在一實施例中，第二區域B之成分係由96~99.79wt%之熱塑性聚合物、0.1~1.5wt%之交聯劑、0.1~1.5wt%之分散劑、以及0.01~1wt%之交聯起始劑所形成。 In one embodiment, the composition of the second region B is from 96 to 99.79 wt% of the thermoplastic polymer, from 0.1 to 1.5 wt% of the crosslinker, from 0.1 to 1.5 wt% of the dispersant, and from 0.01 to 1 wt%. Formed with a combination of initiators.

在一些實施例中，熱塑性聚合物在第二區域B之成分中所佔的重量百分比可為約96.0、96.5、97.0、97.5、98.0、98.5、99.0、99.5或99.79wt%。熱塑性聚合物可為一親水性熱塑性聚合物，例如：乙烯-乙烯醇共聚物(EVOH)。在一些實施例中，乙烯-乙烯醇共聚物(EVOH)的乙烯莫耳百分比可例如為25~50%、或者35~45%。 In some embodiments, the thermoplastic polymer can comprise about 96.0, 96.5, 97.0, 97.5, 98.0, 98.5, 99.0, 99.5, or 99.79% by weight of the component of the second region B. The thermoplastic polymer can be a hydrophilic thermoplastic polymer such as ethylene vinyl alcohol copolymer (EVOH). In some embodiments, the ethylene-vinyl alcohol copolymer (EVOH) may have a vinyl mole percentage of, for example, 25 to 50%, or 35 to 45%.

在一些實施例中，交聯劑在第二區域B之成分中所佔的重量百分比可為約0.1，0.2、0.3、0.4，0.5、0.6、0.7、0.8、0.9、1.0、1.1、1.2、1.3、1.4或1.5wt%。在一些實施例中，交聯劑可包括：三丙烯基酯類化合物、三丙烯基胺類化合物、或前述之組合。例如，三丙烯基酯類化合物可包括：異三聚氰酸三烯丙酯(triallyl isocynaurate；TAIC)、三聚氰酸三烯丙酯(triallyl cyanurate；TAC)、對稱苯三甲酸三烯丙酯(triallyl trimesate；TAM)、或前述之組合。例如，三丙烯基胺類化合物可包括：三烯丙胺(triallyl amine)、三丙烯三聚氰胺 (triallyl-ammoniumcyanurate)、或前述之組合。 In some embodiments, the crosslinking agent may comprise about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3 by weight of the components of the second region B. , 1.4 or 1.5 wt%. In some embodiments, the crosslinking agent can include a tripropenyl ester compound, a tripropylene amine compound, or a combination of the foregoing. For example, the tripropenyl ester compound may include: triallyl isocynaurate (TAIC), triallyl cyanurate (TAC), and tricresyl trimellitate. (triallyl trimesate; TAM), or a combination of the foregoing. For example, the tripropyleneamine compound may include: triallyl amine, tripropylene melamine (triallyl-ammoniumcyanurate), or a combination of the foregoing.

在一些實施例中，分散劑在第二區域B之成分中所佔的重量百分比可為約0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9、1.0或1.5wt%。在一些實施例中，分散劑可包括：C15-38烷類、C15-38酯類、或前述之混合物。添加分散劑有助於第二區域B之成分中各組分的均勻分散。詳細而言，添加分散劑可使交聯劑本身不產生凝集，進一步促使交聯反應能均勻作用。 In some embodiments, the dispersant may comprise from about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.5 wt% of the weight of the second region B component. In some embodiments, the dispersing agent can include: a C 15-38 alkane, a C 15-38 ester, or a mixture of the foregoing. The addition of a dispersant contributes to the uniform dispersion of the components of the components of the second zone B. In detail, the addition of the dispersing agent allows the crosslinking agent itself to not agglomerate, further promoting the crosslinking reaction to function uniformly.

在一些實施例中，交聯起始劑在第二區域B之成分中所佔的重量百分比可為約0.01、0.05、0.1、0.2、0.3、0.4、0.5、1wt%。在一些實施例中，交聯起始劑可包括：過氧化苯(benzoyl peroxide)、過氧化二異丙苯(dicumyl peroxide)、偶氮雙異丁腈(azobisisobutyronitrile)、或前述之組合。所採用的交聯起始劑種類取決於所使用的交聯劑種類。交聯起始劑的添加有利於交聯反應的進行。 In some embodiments, the weight percent of the crosslinking initiator in the second region B component can be about 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 1 wt%. In some embodiments, the crosslinking initiator can include: benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, or a combination of the foregoing. The type of crosslinking initiator used will depend on the type of crosslinking agent used. The addition of the crosslinking initiator facilitates the progress of the crosslinking reaction.

經過交聯反應後，此第二區域B之成分在190~220℃下之剪切力(熔融黏度(η)×剪切速率)可為120~20Pa．s×4000~12000s-1。 After the crosslinking reaction, the shear force (melt viscosity (η) × shear rate) of the composition of the second region B at 190 to 220 ° C may be 120 to 20 Pa. s × 4000 ~ 12000s -1 .

