JP2010111967A - Method for producing woven or knitted fabric of cellulose ester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a woven or knitted fabric of a cellulose ester fiber by which the woven or knitted fabric having excellent feeling, bulking feeling and color development can be diversified by using a multifilament yarn comprising a cellulose ester. <P>SOLUTION: The method for producing the woven or knitted fabric of the cellulose ester fiber includes carrying out the weaving or knitting by using, as a warp yarn, a multifilament yarn obtained by subjecting a multifilament yarn obtained by melt spinning and comprising the cellulose ester to hot drawing in the warping, or to hot drawing at the same time with the drying after being soaked in a sizing bath. The drawing ratio at the hot drawing is regulated so as to be 1.02-1.15 times. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  In the production of a cellulose ester fiber knitted fabric using a multifilament yarn composed of cellulose ester obtained by melt spinning as warp yarn, the present invention is hot-drawn in a warp yarn weaving preparation step, or immersed in a paste bath, Heat drawing at the same time as drying, and using the resulting multifilament yarn as warp yarn, weaving and weaving make it possible to achieve high color development and no physical problems even after high-pressure dyeing at a temperature of 100 ° C or higher The present invention relates to a method for producing a woven or knitted fabric having

  Cellulosic materials such as cellulose esters and cellulose ethers have recently attracted a great deal of attention as biomass materials that are produced most in the world and as biodegradable materials in natural environments. In addition, since the cellulosic material has a low refractive index, when it is made into a fiber, it has an advantage of being excellent in vivid color development.

  Such cellulosic fibers can be produced by a solution spinning method or a melt spinning method. However, all of the cellulosic fibers obtained by the melt spinning method are not capable of high-pressure dyeing. When high-temperature dyeing is performed, there is a problem that physical properties such as strength and elongation are greatly reduced so that they cannot be used for clothing products. Further, high-pressure dyeing at a temperature of less than 100 ° C. has a problem in that disperse dyes, particularly compounded disperse dyes, are poor in exhaustibility and cannot provide sufficient color development.

  Conventionally, it is known that the dyeing temperature of cellulose acetate propionate fiber which is a cellulose fatty acid ester fiber is 90 ° C. (Example), and the dyeing temperature of polyethylene terephthalate fiber is 130 ° C. (Comparative Example) ( (See Patent Document 1). The composite fabric using these fibers in combination cannot perform high-temperature and high-pressure dyeing at 100 ° C. or higher due to the characteristics of cellulose ester fiber, so that the dispersibility of the disperse dye is insufficient and color development cannot be obtained. There is a problem that a variety of textures cannot be obtained.

Further, there is no specific description of the weaving process regarding the woven fabric lining using cellulose ester fibers for warp and weft yarns, but the dyeing temperature was dyed at a temperature of 90 ° C. using Kayalon Polyester Blue dye, and triacetate There is a document describing a comparative example in which fibers are dyed at a temperature of 110 ° C. (see Patent Document 2). This document relates to dyeing cellulose ester fibers with disperse dyes at temperatures below 100 ° C. under high pressure. Is not shown.
JP 2004-169242 A (pages 6 to 8) JP 2005-336696 A

  The object of the present invention is to solve the above-mentioned problems of the prior art and to enable dyeing with a disperse dye at a temperature of 100 ° C. or higher under high pressure, thereby providing a high color development characteristic of multifilament yarn made of cellulose ester. Another object of the present invention is to provide a method for producing a cellulose ester fiber woven or knitted fabric having practical physical properties.

  The present invention aims to achieve the above object, and the method for producing a cellulose ester fiber woven or knitted fabric of the present invention uses a multifilament yarn made of cellulose ester obtained by melt spinning as a warp yarn. A method for producing a woven or knitted cellulose ester fiber, characterized in that a multifilament yarn obtained by hot drawing during production is used as a warp yarn when knitting or weaving.

  According to the preferable aspect of the manufacturing method of the cellulose-ester-fiber-woven-knitted fabric of this invention, the draw ratio in the said heat drawing is 1.02-1.15 times.

  In addition, the method for producing a cellulose ester fiber woven or knitted fabric of the present invention is obtained by immersing a multifilament yarn made of cellulose ester obtained by melt spinning in a glue bath and then hot-drawing simultaneously with drying. It is a manufacturing method characterized by using the yarn and knitting and weaving.

