WO2019104753A1 - 光致变色复合纤维 - Google Patents

光致变色复合纤维 Download PDF

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Publication number
WO2019104753A1
WO2019104753A1 PCT/CN2017/115575 CN2017115575W WO2019104753A1 WO 2019104753 A1 WO2019104753 A1 WO 2019104753A1 CN 2017115575 W CN2017115575 W CN 2017115575W WO 2019104753 A1 WO2019104753 A1 WO 2019104753A1
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Prior art keywords
photochromic
core
fiber
polymer
composite fiber
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PCT/CN2017/115575
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English (en)
French (fr)
Inventor
李伟
吴边鹏
李浩铭
边俊民
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天津孚信阳光科技有限公司
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Publication of WO2019104753A1 publication Critical patent/WO2019104753A1/zh

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent

Definitions

  • the invention relates to the technical field of textiles, in particular to a photochromic composite fiber.
  • Photochromic fiber has a unique visual effect, which not only satisfies consumers' pursuit of novelty, diversity and variability of clothing color, but also can be widely used in anti-counterfeiting, advertising, military camouflage and other fields.
  • the principle of photochromic fiber is mainly divided into two types: one is to fabricate fiber by liquid crystal spinning, and the liquid crystal structure inside has different reflection effects on incident light to form photochromism at different angles; the other is internal addition of fiber or The surface adheres to the photochromic substance and can display different colors as the ambient light conditions change.
  • photochromic materials have been applied on fabrics, mainly by coating adhesives for high-temperature baking, or by coating printing and coating.
  • color fastness is poor
  • hand feel is hard
  • weather resistance is poor
  • lasting Defects such as poor performance and poor air permeability.
  • a small number of photochromic fibers are produced by liquid crystal spinning, electrospinning, grafting of spirooxazine groups or spiropyran groups, addition of fluorescent agents or surface-adhesive special microcapsules, but the preparation process is complicated. It has great harm to the environment and has potential harm to human health. In addition, it has defects such as easy damage to surface structure, poor fatigue resistance and short service life.
  • Chinese patent ZL200580011656 John et al.
  • Chinese patent CN101701052A Sun Binbin et al. used a chemical grafting method to initiate polymerization of oxazide group-containing acrylate dye monomer by benzoyl peroxide, grafted to nitrocellulose macromolecular backbone, and used to prepare photoinduced The color changing film and coating, the method is complicated, a large amount of organic solvent is used, and the grafting rate cannot be ensured.
  • the photochromic viscose fiber After mixing the photochromic microcapsule emulsion with the viscose solution, the photochromic viscose fiber is obtained by acid spinning.
  • the method belongs to solution spinning, the process is complicated, and the environment is polluted.
  • the prepared fiber has a low strength, which greatly limits its application.
  • Chinese patent CN104047069A Weng Junqiang et al. melt-blended granules of photochromic dyes and low-melting nylon sheets to prepare masterbatch, and then melt-spinned with low-melting pellets, and obtained photochromic POY filaments by drawing. The method greatly improves the spinning efficiency, and the melt spinning does not pollute the environment.
  • the photochromic dye is irregularly distributed in the fiber, and the dye distributed on the surface not only reduces the photochromism. Functional weather resistance, low color fastness, easy to discolor, affecting the human body, wearing or the environment.
  • Chen Chajiao et al. used fiber grade polyethylene terephthalate as the core layer in the invention patent CN103556300A, and added polyethylene terephthalate of phenoxynaphthoquinone photochromic material.
  • a photochromic fiber is prepared as a skin layer.
  • the method is a hot-bonded fiber, which mainly functions as a bonding material and a support, and cannot be applied to the surface of the product and the texture design of the flower, and has a limited limitation.
  • the distribution of the dye to the cortex reduces the weather resistance of the discoloration function, the color fastness is low, and the color is easily discolored, which also causes harm to human health, wearing comfort and the environment.
  • the object of the present invention is to solve the defects of poor color resistance, low color fastness and easy discoloration of the existing composite fiber discoloration function, and to provide a photochromic composite fiber.
  • the technical solution of the present invention is: a photochromic composite fiber, wherein the cortex and the core layer have a concentric structure in a cross section of the fiber, and the skin layer closely covers the core layer; the skin layer is a fiber-forming polymer, and the polyolefin is selected.
  • the core layer is a thermoplastic fiber-forming polymer, polyolefin, polyester, poly At least one of an amide and a polyurethane, and a photochromic dye, an antioxidant, a spinner, a heat stabilizer, and a sensitizer are added in a certain ratio.
  • the skin layer and the core layer are formed by a melt spinning process.
  • the outer layer of the photochromic dye is coated with a flexible transparent polymer outer shell, and the flexible transparent polymer outer shell and the photochromic dye have a mass ratio of 5:95 to 95:5 and a particle size distribution of 0.1 to At 5 microns, a photochromic microcapsule or nanocapsule is formed which has a pressure responsive property that expands or contracts according to the volume change of the photochromic dye.
  • the polymer is generally selected from a polyolefin polymer such as a polyolefin or a copolymer thereof, a polyester or a copolymer thereof, a polyamide, a polyurethane, an acrylonitrile copolymer, an amino resin, a polyurea or the like, or a low cross-linking polymer. At least one of them is preferably a polyester or polyurethane type polymer outer casing.
  • the core layer fiber-forming polymer preferably has a low melting point polymer having a melting point of less than 250 ° C, at least one of polyethylene, polypropylene, ethylene propylene rubber, low melting point polyester, low melting point polyamide; the skin layer in the sheath core structure
  • the mass ratio to the core material is 5:95 to 95:5.
  • the sensitizer is selected from aromatic or aliphatic esters, specifically at least one of 1-hydroxy-2-naphthoic acid phenyl ester, dibenzyl oxalate, and p-benzylbiphenyl.
  • the softener is at least one of a monoalkyl quaternary ammonium salt, a dialkyl quaternary ammonium salt, an alkyl acyl quaternary ammonium salt, a pyridine quaternary ammonium salt type or an imidazole type softening agent.