前述透過親水性熱塑性聚合物的交聯改質，可改善兩材料間界面分離的現象，其一原因是透過第一區域A和第二區域B各自具有之官能基而在兩材料間產生凡德瓦爾力。應注意的是，上述官能基之間產生之凡德瓦爾力增加第一區域A和第二區域B間的界面接著力，使得第一區域A和第二區域B具有較佳的連結，改善原本界面的分離現象，使得第一區域A和第二區域B間的界面變得不明顯。舉例來說，若第一區域A中 所使用的樹脂與第二區域B成分中所使用的交聯劑皆具有苯環結構，兩個區域之間的凡德瓦爾力增強，進而有助於第一區域A和第二區域B間的連結。 The cross-linking modification of the hydrophilic thermoplastic polymer can improve the phenomenon of interfacial separation between the two materials, which is caused by the functional groups of the first region A and the second region B to generate virgin between the two materials. Valli. It should be noted that the van der Waals force generated between the above functional groups increases the interfacial adhesion between the first region A and the second region B, so that the first region A and the second region B have better bonding, improving the original The separation phenomenon of the interface makes the interface between the first area A and the second area B become inconspicuous. For example, if the first area A Both the resin used and the crosslinking agent used in the second region B component have a benzene ring structure, and the van der Waals force between the two regions is enhanced, thereby contributing to the relationship between the first region A and the second region B. link.

本揭露實施例提供之複合纖維可包括但不限於：部份延伸絲(POY)、全延伸絲(FOY)、紡延絲(SDY)、假撚絲(DTY)、或空氣加工絲(ATY)。 The composite fibers provided by the embodiments may include, but are not limited to, partially extended filament (POY), fully extended filament (FOY), spun filament (SDY), false twisted silk (DTY), or air processed silk (ATY). .

於複合纖維之一橫截面中，第一區域A和第二區域B之面積比可為10：90~90：10。在一些實施例中，第一區域A和第二區域B之面積比可為10：90、20：80、30：70、40：60、50：50、60：40、70：30、80：20、或90：10。在一實施例中，於複合纖維之一橫截面中，至少一部份之第二區域位於該橫截面之外周部。於複合纖維之一橫截面中，只要第二區域B位於橫截面之外周部，即可達到透過第二區域B中交聯之熱塑性聚合物的保護功能，進而改善傳統化學纖維的耐摩擦堅牢度不良、水洗堅牢度不良及非永久型吸濕排汗性等問題。在一實施例中，於複合纖維之橫截面中，第一區域A為一芯部，且第二區域B為一鞘部。 In a cross section of the composite fiber, the area ratio of the first region A to the second region B may be 10:90 to 90:10. In some embodiments, the area ratio of the first area A and the second area B may be 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80: 20, or 90:10. In one embodiment, at least a portion of the second region of the composite fiber is located at a periphery of the cross-section. In the cross-section of one of the composite fibers, as long as the second region B is located at the outer periphery of the cross-section, the protective function of the thermoplastic polymer cross-linked through the second region B can be achieved, thereby improving the rubbing fastness of the conventional chemical fiber. Poor, poor washing fastness and non-permanent moisture wicking. In one embodiment, in the cross section of the composite fiber, the first region A is a core and the second region B is a sheath.

第1A圖至第1E圖顯示本揭露提供之複合纖維之橫截面示意圖。根據第一區域A和第二區域B在複合纖維橫截面上配置的不同，複合纖維的型態可包括：鞘芯型(sheath/core)、分割型(segment pie)、或海島型(island-in-sea)。例如，在一些實施例中，複合纖維可為如第1A圖所示的同心鞘芯型纖維，或是如第1B圖所示的偏心鞘芯型纖維。在另一些實施例中，複合纖維可為如第1C、1D圖所示的分割型纖維。在另一些實施例中，複合纖維可為如第1E圖所示的海島型纖維。應注意的是， 第1A圖至第1E圖所示僅作為示例而不用於限定本揭露，只要複合纖維中包括交聯的熱塑性聚合物成分的第二區域B配置在複合纖維整個表面，即可使用於本揭露中。舉例來說，第1C、1D圖所示的分割型纖維的分割數、以及第1E圖所示的海島型纖維的島嶼狀個數，皆可由本技術領域具有通常知識者依實際需要而調整。又，本技術領域具有通常知識者可藉由噴嘴孔的形狀、尺寸來任意設定所得到的複合纖維之橫截面形狀與直徑。 1A to 1E are cross-sectional views showing the composite fiber provided by the present disclosure. Depending on the configuration of the first region A and the second region B in the cross section of the composite fiber, the type of the composite fiber may include: sheath/core, segment pie, or island-type (island- In-sea). For example, in some embodiments, the composite fiber can be a concentric sheath core fiber as shown in Figure 1A or an eccentric sheath core fiber as shown in Figure 1B. In other embodiments, the composite fibers may be split fibers as shown in Figures 1C and 1D. In other embodiments, the composite fiber may be an island-in-the-sea fiber as shown in Figure 1E. It should be noted that 1A to 1E are shown by way of example only and are not intended to limit the disclosure, as long as the second region B including the crosslinked thermoplastic polymer component in the composite fiber is disposed on the entire surface of the composite fiber, and can be used in the present disclosure. . For example, the number of divisions of the split fibers shown in FIGS. 1C and 1D and the number of islands of the sea-island fibers shown in FIG. 1E can be adjusted by those skilled in the art according to actual needs. Further, those skilled in the art can arbitrarily set the cross-sectional shape and diameter of the obtained composite fiber by the shape and size of the nozzle hole.