  According to the preferable aspect of the manufacturing method of the cellulose ester fiber woven or knitted fabric of the present invention, in the step of heat drawing simultaneously with the drying, the draw ratio is 1.02 to 1.15 times, and the drying temperature is 90 to 150 ° C. It is to be.

  According to a preferred aspect of the method for producing a cellulose ester fiber woven or knitted fabric of the present invention, the warp yarn is composed of a yarn formed by combining a multifilament yarn made of cellulose ester and a polyester fiber that can be drawn or drawn simultaneously. It will be.

  According to the preferable aspect of the manufacturing method of the cellulose ester fiber woven or knitted fabric of the present invention, at least a part of the acyl group of the cellulose ester is an acyl group having 3 to 18 carbon atoms.

  According to a preferred embodiment of the method for producing a cellulose ester fiber woven or knitted fabric of the present invention, the cellulose ester is cellulose acetate propionate or cellulose acetate butyrate.

  According to the present invention, it is possible to obtain a cellulose ester fiber woven or knitted fabric using a multifilament yarn made of cellulose ester having high color development properties and physical properties that have no practical problems even after high-pressure dyeing at a temperature of 100 ° C. or higher. It is possible to diversify the knitted and knitted fabrics having excellent texture, bulge and color development. Therefore, it becomes possible to obtain a woven or knitted fabric in combination with a polyester fiber yarn or the like that requires high-pressure dyeing.

  According to the present invention, the warp yarn is glued in the knitting and weaving process to make it difficult for the yarn to fluff or fluff, and the same effect as the improvement of the knitting property by improving the fiber convergence can be obtained.

  According to the present invention, as a new effect, thermal brittleness is suppressed even when dyeing at 100 ° C. or higher under high pressure when dyeing a woven or knitted fabric of a multifilament yarn made of cellulose ester obtained by conventional melt spinning. Can maintain the strength of the woven or knitted fabric necessary for fibrillation and actual wearing of the sewn product using the obtained cellulose ester fiber woven or knitted fabric, and is capable of exhausting disperse dyes at temperatures below 100 ° C under high pressure. It becomes easy to combine with low-polyester fibers and the like, and it is possible to expand the variation of the woven or knitted fabric.

  Next, the manufacturing method of the woven or knitted fabric of the present invention will be described in detail.

  The method for producing a woven or knitted cellulose ester fiber knitted fabric of the present invention is obtained by subjecting a multi-filament yarn made of cellulose ester obtained by melt spinning to hot drawing with the passage of time, or after being immersed in a paste bath and hot drawing simultaneously with drying. A method for producing a knitted or knitted fabric, wherein the obtained multifilament yarn is knitted and woven using warp yarn.

  In the cellulose ester constituting the multifilament yarn comprising cellulose ester obtained by melt spinning used in the present invention, at least a part (part or all) of three hydroxyl groups per glucose unit of cellulose is substituted with an ester bond. Say what you are. In the present invention, a cellulose ester in which two or more of three hydroxyl groups per glucose unit of cellulose are substituted with an ester bond is preferably used. In the present invention, the remaining hydroxyl groups not substituted with ester bonds may be those not substituted with ester bonds, or those substituted with carbamates or ether bonds.

  The cellulose ester used in the present invention may be a cellulose fatty acid ester or a cellulose aromatic acid ester, but a cellulose fatty acid ester is preferably used.

  Examples of fatty acids that form ester bonds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. It is done. Examples of the aromatic acid that forms a ceester bond include benzoic acid, toluic acid, salicylic acid, cinnamic acid, naphthoic acid, phthalic acid, and furanic acid.

  In the present invention, a mixed (mixed) ester using a plurality of the above-mentioned acids can also be used. For example, a mixed ester of a lower fatty acid can be obtained by reacting a mixture of an acid anhydride of one acid and another acid with cellulose.

  The cellulose ester used in the present invention is preferably a cellulose ester in which at least a part (part or all) of three hydroxyl groups per glucose unit of cellulose is an acyl group having 3 to 18 carbon atoms. By using a cellulose ester having at least part of an acyl group having 3 to 18 carbon atoms, a more flexible fiber can be obtained. Furthermore, it is preferable to use a cellulose ester of an acyl group having 3 to 10 carbon atoms from the surface of the texture in the case of a woven or knitted fabric.