  • the spinning aid mainly includes a dispersing agent, a coupling agent, and the like.
  • the spinning aid is a titanate series, a silane series, and a hard At least one of a series of a fatty acid ester series, isopropyl isostearyl-methacrylic titanate, and the silane series includes bis-( ⁇ -triethoxysilylpropyl)tetrasulfide, ⁇ - Mercapto trimethoxysilane, ⁇ -methacryloyl trimethoxysilane, ⁇ -glycidoxy trimethoxysilane, and ⁇ -aminopropyltriethoxysilane; stearate series include stearic acid, glycerin At least one of monostearate and glyceryl tristearate. The amount of the spinner added is from 1 to 10% by mass of the core fiber-forming polymer.
  • the antioxidants are tert-butylhydroxyanisole (BHA), dibutylhydroxytoluene (BHT), tert-butyl hydroquinone (TBHQ), propyl gallate (PG), ascorbyl palmitate (AP). And at least one of thiodipropionic acid dilaurate (DLTP) and 4-hexyl resorcinol (4-HR).
  • BHA tert-butylhydroxyanisole
  • BHT dibutylhydroxytoluene
  • TBHQ tert-butyl hydroquinone
  • PG propyl gallate
  • AP ascorbyl palmitate
  • DLTP thiodipropionic acid dilaurate
  • 4-hexyl resorcinol (4-HR) 4-hexyl resorcinol
  • the airtightness-improving agent added to the skin layer is an organic ester solution of at least one of polyethylene naphthalate, diisopropyl compound, and ethylene propylene diene monomer.
  • each component of the core layer is: the mass ratio of each component of the core layer to the fiber-forming polymer is: 1 to 10% of the photochromic dye, 0.22 to 0.62% of the spinning aid (including 0.2 to 0.22 of the dispersing agent) 0.5%, coupling agent 0.02 to 0.12%), heat stabilizer 0.03 to 0.3%, antioxidant 0.01 to 0.09%, and sensitizer 0.1 to 5%.
  • the mass ratio of each component of the skin layer to the fiber-forming polymer is: 0.1 to 2% of the airtightness improving agent, 0 to 0.5% of the flame retardant, and 0.04 to 0.4% of the softening agent.
  • the obtained composite fiber had a POY strength of 1.5 to 3.5 cN/dtex, and the treated fiber DTY was 2.0 to 5.0 cN/dtex.
  • the photochromic composite fiber is prepared by the following preparation method:
  • the melt-processable fiber-forming polymer as a skin layer is first dried to have a water content of less than 50 ppm after drying, and then 0.1 to 2% of the air-tightness improving agent is added according to the mass percentage of the fiber-forming polymer, and the flame retardant is 0. ⁇ 0.5%, softener 0.04 ⁇ 0.4%, after mixing and melting, granulation, the cortex material can be obtained;
  • the core material is low-melting into a fiber polymer and vacuum-dried so that the moisture content after drying is less than 50 ppm, and then the photochromic dye is added in an amount of 1 to 10%, the dispersing agent is 0.2 to 0.5%, and the coupling agent is 0.02. ⁇ 0.12%, heat stabilizer 0.03 ⁇ 0.3%, antioxidant 0.01 ⁇ 0.09%, after mixing uniformly, melt granulation, the core layer material can be obtained; 3.
  • Spinning by melt spinning adjust torque flow
  • the temperature of each zone of the transformer and the screw extruder is respectively extruded, and the core material and the skin material with the photochromic material are respectively extruded, and then the mass ratio of the skin layer to the core layer is measured and controlled by the melt distribution pipe to enter the concentric core core.
  • the composite spin pack, the two melts are combined and extruded at the orifice of the assembly to control the appropriate extrusion speed, so that the skin layer uniformly and tightly covers the core layer containing the photochromic dye, and then the side blow Cooling, wind speed is 0.3 ⁇ 0.03m/s, humidity is 75% ⁇ 95%RH, temperature is 15 ⁇ 25°C
  • the photochromic composite fiber can be obtained by stretching, oiling, winding, and drawing at a ratio of 1 to 5.
  • Photochromic dyes of the invention include, but are not limited to, the following broad class of photochromic compounds:
  • R 1 H,CH 3 ,OCH 3 ,halogen
  • R 2 C 1 -C 6 alkyl, C 1 -C 6 alkyl heterocycle
  • R 3 nitrogen heterocycle, C 1 -C 6 alkyl diamine
  • R 4 C 1 -C 6 alkoxy
  • Patent in China ZL97120274.5 spiro-type photochromic compound and preparation method thereof; ZL200410072348.86'-heterocyclic substituted spirooxazine photochromic compound and preparation method thereof; 201110058243.7 substituted spirooxazine photochromic compound The preparation method is described in detail.
  • R 1 H,CH 3 ,OCH 3 ,halogen
  • R 2 C 1 -C 6 alkyl, C 1 -C 6 alkyl heterocycle
  • R 3 nitrogen heterocycle, C 1 -C 6 alkyl diamine
  • R 1 H,CH 3 ,OCH 3 ,halogen
  • R 2 C 1 -C 6 alkyl, C 1 -C 6 alkyl heterocycle
  • R 3 nitrogen heterocycle, C 1 -C 6 alkyl diamine
  • R 1 2-C 1 -C 8 alkoxy
  • R 2 4-C 1 -C 8 alkoxy
  • R 1 2-halogen
  • R 2 4-C 1 -C 8 alkoxy or C 1 -C 8 alkyl
  • R 1 2-C 1 -C 8 alkoxy
  • R 2 4-C 1 -C 8 alkyl
  • R 1 2-aryloxy
  • R 2 4-aryloxy
  • R 1 H
  • R 2 4-C 1 -C 8 alkoxy
  • R 1 H, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy
  • R 2 C 1 -C 8 alkyl, C 1 -C 8 alkoxyaromatic
  • R 1 H, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy
  • R 2 C 1 -C 8 alkyl, C 1 -C 8 alkoxyaromatic
  • the invention has the advantages and positive effects that the fiber adopts a sheath-core composite structure, and the photochromic material and the functional additive are doped in the core layer material, and then the sheath-core composite structure is constructed by melt spinning, and the functional additive is used.