在本揭露另一實施例中，提供一種複合纖維的製造方法。第2圖為根據本揭露一實施例顯示複合纖維之製造方法200流程圖。首先，方法200進行至步驟202，混合96~99.79wt%之熱塑性聚合物、0.1~1.5wt%之交聯劑、0.1~1.5wt%之分散劑以形成一混合物。接著，進行至步驟204，添加0.01~1wt%之交聯起始劑至混合物中並進行混練以形成一交聯之熱塑性聚合物。為達簡明的目的，關於方法200中所添加的熱塑性聚合物、交聯劑、分散劑、及交聯起始劑的種類及功能可參照前述相關段落，不在此贅述。 In another embodiment of the present disclosure, a method of making a composite fiber is provided. 2 is a flow chart showing a method of manufacturing a composite fiber 200 in accordance with an embodiment of the present disclosure. First, the method 200 proceeds to step 202 by mixing 96 to 99.79 wt% of the thermoplastic polymer, 0.1 to 1.5 wt% of the crosslinking agent, and 0.1 to 1.5 wt% of the dispersant to form a mixture. Next, proceeding to step 204, 0.01 to 1% by weight of a crosslinking initiator is added to the mixture and kneaded to form a crosslinked thermoplastic polymer. For the purpose of brevity, the types and functions of the thermoplastic polymer, the crosslinking agent, the dispersing agent, and the crosslinking initiator added in the method 200 can be referred to the aforementioned related paragraphs, and are not described herein.

於步驟204中，混練可利用例如：雙螺桿混練機、或其他合適的混練機來進行。螺桿轉速可例如為200~300rpm。混練之時間可約為1~10分鐘，混練之溫度可約為170~230℃。於一實施例中，混練之時間可約為10分鐘，混練之溫度可約為200~230℃。然而，上述混煉之各製程參數可依照實際需求進行調整，並不限於此。 In step 204, the kneading can be performed using, for example, a twin-screw kneader, or other suitable kneading machine. The screw rotation speed can be, for example, 200 to 300 rpm. The mixing time can be about 1 to 10 minutes, and the mixing temperature can be about 170 to 230 °C. In one embodiment, the time of the kneading can be about 10 minutes, and the temperature of the kneading can be about 200 to 230 °C. However, the process parameters of the above mixing may be adjusted according to actual needs, and are not limited thereto.

應注意的是，在混練過程中，熱塑性聚合物會呈現熔融狀，此時交聯劑會透過其-C=C雙鍵官能基和呈熔融狀的 熱塑性聚合物進行交聯反應，使熱塑性聚合物成為交聯之熱塑性聚合物。透過控制熱塑性聚合物和交聯劑之添加比例，使得交聯之熱塑性聚合物在整體交聯之熱塑性聚合物中所佔的比例能夠使交聯之熱塑性聚合物具有流動的特性。若交聯劑的比例過高，熱塑性聚合物大部分都形成網狀結構，將導致交聯之熱塑性聚合物失去流動性，無法抽絲製成纖維。若交聯劑的比例過低，熱塑性聚合物產生交聯反應的比例過低，則無法達到對熱塑性聚合物改質的目的。 It should be noted that during the kneading process, the thermoplastic polymer will melt and the crosslinker will pass through its -C=C double bond functional group and melt. The thermoplastic polymer undergoes a crosslinking reaction to make the thermoplastic polymer a crosslinked thermoplastic polymer. By controlling the ratio of addition of the thermoplastic polymer to the crosslinking agent, the proportion of the crosslinked thermoplastic polymer in the integrally crosslinked thermoplastic polymer enables the crosslinked thermoplastic polymer to have flow characteristics. If the proportion of the crosslinking agent is too high, most of the thermoplastic polymer forms a network structure, which will cause the crosslinked thermoplastic polymer to lose fluidity and cannot be drawn into fibers. If the proportion of the crosslinking agent is too low and the proportion of the crosslinking reaction of the thermoplastic polymer is too low, the purpose of modifying the thermoplastic polymer cannot be achieved.

於步驟204中，前述包含交聯之熱塑性聚合物的交聯之熱塑性聚合物在190~220℃下之剪切力(熔融黏度(η)×剪切速率)可為120~20Pa．s×4000~12000s-1，且交聯之熱塑性聚合物內無法溶解的膠體粒子的平均粒徑控制為1000nm，使不會阻礙後續的纖維成型加工。 In step 204, the shearing force (melt viscosity (η) × shear rate) of the crosslinked thermoplastic polymer comprising the crosslinked thermoplastic polymer at 190 to 220 ° C may be 120 to 20 Pa. s × 4000~12000s -1 , and the average particle size of the colloidal particles which are insoluble in the crosslinked thermoplastic polymer is controlled to 1000nm, so as not to hinder the subsequent fiber forming process.

接著，方法200進行至步驟206，將交聯之熱塑性聚合物進行拉條及切粒以形成一交聯改質造粒物。拉條及切粒步驟可依照本技術領域習知的方式及條件進行。 Next, the method 200 proceeds to step 206 where the crosslinked thermoplastic polymer is drawn and diced to form a crosslinked modified granulated product. The stranding and pelletizing steps can be carried out in accordance with the manner and conditions well known in the art.

最後，方法200進行至步驟208，對交聯改質造粒物與一含色料(在另一實施例中不含色料)樹脂進行複合熔融紡絲。前述含色料樹脂可為經由習知生產流程形成之色母粒。前述含色料樹脂之色料在含色料樹脂中的重量百分比12wt%、或者8wt%，其種類可參照前述相關段落。 Finally, method 200 proceeds to step 208 where the crosslinked modified granules are compound melt spun with a colorant (in another embodiment, no colorant) resin. The aforementioned color-containing resin may be a masterbatch formed through a conventional production process. The weight percentage of the colorant resin-containing colorant in the colorant-containing resin 12wt%, or 8wt%, the type can refer to the relevant paragraphs mentioned above.

本揭露實施例所提供的複合纖維，不需使用二醛化合物透過後處理方式以對纖維表層的乙烯-乙烯醇共聚物(EVOH)的羥基進行縮醛化。相對地，本揭露實施例是先形成 交聯改質之熱塑性聚合物，再與樹脂進行複合熔融紡絲形成複合纖維。所形成的複合纖維的兩材料間透過交聯改質之熱塑性聚合物，會改善習知複合纖維的界面分離現象。本揭露實施例提供的複合纖維得以深色化、成品布之手感及外觀良好，並且兼具良好的吸濕排汗性。 In the conjugate fiber provided by the embodiment, the hydroxyl group of the ethylene-vinyl alcohol copolymer (EVOH) of the fiber surface layer is acetalized without using a dialdehyde compound through a post-treatment method. In contrast, the disclosed embodiment is formed first. The modified thermoplastic polymer is crosslinked and then composite melt-spun with the resin to form a composite fiber. The cross-linked modified thermoplastic polymer between the two materials of the formed composite fiber improves the interfacial separation phenomenon of the conventional composite fiber. The composite fiber provided by the embodiment has a dark color, a good feel and a good appearance of the finished fabric, and has good moisture wicking property.

以下列舉各實施例與比較例說明本揭露提供之複合纖維及其特性： The composite fibers and characteristics thereof provided by the present disclosure are illustrated by the following examples and comparative examples:

製備例1~4：交聯改質造粒(以三丙烯基酯類化合物為交聯劑) Preparation Examples 1 to 4: Crosslinking modified granulation (with a tripropylene acrylate compound as a crosslinking agent)

首先，將交聯劑異三聚氰酸三烯丙酯(TAIC)、乙烯-乙烯醇共聚物(EVOH)(乙烯莫耳百分比為44%)以及分散劑混合以得到一混合物。接著，在上述混合物中加入交聯起始劑過氧化二異丙苯，並進行混練。混練時間約10分鐘，混練溫度為約200~230℃。之後，將混練的產物進行拉條與切粒，即可得到製備例1的交聯改質EVOH粒子。 First, a cross-linking agent, isocyanurate (TAIC), an ethylene-vinyl alcohol copolymer (EVOH) (44% ethylene molar percentage), and a dispersing agent were mixed to obtain a mixture. Next, a crosslinking initiator dicumyl peroxide was added to the above mixture, followed by kneading. The mixing time is about 10 minutes, and the mixing temperature is about 200 to 230 °C. Thereafter, the kneaded product was subjected to stranding and pelletizing to obtain the crosslinked modified EVOH pellet of Preparation Example 1.

製備例2~4的製備方式同製備例1，惟各製備例中異三聚氰酸三烯丙酯(TAIC)和乙烯-乙烯醇共聚物(EVOH)的組成比例依表1所示進行調整。於製備例1~4中，分散劑的添加比例均為0.5wt%。於製備例1~4中，交聯起始劑過氧化二異丙苯的添加比例均為0.05wt%，以交聯劑、乙烯-乙烯醇共聚物(EVOH)、和分散劑之總重量為基準。 Preparations 2 to 4 were prepared in the same manner as in Preparation Example 1, except that the composition ratios of triallyl isocyanurate (TAIC) and ethylene-vinyl alcohol copolymer (EVOH) were adjusted as shown in Table 1. . In Preparation Examples 1 to 4, the addition ratio of the dispersant was 0.5% by weight. In Preparation Examples 1 to 4, the crosslinking initiator dicumyl peroxide was added in an amount of 0.05% by weight, based on the total weight of the crosslinking agent, the ethylene-vinyl alcohol copolymer (EVOH), and the dispersing agent. Benchmark.

聚合物經交聯反應後會產生膠體，此等膠體不溶於溶劑。以雷射測徑儀測量製備例1~4中混練所得產物中的膠體粒徑，測量結果如表1所示。 The polymer undergoes a cross-linking reaction to produce a colloid which is insoluble in the solvent. The colloidal particle size in the product obtained by the mixing in Preparation Examples 1 to 4 was measured by a laser caliper, and the measurement results are shown in Table 1.

製備例5：交聯改質造粒(以三丙烯基胺類化合物為交聯劑) Preparation Example 5: Crosslinked modified granulation (with a tripropylene amide compound as a crosslinking agent)

製備例5的製備方式同製備例1，惟將異三聚氰酸三烯丙酯(TAIC)替換為三烯丙胺(triallyl amine)。以雷射測徑儀測量製備例5中混練所得產物中的膠體粒徑，測得之平均粒徑為45nm。 Preparation 5 was prepared in the same manner as in Preparation 1, except that triallyl isocyanurate (TAIC) was replaced with triallyl amine. The colloidal particle size in the product obtained by the kneading in Preparation Example 5 was measured by a laser caliper, and the average particle diameter was measured to be 45 nm.