  • the skin layer encapsulates the core layer to improve the stability of the photochromic material in the core material, while the pressure-responsive photochromic microcapsule or nanocapsule solution can avoid photochromism during melt spinning.
  • the fiber of the invention has ultraviolet light higher than 4000 ⁇ W/cm 2 , temperature 40 ° C, and normal humidity. Accelerated aging test, the color change ability can be maintained for 70-110 hours, and the optically variable materials currently on the market are measured under the same conditions.
  • the fibers of the present invention is extremely weather resistance, while having excellent photochromic properties, fast response time, repeatable, long service life, excellent mechanical properties.
  • the use of melt-sheath composite spinning not only improves the spinning rate and fiber strength, but also has no pollution to the environment, and the composite fiber of the sheath-core structure has almost no influence on fiber strength, wearing comfort and washing durability.
  • the fiber of the invention can be widely applied in the fields of advertising, anti-counterfeiting, clothing and military camouflage, and has high safety value, economic value and military value.
  • Figure 1 is an electron micrograph of a fiber obtained in Example 1 of the present invention.
  • Figure 2 is an electron micrograph of a cross section of a fiber obtained in Example 1 of the present invention.
  • Figure 3 is an electron micrograph of the fiber obtained in Example 5 of the present invention.
  • Figure 4 is an electron micrograph of a cross section of a fiber obtained in Example 5 of the present invention.
  • the photochromic composite fiber of the invention comprises a skin layer and a core layer, the skin layer and the core layer have a concentric structure, and the skin layer closely covers the core layer;
  • the skin layer material is a polyolefin, a polyamide, a polyurethane, a polyester polymer.
  • the core material is a low melting point thermoplastic polymer material polyethylene, polypropylene, ethylene propylene rubber, low melting point polyester, low melting point At least one of the polyamides, and a photochromic dye, an antioxidant, a spinner, a heat stabilizer, and a sensitizer are added in a certain ratio, and the skin layer and the core layer are formed by a melt spinning process.
  • the skin material is dried and crystallized by using polyethylene terephthalate, the drying temperature is 200 ° C, the water content after drying is less than 30 ppm, and then the airtightness improver diisopropyl oxide is added in a mass ratio of 2%. After the flame retardant is 0.5% and the softener is 0.4% mixed, the skin material can be obtained.
  • the hole is merged and extruded to control the appropriate extrusion speed, so that the skin layer uniformly covers the core layer containing the photochromic dye, and then the side air blow is performed for the cooling wind speed of 0.32 m/s and the humidity of 95% RH.
  • the photochromic composite fiber can be obtained by stretching at a temperature of 25 ° C at a cooling, oiling, winding and drawing ratio of 1:2.
  • the accelerated aging test was carried out under the condition that the ultraviolet light was higher than 4000 ⁇ W/cm 2 , the temperature was 40 ° C, and the humidity was normal, and it was found that the weather resistance of the composite fiber added with the functional additive was as high as 109 hours, compared with no addition.
  • the weather resistance of the composite fiber of the additive is increased by more than 10 times.
  • the skin material polypropylene is dried and crystallized so that the moisture content after drying is less than 50 ppm, and then the airtightness improver is added to the polyethylene terephthalate 1%, the flame retardant 0.2%, and the softener according to the mass ratio.
  • the cortical material can be obtained by uniformly mixing 0.04%.
  • a photochromic composite fiber can be obtained by stretching at a ratio of 1:1.
  • the POY strength of the sheath-core composite fiber was 1.8 cN/dtex, and the treated fiber DTY was 2.6 cN/dtex.
  • the accelerated aging test was carried out under the condition that the ultraviolet ray was higher than 4000 ⁇ W/cm 2 , the temperature was 40 ° C, and the humidity was normal, and the weather resistance of the conjugate fiber of the present example was as high as 106 hours.
  • the skin material polycaprolactam is dried and crystallized so that the water content after drying is less than 50 ppm, and then the skin layer material is obtained by adding 1% of the airtightness improving agent and 0.3% of the softener according to the mass ratio.
  • the POY strength of the sheath-core composite fiber was 2.2 cN/dtex, and the treated fiber DTY was 3.4 cN/dtex.
  • the accelerated aging test was carried out under the condition that the ultraviolet ray was higher than 4000 ⁇ W/cm 2 , the temperature was 40 ° C, and the humidity was normal, and the weather resistance of the conjugate fiber of the present embodiment was as high as 97 hours.
  • the skin material polybutylene terephthalate is dried and crystallized so that the water content after drying is less than 50 ppm, and then 0.8% of the airtightness improving agent, 0.3% of the flame retardant, and 0.05% of the softener are added according to the mass ratio.
  • the skin material can be obtained by mixing evenly.
  • a photochromic composite fiber can be obtained by stretching at 1:5.
  • test sheath core composite fiber was 2.3 cN/dtex
  • treated fiber DTY was 3.5 cN/dtex
  • the skin material polyethylene terephthalate is dried and crystallized so that the water content after drying is less than 50 ppm, and then 0.8% of the airtightness improving agent, 0.3% of the flame retardant, and 0.05% of the softener are added according to the mass ratio.
  • the skin material can be obtained after homogenization.
  • both POY and DTY are lower than the conventional sheath-core composite fibers which are not added, but the decline range is controllable, and the average is maintained within 15%, and most of them are within 10%. This is quite good.
  • the diameter of the microcapsules is larger than that of the dye.
  • the POY and DTY should be reduced more, but through the adjustment of various additives, Its performance is basically the same as the data directly added to the dye.