比較例1：複合纖維---未經交聯改質EVOH(P-EVOH)/PET Comparative Example 1: Composite fiber--- uncrosslinked modified EVOH (P-EVOH)/PET

以乙烯莫耳百分比為44%之未經交聯改質之EVOH粒子(之後簡稱為P-EVOH)作為複合纖維之鞘成份材料，並以聚對苯二甲酸乙二醇酯(polyethylene terephthalate；PET)粒子(本質黏度(IV)值：0.64)做為複合纖維之芯成份材料，將上述兩種材料進行複合熔融紡絲。首先，經2800m/min捲繞後，再於80℃延伸、於150℃定型成全延伸絲(FOY)。至此，完成複合纖維的製造。所得之複合纖維規格為：丹尼80D/36F、強度2.8(g/d)、伸度25±5(%)。 An uncrosslinked modified EVOH particle (hereinafter referred to as P-EVOH) having a vinyl ether percentage of 44% is used as a sheath component material of the composite fiber, and polyethylene terephthalate (PET) is used. The particles (intrinsic viscosity (IV) value: 0.64) are used as the core material of the composite fiber, and the above two materials are subjected to composite melt spinning. First, after winding at 2,800 m/min, it was further extended at 80 ° C and fixed at 150 ° C to form a fully extended yarn (FOY). So far, the manufacture of the composite fiber has been completed. The obtained composite fiber specifications were: Danny 80D/36F, strength 2.8 (g/d), and elongation 25 ± 5 (%).

實施例1：複合纖維---交聯改質EVOH(M-EVOH)/PET Example 1: Composite fiber--- crosslinked modified EVOH (M-EVOH)/PET

以製備例2之乙烯莫耳百分比為44%之交聯改質EVOH粒子(之後簡稱為M-EVOH)作為複合纖維之鞘成份材料，並以聚對苯二甲酸乙二醇酯(PET)粒子(IV值：0.64)做為複合纖維之芯成份材料，將上述兩種材料進行複合熔融紡絲。首先，經2800m/min捲繞後，再於80℃延伸、於150℃定型成全延伸絲(FOY)。至此，完成複合纖維的製造。所得之複合纖維規格為：丹尼80D/36F、強度3.2(g/d)、伸度25±5(%)。 The crosslinked modified EVOH particles (hereinafter abbreviated as M-EVOH) having a percentage of ethylene molar of 44% in Preparation Example 2 were used as a sheath component material of the composite fiber, and polyethylene terephthalate (PET) particles were used. (IV value: 0.64) As a core material of the composite fiber, the above two materials were subjected to composite melt spinning. First, after winding at 2,800 m/min, it was further extended at 80 ° C and fixed at 150 ° C to form a fully extended yarn (FOY). So far, the manufacture of the composite fiber has been completed. The obtained composite fiber specifications were: Danny 80D/36F, strength 3.2 (g/d), and elongation 25 ± 5 (%).

第3A~3B圖顯示比較例1所製得複合纖維在不同倍率下之橫截面掃描式電子顯微影像圖，可看出比較例1之P-EVOH/PET鞘芯界面分離現象明顯。相較之下，第4A~4B圖顯示實施例1所製得複合纖維在不同倍率下之橫截面掃描式電子顯微影像圖，可看出實施例1之M-EVOH/PET鞘芯間的界面變得不明顯，相較於比較例1，鞘芯間的界面分離現象獲得顯著改善。 Figures 3A to 3B show cross-sectional scanning electron micrographs of the composite fibers obtained in Comparative Example 1 at different magnifications. It can be seen that the P-EVOH/PET sheath core interface separation phenomenon of Comparative Example 1 is remarkable. In contrast, Figures 4A to 4B show cross-sectional scanning electron micrographs of the composite fibers obtained in Example 1 at different magnifications, and it can be seen that the M-EVOH/PET sheath core of Example 1 is The interface became inconspicuous, and the interface separation phenomenon between the sheath cores was significantly improved as compared with Comparative Example 1.

實施例2：複合纖維---M-EVOH/PA Example 2: Composite fiber --- M-EVOH/PA

以製備例5(交聯劑為三丙烯基胺類化合物)之乙烯莫耳百分比為44%之M-EVOH作為複合纖維之鞘成份材料，並以聚醯胺樹脂(polyamide resin)(台化；Sunylon 2NBR Nylon 6)粒子(RV值：2.4)做為複合纖維之芯成份材料，將上述兩種材料進行複合熔融紡絲。首先，經3800m/min捲繞後，再於50℃延伸、於150℃定型成全延伸絲(FOY)，完成複合纖維的製造。 所得之複合纖維規格為：丹尼80D/36F、強度3.5(g/d)、伸度25±5(%)。 In Preparation Example 5 (crosslinking agent is a trisacrylamide compound), M-EVOH having a percentage of vinyl mole of 44% is used as a sheath component material of the composite fiber, and is a polyamide resin (Taiwan; Sunylon 2NBR Nylon 6) particles (RV value: 2.4) are used as the core material of the composite fiber, and the above two materials are compound melt-spun. First, after winding at 3,800 m/min, the film was further extended at 50 ° C and fixed at 150 ° C to form a full-length yarn (FOY) to complete the production of the composite fiber. The obtained composite fiber specifications were: Danny 80D/36F, strength 3.5 (g/d), and elongation 25 ± 5 (%).

實施例3：複合纖維---M-EVOH/含色料PBT Example 3: Composite fiber --- M-EVOH / color containing material PBT

以製備例2之乙烯莫耳百分比為44%之M-EVOH作為複合纖維之鞘成份材料，並以含0.025wt%淺紫色色粉(大恭化學；PV 23)之聚對苯二甲酸丁二醇酯(polybutylene terephthalate；PBT)粒子(IV值：0.9)做為複合纖維之芯成份材料，將上述兩種材料進行複合熔融紡絲。首先，經2800m/min捲繞成部分延伸絲(POY)後，再於70℃延伸、於150℃定型成全延伸絲(FOY)。至此，完成複合纖維的製造。 M-EVOH having a percentage of ethylene molar of 44% in Preparation Example 2 was used as a sheath component material of the composite fiber, and a polybutylene terephthalate containing 0.025% by weight of a light purple toner (Dagong Chemical; PV 23) Polybutylene terephthalate (PBT) particles (IV value: 0.9) are used as the core material of the composite fiber, and the above two materials are compound melt-spun. First, after being wound into a partially stretched yarn (POY) at 2,800 m/min, it was further extended at 70 ° C and shaped into a full stretched yarn (FOY) at 150 ° C. So far, the manufacture of the composite fiber has been completed.

實施例4~6：複合纖維---M-EVOH/含色料PBT Examples 4 to 6: Composite fiber --- M-EVOH / coloring material PBT

實施例4~6的製備方式同實施例3，惟於實施例4中將淺紫色色粉替換為淺綠色色粉(大恭化學；PG-7)，於實施例5中將淺紫色色粉替換為橘色色粉(大恭化學；PO-16)，實施例6中將淺紫色色粉替換為黃色色粉(大恭化學；PY3)。 Examples 4 to 6 were prepared in the same manner as in Example 3 except that in Example 4, the pale purple toner was replaced with a light green toner (Dagong Chemical; PG-7), and in Example 5, the light purple toner was used. Replaced with orange toner (Tai Kung Chemical; PO-16), in Example 6, the light purple toner was replaced with yellow toner (Da Kung Chemical; PY3).

上述實施例3~6所得之部分延伸絲(POY)複合纖維規格顯示於表2，上述實施例3~6所得之全延伸絲(FOY)複合纖維規格顯示於表3。 The specifications of the partially stretched silk (POY) composite fibers obtained in the above Examples 3 to 6 are shown in Table 2, and the specifications of the fully expanded yarn (FOY) composite fibers obtained in the above Examples 3 to 6 are shown in Table 3.

觀察實施例3~6所製得之有色複合纖維外觀，並透過掃描式電子顯微鏡觀察其橫截面影像，如第5~8圖所示。可發現實施例3~6所製得之有色複合纖維成型良好，M-EVOH/PBT鞘芯間的界面不明顯，相較於比較例1，鞘芯間的界面分離現象獲得顯著改善。 The appearance of the colored composite fibers obtained in Examples 3 to 6 was observed, and the cross-sectional images thereof were observed by a scanning electron microscope, as shown in Figs. It can be found that the colored composite fibers obtained in Examples 3 to 6 are well formed, and the interface between the M-EVOH/PBT sheath cores is not conspicuous, and the interface separation phenomenon between the sheath cores is remarkably improved as compared with Comparative Example 1.

實施例7：複合纖維---M-EVOH/含色料PA Example 7: Composite fiber --- M-EVOH / coloring material PA

以製備例5(交聯劑為三丙烯基胺類化合物)之乙烯莫耳百分比為44%之M-EVOH作為複合纖維之鞘成份材料，並以含0.025wt%藍色粉(大恭化學；PB-15)之聚醯胺樹脂(polyamide resin)(台化；N6)粒子(RV值：2.4)做為複合纖維之芯成份材料，將上述兩種材料進行複合熔融紡絲。首先，經 3800m/min捲繞成部分延伸絲(POY)後，再於50℃延伸、於150℃定型成全延伸絲(FOY)。至此，完成複合纖維的製造。所得之複合纖維規格為：丹尼80D/36F、強度3.4(g/d)、伸度25±5(%)。觀察實施例7所製得之有色複合纖維外觀，並透過掃描式電子顯微鏡觀察其橫截面影像，如第9圖所示。可看出實施例9所製得之有色複合纖維成型良好，M-EVOH/PA鞘芯間的界面不明顯，相較於比較例1，鞘芯間的界面分離現象獲得顯著改善。 In the preparation example 5 (crosslinking agent is a tripropenylamine compound), M-EVOH having a percentage of vinyl mole of 44% is used as a sheath component material of the composite fiber, and contains 0.025% by weight of blue powder (Da Gong Chemical; PB-15) Polyamide resin (Taiwan; N6) particles (RV value: 2.4) as a core material of the composite fiber, the above two materials are compound melt-spun. First, by After 3800 m/min was wound into a partially stretched yarn (POY), it was further extended at 50 ° C and shaped into a full stretch yarn (FOY) at 150 ° C. So far, the manufacture of the composite fiber has been completed. The obtained composite fiber specifications were: Danny 80D/36F, strength 3.4 (g/d), and elongation 25 ± 5 (%). The appearance of the colored composite fiber obtained in Example 7 was observed, and the cross-sectional image thereof was observed by a scanning electron microscope as shown in Fig. 9. It can be seen that the colored composite fiber obtained in Example 9 is well formed, and the interface between the M-EVOH/PA sheath core is not conspicuous, and the interface separation phenomenon between the sheath cores is remarkably improved as compared with Comparative Example 1.