  • the weather resistance is excellent, and the weather resistance of the fiber directly added to the dye is increased by 10-20 times, which can fully satisfy clothing, shoes and hats, wearable equipment, anti-counterfeiting, Military and other needs.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Multicomponent Fibers (AREA)
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Abstract

一种光致变色复合纤维，包括皮层与芯层，所述皮层为成纤聚合物，添加适当的阻燃剂、柔顺剂和气密性增进剂，所述芯层为热塑性成纤聚合物，并按照一定比例添加光致变色染料、抗氧化剂、助纺剂、热稳定性剂、增感剂。该纤维将光致变色材料与功能添加剂掺杂在芯层材料中，然后通过熔融纺丝构建皮芯复合结构，用含功能助剂的皮层对芯层进行封装，从而提高了芯层材料中光致变色材料的稳定性，在紫外线高于4000μW/cm 2，温度40℃，湿度正常情况下加速老化测试，其变色能力可以保持70-110小时，同时具有优异的光致变色性、响应时间快、重复性强、使用寿命长、力学性能优良等优点。

Description

光致变色复合纤维 技术领域
本发明涉及纺织技术领域，具体涉及一种光致变色复合纤维。
背景技术
社会生产力的进步与科技的快速发展，对纺织品的传统性能提出了更高的要求，同时对纺织品的功能性也有越来越多的需求。传统功能纤维已经不能满足人们对于舒适性和功能性的需求，光致变色纤维应运而生。光致变色纤维具有独特的视觉效果，不仅能满足消费者对服饰色彩新奇性、多样性和变化性的追求而且可以广泛应用在防伪、广告、军事伪装等领域。光致变色纤维原理主要分为两种：一种是采用液晶纺制造纤维，内部含液晶结构，对入射的光具有不同的反射效果，形成不同角度光致变色；另一种是纤维内部添加或表面粘附光致变色物质，能够随着外界光照环境条件的变化而显示出不同颜色。
目前，光致变色材料已经在面料上进行应用，主要是采用涂料添加粘合剂进行高温焙烘，或者采用涂料印花和涂层来实现，普遍存在色牢度差、手感硬、耐候性差、持久性差、透气性差等缺陷。另有少部分光致变色纤维是通过液晶纺、静电纺、接枝螺噁嗪基团或螺吡喃基团、添加荧光剂或者是表面粘附特殊微胶囊生产制备，但是其制备工艺较为复杂、对环境具有较大危害、具有损害人体健康的潜在危害，此外还有表面结构易损坏、耐疲劳性差和使用寿命短等缺陷。例如中国专利ZL200580011656，约翰等采用静电纺丝法制备光致变色纤维，该方法只能制备超细短纤，且产量很低，生产过程复杂。中国专利CN101701052A孙宾宾等人采用化学接枝方法，将含螺噁嗪基团的丙烯酸酯染料单体通过过氧化苯甲酰引发聚合，接枝于硝化纤维素大分子主链，用于制备光致变色薄膜和涂层，该方法工艺复杂，使用大量有机溶剂，且无法保证接枝率。中国专利CN104357936A谢跃亭等人将光致变色微胶囊乳液与黏胶溶液混合均匀后，通过酸液纺丝得到光致变色黏胶纤维，该方法属于溶液法纺丝，工艺复杂，且污染环境，此外，制备的纤维强度偏低，大大限制了其应用。中国专利CN104047069A中，翁俊强等人将光致变色染料与低熔点尼龙切片熔融共混造粒制备母粒，然后与低熔点切粒共混熔融纺丝，经过牵伸得到光致变色POY丝，该法大大提升了纺丝效率，熔融纺丝亦不会对环境造成污染，然而光致变色染料无规律分布于纤维中，分布于表面的染料不仅降低了光致变色 功能耐候性，而且色牢度低，易脱色，会对人体、穿着或环境造成影响。陈茶娇等人在发明专利CN103556300A中选用纤维级聚对苯二甲酸乙二醇酯作为芯层，添加了苯氧基萘并萘醌类光致变色材料的聚对苯二甲酸乙二醇酯作为皮层，制备了光致变色纤维，该种方法制备的为热粘纤维，主要起粘结其他材料与支撑的作用，无法应用于产品表面及花型纹理设计，局限性较大，另外其光变染料分布于皮层降低了变色功能的耐候性，色牢度低，易脱色，也对人体健康、穿着舒适性及环境造成危害。
发明内容
本发明的目的是解决现有复合纤维变色功能耐候性差、色牢度低、易脱色等缺点，提供一种光致变色复合纤维。
本发明的技术方案是：光致变色复合纤维，所述纤维的横截面中，皮层和芯层呈同心圆结构，皮层紧密包覆着芯层；所述皮层为成纤聚合物，选用聚烯烃、聚酰胺、聚酯或聚氨酯类聚合物的至少一种，并添加适当的阻燃剂、柔顺剂和气密性增进剂；所述芯层为热塑性成纤聚合物，聚烯烃、聚酯、聚酰胺、聚氨酯中的至少一种，并按照一定比例添加光致变色染料、抗氧化剂、助纺剂、热稳定性剂、增感剂。所述皮层和芯层通过熔融纺丝工序制备成型。
进一步的，所述光致变色染料外层包覆柔韧性透明聚合物外壳，所述柔韧性透明聚合物外壳与光致变色染料质量比为5:95～95:5，粒径分布在0.1～5微米，形成光致变色微胶囊或纳米胶囊，该外壳具有压力响应性能，根据光致变色染料的体积变化而膨胀或收缩。该聚合物一般选用聚烯烃高分子如聚烯烃或其共聚物，聚酯或其共聚物，聚酰胺，聚氨酯、丙烯腈共聚物、氨基树脂、聚脲等线型或低交联度高聚物中的至少一种，优选聚酯类或聚氨酯类聚合物外壳。
芯层成纤聚合物优选熔点低于250℃的低熔点聚合物，聚乙烯、聚丙烯、乙丙橡胶、低熔点聚酯，低熔点聚酰胺中的至少一种；皮芯结构中所述皮层与所述芯层材料质量比为5:95～95:5。
所述增感剂选用芳香族或脂肪族的酯类，具体为1-羟基-2萘甲酸苯酯、乙二酸二苄酯、对苄基联苯中的至少一种。
所述柔顺剂为单烷基季铵盐、二烷基季铵盐、烷基酰基季铵盐、吡啶季铵盐型或咪唑型柔软剂中的至少一种。