由上述實施例結果可證明本揭露透過對熱塑性聚合物的交聯改質，將此交聯改質熱塑性聚合物與樹脂進行複合熔融紡絲所形成之複合纖維，其界面之間的分離現象獲得改善，纖維成型良好，並具有良好的紡絲性及延伸性等物性。此外，本揭露使用之含色料樹脂與交聯改質熱塑性聚合物形成之複合纖維，得以獲得深色化纖維、成品布之手感及外觀良好，並且兼具良好的吸濕排汗性。 From the results of the above examples, it can be confirmed that the cross-linking phenomenon of the thermoplastic polymer is cross-linked and modified, and the composite fiber formed by the composite melt-spinning of the cross-linked modified thermoplastic polymer and the resin is obtained. Improved, good fiber formation, and good physical properties such as spinnability and elongation. In addition, the composite fiber formed by the coloring resin and the crosslinked modified thermoplastic polymer used in the present disclosure can obtain a dark fiber, a finished cloth, and a good appearance, and has good moisture wicking property.

雖然本揭露已以數個實施例揭露如上，然其並非用以限定本揭露，任何所屬技術領域中具有通常知識者，在不脫離本揭露之精神和範圍內，當可作任意之更動與潤飾，因此本揭露之保護範圍當視後附之申請專利範圍所界定者為準。 The disclosure has been disclosed in the above several embodiments, but it is not intended to limit the disclosure, and any person skilled in the art can make any changes and refinements without departing from the spirit and scope of the disclosure. Therefore, the scope of protection of this disclosure is subject to the definition of the scope of the patent application.

Claims (20)