所述助纺剂主要包括分散剂、偶联剂等。所述助纺剂为钛酸酯系列、硅烷系列、硬 脂酸酯系列、异丙基异硬脂酰基-甲基丙烯基钛酸酯等系列中的至少一种，硅烷系列包括双-(γ-三乙氧基硅基丙基)四硫、γ-巯基三甲氧基硅烷、γ-甲基丙烯酰基三甲氧基硅烷、γ-缩水甘油氧基三甲氧基硅烷和γ-氨丙基三乙氧基硅烷；硬脂酸酯系列包括硬脂酸、甘油单硬脂酸酯和甘油三硬脂酸酯等中的至少一种。助纺剂添加量为芯层成纤聚合物质量的1～10％。
所述的抗氧化剂为叔丁基羟基茴香醚(BHA)、二丁基羟基甲苯(BHT)、叔丁基对苯二酚(TBHQ)、没食子酸丙酯(PG)、抗坏血酸棕榈酸酯(AP)、硫代二丙酸二月桂酸酯(DLTP)、4-己基间苯二酚(4-HR)中的至少一种。
所述皮层添加的气密性增进剂为聚萘二甲酸乙二醇酯，双异丙基化合物，三元乙丙橡胶之中至少一种的有机酯溶液。
所述芯层各组分的含量为：所述芯层各组分占成纤聚合物的质量比为：光致变色染料1～10％、助纺剂0.22～0.62％(其中分散剂0.2～0.5％、偶联剂0.02～0.12％)、热稳定剂0.03～0.3％、抗氧化剂0.01～0.09％、增感剂0.1～5％。
所述皮层各组分占成纤聚合物的质量比为：气密性增进剂0.1～2％、阻燃剂0～0.5％，柔顺剂0.04～0.4％。
所获得的复合纤维的POY强度为1.5～3.5cN/dtex，经处理后的纤维DTY为2.0～5.0cN/dtex。
所述光致变色复合纤维由如下制备方法制备得到的：
1、先将作为皮层的可熔融加工的成纤聚合物进行干燥，使干燥后的含水率小于50ppm，然后按照成纤聚合物质量百分比加入气密性增进剂0.1～2％、阻燃剂0～0.5％、柔顺剂0.04～0.4％，混合均匀后熔融造粒，便可得到皮层材料切粒；
2、将芯层材料低熔点成纤聚合物进行真空干燥，使干燥后的含水率小于50ppm，然后按照质量比加入光致变色染料1～10％、分散剂0.2～0.5％，偶联剂0.02～0.12％，热稳定剂0.03～0.3％，抗氧化剂0.01～0.09％，混合均匀后，熔融造粒，便可得到芯层材料；3、通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，分别挤出带有光致变色材料的芯层材料与皮层材料，然后通过熔体分配管计量控制皮层与芯层质量比，使其进入具有同心圆皮芯复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色染料的芯层，然后进行侧吹风进行冷却，风速为0.3±0.03m/s，湿度为75％～95％RH，温度为15～25℃下 冷却、上油、卷绕和牵伸比1～5的拉伸便可得到所述光致变色复合纤维。
本发明涉及的材料均可通过市售途径获得。
本发明所述的光致变色染料包括但不限于下述大类光致变色化合物：
(一)萘并螺噁嗪类
Figure PCTCN2017115575-appb-000001
R1＝H，CH3，OCH3，卤素
R2＝C1-C6烷基，C1-C6烷基杂环
R3＝氮杂环，C1-C6烷基二胺
R4＝C1-C6烷氧基
在中国专利：ZL97120274.5螺环类光致变色化合物及其制备方法；ZL200410072348.86’-杂环取代螺噁嗪类光致变色化合物及其制备方法；201110058243.7取代螺噁嗪类光致变色化合物的制备方法中详细记载。
(二)喹啉并螺噁嗪类
Figure PCTCN2017115575-appb-000002
R1＝H，CH3，OCH3，卤素
R2＝C1-C6烷基，C1-C6烷基杂环
R3＝氮杂环，C1-C6烷基二胺
在201110058251.1喹啉并螺噁嗪类光致变色化合物及其制备方法中有详细记载
(三)苯并螺噁嗪类
Figure PCTCN2017115575-appb-000003
R1＝H，CH3，OCH3，卤素
R2＝C1-C6烷基，C1-C6烷基杂环
R3＝氮杂环，C1-C6烷基二胺
(四)二芳杂环基乙烯类化合物
Figure PCTCN2017115575-appb-000004
X＝Y＝S                    X＝S       Y＝N
R1＝R2＝R3＝CH3          R1＝R2＝R3＝CH3
R1＝R3＝CH3             R1＝R2＝CH3
R1＝H                       R2＝H
R2＝R1＝CH3，R3＝H         R2＝R1＝CH3，R3＝H
Figure PCTCN2017115575-appb-000005
X＝Y＝S                      X＝S      Y＝N
R1＝R2＝R3＝CH3           R1＝R2＝R3＝CH3
R1＝R3＝CH3              R1＝R3＝CH3
R1＝H                      R2＝H
Figure PCTCN2017115575-appb-000006
X＝Y＝S                       X＝S     Y＝N
R＝CH3                       R＝CH3
Figure PCTCN2017115575-appb-000007
X＝Y＝S                  X＝S     Y＝N
R＝CH3           R＝CH3
Figure PCTCN2017115575-appb-000008
X＝Y＝S                  X＝N     Y＝S
R1＝R2＝R3＝CH3       R1＝R2＝R3＝CH3
R4＝H                     R4＝OCH3
R1＝R2＝CH3           R1＝R2＝CH3
R3＝CN，CHO             R3＝CN，CHO
R4＝H                     R4＝OCH3
                    R1＝CH3，R2＝H，R3＝CN，CHO，R4＝OCH3