一種複合纖維，包括：一第一區域，該第一區域之成分包括一樹脂；以及一第二區域，該第二區域之成分包括交聯之一熱塑性聚合物，其中該第二區域之成分係由96~99.79wt%之該熱塑性聚合物、0.1~1.5wt%之交聯劑、0.1~1.5wt%之分散劑、以及0.01~1wt%之交聯起始劑所形成；其中該交聯之熱塑性聚合物包括平均粒徑不大於1000nm之膠體粒子，其中該第一區域和該第二區域透過各自具有之官能基而在該第一區域和該第二區域間產生之凡德瓦爾力而連結。 A composite fiber comprising: a first region, the composition of the first region comprising a resin; and a second region, the component of the second region comprising a crosslinked thermoplastic polymer, wherein the composition of the second region Forming from 96 to 99.79 wt% of the thermoplastic polymer, 0.1 to 1.5 wt% of a crosslinking agent, 0.1 to 1.5 wt% of a dispersing agent, and 0.01 to 1 wt% of a crosslinking initiator; wherein the crosslinking The thermoplastic polymer includes colloidal particles having an average particle diameter of not more than 1000 nm, wherein the first region and the second region are linked by a van der Waals force generated between the first region and the second region through a functional group each having a functional group . 如申請專利範圍第1項所述之複合纖維，其中該第一區域之成分更包括一色料。 The conjugate fiber of claim 1, wherein the component of the first region further comprises a colorant. 如申請專利範圍第2項所述之複合纖維，其中該色料於該第一區域之成分中之重量百分比12wt%。 The composite fiber according to claim 2, wherein the color percentage of the colorant in the first region is 12wt%. 如申請專利範圍第1項所述之複合纖維，其中該樹脂包括：聚酯樹脂(polyester resin)、聚醯胺樹脂(polyamide resin)、聚烯烴樹脂(polyolefin resin)、或前述各類樹脂之共聚物。 The conjugate fiber according to claim 1, wherein the resin comprises: a polyester resin, a polyamide resin, a polyolefin resin, or a copolymer of the foregoing various resins. Things. 如申請專利範圍第1項所述之複合纖維，其中該熱塑性聚合物為乙烯-乙烯醇共聚物(EVOH)，且該乙烯-乙烯醇共聚物之乙烯莫耳百分比為25~50%。 The conjugate fiber according to claim 1, wherein the thermoplastic polymer is an ethylene-vinyl alcohol copolymer (EVOH), and the ethylene-vinyl alcohol copolymer has a vinyl mole percentage of 25 to 50%. 如申請專利範圍第1項所述之複合纖維，其中該交聯劑係為三丙烯基酯類化合物、三丙烯基胺類化合物、或前述之組合。 The conjugate fiber according to claim 1, wherein the crosslinking agent is a tripropylene acrylate compound, a tripropylene amide compound, or a combination thereof. 如申請專利範圍第6項所述之複合纖維，其中該三丙烯基酯類化合物包括異三聚氰酸三烯丙酯(triallyl isocynaurate；TAIC)、三聚氰酸三烯丙酯(triallyl cyanurate；TAC)、對稱苯三甲酸三烯丙酯(triallyl trimesate；TAM)、或前述之組合，該三丙烯基胺類化合物包括三烯丙胺(triallyl amine)、三丙烯三聚氰胺(triallyl-ammoniumcyanurate)、或前述之組合。 The conjugate fiber according to claim 6, wherein the tripropenyl ester compound comprises triallyl isocynaurate (TAIC), triallyl cyanurate; TAC), triallyl trimesate (TAM), or a combination of the foregoing, the tripropyleneamine compound including triallyl amine, triallyl-ammonium cyanurate, or the foregoing The combination. 如申請專利範圍第1項所述之複合纖維，其中該分散劑包括C15-38烷類、C15-38酯類、或前述之混合物。 The conjugate fiber of claim 1, wherein the dispersing agent comprises a C 15-38 alkane, a C 15-38 ester, or a mixture of the foregoing. 如申請專利範圍第1項所述之複合纖維，其中該交聯起始劑包括過氧化苯(benzoyl peroxide)、過氧化二異丙苯(dicumyl peroxide)、偶氮雙異丁腈(azobisisobutyronitrile)、或前述之組合。 The conjugate fiber according to claim 1, wherein the crosslinking initiator comprises benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, Or a combination of the foregoing. 如申請專利範圍第1項所述之複合纖維，其中該第二區域之成分在190~220℃下之剪切力(熔融黏度(η)×剪切速率)為120~20Pa．s×4000~12000s-1。 The composite fiber according to claim 1, wherein the composition of the second region has a shearing force (melt viscosity (η) × shear rate) of 120 to 20 Pa at 190 to 220 ° C. s × 4000 ~ 12000s -1 . 如申請專利範圍第1項所述之複合纖維，其中於該複合纖維之一橫截面中，該第一區域和該第二區域之面積比為10：90~90：10。 The composite fiber according to claim 1, wherein in the cross section of the composite fiber, an area ratio of the first region to the second region is 10:90 to 90:10. 如申請專利範圍第1項所述之複合纖維，其中於該複合纖維之一橫截面中，至少一部份之該第二區域位於該橫截面之外周部。 The composite fiber of claim 1, wherein at least a portion of the second region of the composite fiber is located at a periphery of the cross section. 如申請專利範圍第11項所述之複合纖維，其中於該複合纖維之該橫截面中，該第一區域為一芯部，且該第二區域為一鞘部。 The composite fiber according to claim 11, wherein in the cross section of the composite fiber, the first region is a core portion, and the second region is a sheath portion. 一種複合纖維的製造方法，包括：混合96~99.79wt%之熱塑性聚合物、0.1~1.5wt%之交聯劑、0.1~1.5wt%之分散劑以形成一混合物；添加0.01~1wt%之交聯起始劑至該混合物中並進行混練以形成一交聯之熱塑性聚合物；將該交聯之熱塑性聚合物進行拉條及切粒以形成一交聯改質粒子；以及對該交聯改質粒子與一樹脂進行複合熔融紡絲。 A method for producing a composite fiber comprising: mixing 96 to 99.79 wt% of a thermoplastic polymer, 0.1 to 1.5 wt% of a crosslinking agent, and 0.1 to 1.5 wt% of a dispersing agent to form a mixture; adding 0.01 to 1 wt% of the mixture Coordinating the initiator into the mixture and kneading to form a crosslinked thermoplastic polymer; subjecting the crosslinked thermoplastic polymer to stranding and pelletizing to form a crosslinked modified particle; and modifying the crosslinking The particles are subjected to compound melt spinning with a resin. 如申請專利範圍第14項所述之複合纖維的製造方法，其中該熱塑性聚合物為乙烯-乙烯醇共聚物(EVOH)，且該乙烯-乙烯醇共聚物之乙烯莫耳百分比為25~50%。 The method for producing a conjugate fiber according to claim 14, wherein the thermoplastic polymer is an ethylene-vinyl alcohol copolymer (EVOH), and the ethylene-vinyl alcohol copolymer has a vinyl mole percentage of 25 to 50%. . 如申請專利範圍第14項所述之複合纖維的製造方法，其中該交聯劑包括：三丙烯基酯類化合物、三丙烯基胺類化合物、或前述之組合。 The method for producing a conjugate fiber according to claim 14, wherein the crosslinking agent comprises a tripropylene acrylate compound, a tripropylene amide compound, or a combination thereof. 如申請專利範圍第16項所述之複合纖維的製造方法，其中該三丙烯基酯類化合物包括異三聚氰酸三烯丙酯(triallyl isocynaurate；TAIC)、三聚氰酸三烯丙酯(triallyl cyanurate；TAC)、對稱苯三甲酸三烯丙酯(triallyl trimesate；TAM)、或前述之組合，該三丙烯基胺類化合物包括三烯丙胺(triallyl amine)、三丙烯三聚氰胺(triallyl-ammoniumcyanurate)、或前述之組合。 The method for producing a conjugate fiber according to claim 16, wherein the tripropenyl ester compound comprises triallyl isocynaurate (TAIC), triallyl cyanurate ( Triallyl cyanurate; TAC), triallyl trimesate (TAM), or a combination thereof, including trilylamine, triallyl-ammoniumcyanurate Or a combination of the foregoing. 如申請專利範圍第14項所述之複合纖維的製造方法，其中該混練之時間為1~10分鐘，且該混練之溫度為170~230℃。 The method for producing a conjugate fiber according to claim 14, wherein the kneading time is 1 to 10 minutes, and the kneading temperature is 170 to 230 °C. 如申請專利範圍第14項所述之複合纖維的製造方法，其中該混練係利用一雙螺桿混練機來進行。 The method for producing a conjugate fiber according to claim 14, wherein the kneading is carried out using a twin-screw kneader. 如申請專利範圍第19項所述之複合纖維的製造方法，其中一螺桿轉速為200~300rpm。 The method for producing a conjugate fiber according to claim 19, wherein a screw rotation speed is 200 to 300 rpm.
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