Figure PCTCN2017115575-appb-000009
X＝Y＝S                       X＝N    Y＝S
R1＝R2＝R3＝CH3        R1＝R2＝R3＝CH3
R4＝H                         R4＝OCH3
R3＝R1＝CH3     R2＝R4＝H
R1＝CH3，R2＝R4＝H        R1＝R2＝CH3  R3＝CN，CHO
R3＝CN，CHO              R4＝OCH3
                           R1＝CH3，R2＝H
                           R3＝CN，CHO  R4＝OCH3
(五)芳基取代萘并吡喃类
Figure PCTCN2017115575-appb-000010
R1＝2-C1-C8烷氧基     R2＝4-C1-C8烷氧基
R1＝2-卤素             R2＝4-C1-C8烷氧基或C1-C8烷基
R1＝H                 R2＝SCH3
R1＝2-C1-C8烷氧基     R2＝4-C1-C8烷基
R1＝2-芳基氧           R2＝4-芳基氧
R1＝H                 R2＝4-C1-C8烷氧基
R1＝H                 R2＝4-卤素
R1＝H                 R2＝4-CF3
Figure PCTCN2017115575-appb-000011
R1＝R2＝H
在200510013276.4萘并吡喃光致变色化合物及其制品；200410072350.5 2,2-二芳基萘并吡喃类化合物及其制备方法中有详细记载。
(六)螺吡喃类化合物
Figure PCTCN2017115575-appb-000012
R1＝H，卤素，C1-C6烷基，C1-C6烷氧基
R2＝C1-C8烷基，C1-C8烷氧基芳杂环
相关专利：ZL97120274.5螺环类光致变色化合物及其制备方法
Figure PCTCN2017115575-appb-000013
R1＝H，卤素，C1-C6烷基，C1-C6烷氧基
R2＝C1-C8烷基，C1-C8烷氧基芳杂环
本发明具有的优点和积极效果是：该纤维采用皮芯复合结构，将光致变色材料与功能添加剂掺杂在芯层材料中，然后通过熔融纺丝构建皮芯复合结构，用含功能助剂的皮层对芯层进行封装，从而提高了芯层材料中光致变色材料的稳定性，而采用压力响应型光致变色微胶囊或纳米胶囊的技术方案，可以避免熔融纺丝过程中光致变色染料体积膨胀引起的囊壁破裂，进而降低由于囊芯受热挥发引起的纤维断裂和纤维光致变色性能的衰减；在皮层纤维中添加了气密性增进剂，可以在使用过程中，阻隔外界氧气及其他活性物质与芯层物质中的光致变色染料反应，使光致变色性能不衰减，通过上述技术方案，本发明的纤维在紫外线高于4000μW/cm2，温度40℃，湿度正常情况下加速老化测试，其变色能力可以保持70-110小时，而目前市场上的光变材料在同样条件下测试其变色能力仅可以保持5-10小时，表明本发明的纤维具有极强的耐候性，同时具有优异的光致变色性、响应时间快、重复性强、使用寿命长、力学性能优良。此外，采用熔融皮芯复合纺丝，既提高了纺丝速率和纤维强度，又对环境无污染，且皮芯结构的复合纤维对纤维强度、穿着舒适度、耐洗性几乎无任何影响。本发明的纤维可广泛应用在广告、防伪、服装服饰和军事伪装等领域，具有较高的安全价值、经济价值和军事价值。
附图说明
图1是本发明实施例1获得纤维的电镜照片
图2是本发明实施例1获得纤维横截面的电镜照片
图3是本发明实施例5获得纤维的电镜照片
图4是本发明实施例5获得纤维横截面的电镜照片
具体实施方式
本发明的光致变色复合纤维，包括皮层与芯层，皮层和芯层呈同心圆结构，皮层紧密包覆着芯层；所述皮层材料为聚烯烃、聚酰胺、聚氨酯、聚酯类聚合物的至少一种，并添加适当的阻燃剂、柔顺剂和气密性增进剂，所述芯层材料为低熔点热塑性高分子材料聚乙烯、聚丙烯、乙丙橡胶、低熔点聚酯，低熔点聚酰胺中的至少一种，并按照一定比例添加光致变色染料、抗氧化剂、助纺剂、热稳定性剂、增感剂，所述皮层和芯层通过熔融纺丝工序制备成型。
下面结合具体实施例的制备方法，对本发明的技术方案进行进一步的阐述。
实施例1
(1)皮层材料选用聚对二甲酸乙二醇酯进行干燥结晶，干燥温度200℃，使干燥后的含水率小于30ppm，然后按照质量比加入气密性增进剂双异丙基氧化物2％、阻燃剂0.5％、柔顺剂0.4％混合均匀后，便可得到皮层材料。
(2)将芯层材料聚丙烯进行干燥结晶，干燥温度200℃，使干燥后的含水率小于30ppm，然后按照质量比加入光致变色染料5％、分散剂0.5％，偶联剂0.12％，热稳定剂0.3％，抗氧化剂0.09％，增感剂1％，混合均匀后便可得到芯层材料。
(3)通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，其中芯层材料在螺杆泵下螺杆温度为：一区225℃，二区235℃，三区240℃；皮层材料在螺杆泵下螺杆温度为：一区280℃，二区285℃，三区290℃，四区295℃；箱体温度300℃；分别挤出带有光致变色染料的芯层材料与皮层材料，然后通过熔体分配管计量达控制皮层与芯层质量比50：50，使其进入具有同心圆皮芯型复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色染料的芯层，然后进行侧吹风进行冷却风速为0.32m/s，湿度为95％RH，温度为25℃下冷却、上油、卷绕和牵伸比1：2的拉伸便可得到光致变色复合纤维。
性能测试：
(1)测试复合纤维的表面微观结构，如图1所示，纤维表面光滑，纤维直径均匀，分布在15～20微米；对纤维内部结构进行测试，如图2所示，可见具有明显的皮芯结构，皮层纤维的厚度均匀，约为2.5微米，完整的包裹芯层纤维；
(2)测试复合纤维的POY强度为2.1cN/dtex，经处理后的纤维DTY为3.5cN/dtex。
(3)测试复合纤维的耐候性：在紫外线高于4000μW/cm2，温度40℃，湿度正常情况下进行加速老化测试，发现添加功能添加剂的复合纤维耐候性高达109小时，相比于未添加助剂的复合纤维耐候性提升了10倍以上。
实施例2
(1)皮层材料聚丙烯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入气密性增进剂聚对萘二甲酸乙二醇酯1％、阻燃剂0.2％、柔顺剂0.04％混合均匀后便可得到皮层材料。
(2)将芯层材料聚乙烯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入光致变色染料5％、分散剂0.2％，偶联剂0.02％，热稳定剂0.03％，抗氧化剂 0.01％，增感剂0.1％，混合均匀后便可得到芯层材料。
(3)通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，分别挤出带有光致变色染料的芯层材料与皮层材料，然后通过熔体分配管计量控制皮层与芯层质量比使其进入具有同心圆皮芯型复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色染料的芯层，然后进行侧吹风进行冷却风速为0.3m/s，湿度为75％RH，温度为15℃下冷却、上油、卷绕和牵伸比为1:1的拉伸便可得到光致变色复合纤维。
性能测试：
(1)测试皮芯复合纤维的POY强度为1.8cN/dtex，经处理后的纤维DTY为2.6cN/dtex。
(2)测试复合纤维的耐候性：在紫外线高于4000μW/cm2，温度40℃，湿度正常情况下进行加速老化测试，本实施例的复合纤维耐候性高达106小时。
实施例3
(1)皮层材料聚己内酰胺进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入气密性增进剂1％、柔顺剂0.3％混合均匀后便可得到皮层材料。
(2)将芯层材料低熔点聚酯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入光致变色染料8％、分散剂0.4％，偶联剂0.11％，热稳定剂0.2％，抗氧化剂0.07％，增感剂2％，混合均匀后便可得到芯层材料。
(3)通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，分别挤出带有光致变色染料的芯层材料与皮层材料，然后通过熔体分配管计量达控制皮层与芯层质量比使其进入具有同心圆皮芯型复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色染料的芯层，然后进行侧吹风进行冷却风速为0.31m/s，湿度为85％RH，温度为18℃下冷却、上油、卷绕和牵伸比1：3的拉伸便可得到光致变色复合纤维。
性能测试：
(1)测试皮芯复合纤维的POY强度为2.2cN/dtex，经处理后的纤维DTY为3.4cN/dtex。
(2)测试复合纤维的耐候性：在紫外线高于4000μW/cm2，温度40℃，湿度正常 情况下进行加速老化测试，本实施的复合纤维耐候性高达97小时。
实施例4
(1)皮层材料聚对苯二甲酸丁二醇酯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入气密性增进剂0.8％、阻燃剂0.3％、柔顺剂0.05％混合均匀后便可得到皮层材料。
(2)将芯层材料聚对苯二甲酸丁二醇酯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入光致变色染料9％、分散剂0.3％，偶联剂0.03％，热稳定剂0.04％，抗氧化剂0.03％，增感剂0.5％，混合均匀后便可得到芯层材料。
(3)通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，分别挤出带有光致变色染料的芯层材料与皮层材料，然后通过熔体分配管计量控制皮层与芯层质量比，使其进入具有同心圆皮芯型复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色染料的芯层，然后进行侧吹风进行冷却风速为0.31m/s，湿度为80％RH，温度为18℃下冷却、上油、卷绕和牵伸比为1:5的拉伸便可得到光致变色复合纤维。
性能测试：
(1)测试皮芯复合纤维的POY强度为2.3cN/dtex，经处理后的纤维DTY为3.5cN/dtex。
(2)测试复合纤维的耐候性：在紫外线高于4000μW/cm2，温度40℃，湿度正常情况下进行加速老化测试，发现添加功能添加剂的复合纤维耐候性高达89小时。
实施例5
(1)皮层材料聚对二甲酸乙二醇酯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入气密性增进剂0.8％、阻燃剂0.3％、柔顺剂0.05％混合均匀后便可得到皮层材料。
(2)将芯层材料聚丙烯进行干燥结晶，使干燥后的含水率小于50ppm，然后按照质量比加入丙烯腈共聚物光致变色微胶囊9％、分散剂0.3％，偶联剂0.03％，热稳定剂0.04％，抗氧化剂0.03％，增感剂0.6％，混合均匀后便可得到芯层材料。
(3)通过熔融纺丝的工序进行纺丝，调整转矩流变仪与螺杆挤出机各区温度，分别 挤出带有光致变色微胶囊的芯层材料与皮层材料，然后通过熔体分配管计量达控制皮层与芯层质量比，使其进入具有同心圆皮芯型复合喷丝组件，两种熔体在组件中的喷丝孔处汇合并挤出，控制合适的挤出速度，使得皮层均匀紧密的包覆住含有光致变色微胶囊的芯层，然后进行侧吹风进行冷却风速为0.31m/s，湿度为80％RH，温度为18℃下冷却、上油、卷绕和牵伸比为1:5的拉伸便可得到所述胶囊型光致变色复合纤维。
性能测试：
(1)电镜观察复合纤维的表面微观结构，如图3所示，纤维表面光滑，纤维直径均匀，分布在15～20微米；对纤维内部结构进行测试，如图2所示，可见具有明显的皮芯结构，皮层纤维的厚度均匀，约为2.5微米，完整的包裹芯层纤维；
(2)测试皮芯复合纤维的POY强度为2.1cN/dtex，经处理后的纤维DTY为3.3cN/dtex。
(3)测试复合纤维的耐候性：在紫外线高于4000μW/cm2，温度40℃，湿度正常情况下进行加速老化测试，发现添加柔韧性丙烯腈共聚物微胶囊的复合纤维耐候性高达101小时。
对比试验：同时，申请人还按照实施例1-4的皮芯聚合物选材，制备了常规不添加光致变色材料和助纺剂等助剂的皮芯复合纤维作为空白对照(记为1-1，2-1，3-1，4-1)、只在芯层加入光致变色染料，不加入助纺剂等助剂的皮芯复合纤维(记为1-2，2-2，3-2，4-2)、本申请实施例1-5的复合纤维进行试验数据对比，综合见下表。
表1纤维强度对比表
编号 1 1-1 幅度 2 2-1 幅度 3 3-1 幅度 4 4-1 幅度 5
POY 2.1 2.2 4.55％ 1.8 2.0 10％ 2.2 2.4 8.33％ 2.3 2.5 8％ 2.1
DTY 3.5 3.8 7.89％ 2.6 2.9 10％ 3.4 3.9 12.82％ 3.5 4.0 12.5％ 3.3
由上表可见，本申请的实施例1-4，POY、DTY均比未添加的常规皮芯复合纤维有所下降，但是下降幅度可控，基本维持在15％以内，大部分为10％以内，这一点表现相当出色。而1与5对比，5作为加入了微胶囊颗粒的复合纤维，其微胶囊直径比染料粒径更大，按照理论推断，其POY、DTY应该降低更多，但是通过各类助剂的调整，其性能基本与直接加入染料的数据持平。
同时，还做了耐候性试验的对比数据，见下表
表2耐候性数据对比表
编号 1 1-2 2 2-2 3 3-2 4 4-2 5
耐候性 109 5 106 7 97 8 89 5 101
由上表可见，本申请的实施例1-5，耐候性均表现优异，比直接加入染料的纤维耐候性均提高了10-20倍，完全可以满足服装、鞋帽、可穿戴设备、防伪、军事等方面的需求。
以上对本发明的一个实施例进行了详细说明，但所述内容仅为本发明的较佳实施例，不能被认为用于限定本发明的实施范围。凡依本发明申请范围所作的均等变化与改进等，均应仍归属于本发明的专利涵盖范围之内。

Claims (10)

  1. 光致变色复合纤维，包括皮层与芯层，其特征在于：所述纤维的横截面中，皮层和芯层呈同心圆结构，皮层紧密包覆着芯层；所述皮层为成纤聚合物，添加适当的阻燃剂、柔顺剂和气密性增进剂，所述芯层为热塑性成纤聚合物，并按照一定比例添加光致变色染料、抗氧化剂、助纺剂、热稳定性剂、增感剂。
  2. 根据权利要求1所述的光致变色复合纤维，其特征在于：所述皮层成纤聚合物为聚烯烃、聚酰胺、聚氨酯、聚酯类聚合物的至少一种，所述芯层为低熔点热塑性高分子材料聚烯烃、聚酯、聚酰胺、聚氨酯中的至少一种，并按照一定比例添加光致变色染料、抗氧化剂、助纺剂、热稳定性剂及增感剂，所述皮层和芯层通过熔融纺丝工序制备成型。
  3. 根据权利要求1所述的光致变色复合纤维，其特征在于：所述光致变色染料外层包覆柔韧性透明聚合物外壳，粒径分布在0.1～5微米，具有压力响应性能，所述柔韧性透明聚合物外壳与光致变色染料质量比为5:95～95:5。
  4. 根据权利要求2所述的光致变色复合纤维，其特征在于：所述光致变色染料外层包覆柔韧性透明聚合物外壳，粒径分布在0.1～5微米，具有压力响应性能，所述柔韧性透明聚合物外壳与光致变色染料质量比为5:95～95:5。
  5. 权利要求3或4所述的光致变色复合纤维，其特征在于：所述聚合物外壳选用聚烯烃高分子如聚烯烃或其共聚物、聚酯或其共聚物、聚酰胺、聚氨酯、丙烯腈共聚物、氨基树脂、聚脲等线型或低交联度高聚物中的至少一种。
  6. 权利要求1-4任一项所述的光致变色复合纤维，其特征在于：所述芯层聚合物为熔点低于250℃的低熔点聚合物，选用聚乙烯、聚丙烯、乙丙橡胶、低熔点聚酯、低熔点聚酰胺中的至少一种；所述皮层与所述芯层材料质量比为5:95～95:5。
  7. 权利要求1-4任一项所述的光致变色复合纤维，其特征在于：所述柔顺剂为单烷基季铵盐、二烷基季铵盐、烷基酰基季铵盐、吡啶季铵盐型或咪唑型柔软剂中的至少一种；
    所述抗氧化剂为叔丁基羟基茴香醚、二丁基羟基甲苯、叔丁基对苯二酚、没食子酸丙酯、抗坏血酸棕榈酸酯、硫代二丙酸二月桂酸酯、4-己基间苯二酚中的至少一种；
    所述气密性增进剂为聚萘二甲酸乙二醇酯，双异丙基化合物，三元乙丙橡胶中至少一种的有机酯溶液；
    所述增感剂选用芳香族或脂肪族的酯类，具体为1-羟基-2萘甲酸苯酯、乙二酸二苄酯、对苄基联苯中的至少一种。
  8. 权利要求1-4任一项所述的光致变色复合纤维，其特征在于：所述助纺剂为钛酸酯系列、硅烷系列、硬脂酸酯系列、异丙基异硬脂酰基-甲基丙烯基钛酸酯系列中的至少一种，硅烷选自双-(γ-三乙氧基硅基丙基)四硫、γ-巯基三甲氧基硅烷、γ-甲基丙烯酰基三甲氧基硅烷、γ-缩水甘油氧基三甲氧基硅烷和γ-氨丙基三乙氧基硅烷中的至少一种；硬脂酸酯系列选自硬脂酸、甘油单硬脂酸酯和甘油三硬脂酸酯中的至少一种，助纺剂添加量为芯层成纤聚合物添加质量的1～10％。
  9. 权利要求1-4任一项所述的光致变色复合纤维，其特征在于：所述芯层各组分占成纤聚合物的质量比为：光致变色染料1～10％、助纺剂0.22～0.62％、热稳定剂0.03～0.3％、抗氧化剂0.01～0.09％、增感剂0.1-5％。
  10. 权利要求1-4任一项所述的光致变色复合纤维，其特征在于：所述皮层各组分占成纤聚合物的质量百分比为：气密性增进剂0.1～2％、阻燃剂0～0.5％，柔顺剂0.04～0.4％。
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