  Specific examples of the cellulose ester in which at least a part of the hydroxyl group is substituted with an acyl group having 3 to 18 carbon atoms include cellulose acetate propionate, cellulose propionate, cellulose acetate butyrate, and cellulose butyrate. be able to. Especially, cellulose acetate propionate in which an acetyl group having 2 acyl groups and a propionyl group having 3 acyl groups are bonded to cellulose, and an acetyl group and acyl having 2 acyl groups in cellulose. A fiber (multifilament yarn) made of cellulose acetate butyrate bonded with a butyryl group having a base carbon number of 4 has an appropriate hygroscopic property and good mechanical properties, and therefore is particularly preferably used in the present invention.

  In the present invention, the multifilament yarn mainly composed of cellulose ester is a desirable requirement from the viewpoint of the spinning environment in that it is not necessary to use a harmful agent at the time of production and production by the melt spinning method. .

  In applying the melt spinning method, a plasticizer can be contained in addition to the cellulose ester. As the plasticizer, polyhydric alcohol plasticizers having good compatibility with cellulose esters are preferable, and ester compounds having a glycerin skeleton, polyalkylene glycols, caprolactone compounds, and the like are particularly preferably used.

  In addition to the components described above, the multifilament yarn made of cellulose ester used in the present invention includes other resins containing fatty acid esters having different acyl groups and various additives such as matting agents, deodorants, Foaming agent, color adjusting agent, flame retardant, yarn friction reducing agent, ultraviolet absorber, infrared absorber, crystal nucleating agent, antioxidant, coloring pigment, electrostatic agent, antibacterial agent, antioxidant, flame retardant and lubricant, etc. The additive may be included.

  The boiling water shrinkage of the multifilament yarn made of cellulose ester used in the present invention is preferably 0.2 to 5%. If the boiling water shrinkage rate is 5% or less, it does not shrink greatly during the hot water treatment, and occupies the outer periphery as a mixed fiber structure in a composite fiber or a mixed fiber with other fibers, and is a multifilament yarn made of cellulose ester. The good texture and high color developability possessed by the yarn will be manifested as characteristics of the mixed yarn structure. If the boiling water shrinkage is 0.2% or more, the woven or knitted fabric does not become paper-like due to insufficient shrinkage. The boiling water shrinkage of the multifilament yarn mainly composed of cellulose ester is more preferably 3% or more and 4% or less.

  It is preferable that the single fiber fineness of the fiber which comprises the multifilament yarn which consists of a cellulose ester used by this invention is 0.2-30 dtex. If the single fiber fineness is 0.2 dtex or more, a clear and deep color developability can be obtained by dyeing. The single fiber fineness is more preferably 0.7 dtex or more, and further preferably 1 dtex or more. On the other hand, if the single fiber fineness is 20 dtex or less, flexibility can be obtained. The single fiber fineness is more preferably 10 dtex or less, further preferably 5 dtex or less, and particularly preferably 3 dtex or less.

  The total fiber fineness of the fibers constituting the multifilament yarn made of cellulose ester used in the present invention is preferably 5 dtex to 800 dtex. When the total fiber fineness is less than 5 dtex, it cannot be practically used as a woven or woven physical property, and when the total fiber fineness exceeds 800 dtex or more, there is a disadvantage that it is too heavy. The total fiber fineness is more preferably 20 dtex to 500 dtex, still more preferably 30 dtex to 300 dtex.

  The fiber property of the multifilament yarn made of cellulose ester used in the present invention is preferably 0.5 to 2.0 cN / dtex in strength from the viewpoint of process passability in high-order processing such as weaving and knitting. If the elongation is 8% or more after the stretching heat treatment, there are few troubles due to the occurrence of fuzz and yarn breakage in higher processing steps such as weaving and knitting. The elongation is more preferably 15% or more and 50% or less, and further preferably 15% or more and 40% or less.

  The cross-sectional shape of the fiber constituting the multifilament yarn made of cellulose ester used in the present invention may be a perfect circular circular cross-section, or a multilobal shape, flat shape, elliptical shape, W shape, S Different cross sections such as a letter shape, an X shape, an H shape, a C shape, a paddle shape, a cross beam shape and a hollow shape may be used.

  Further, the multifilament yarn used in the present invention is a different-shrinking mixed yarn composed of two or more components by a composite spinning method, a split filament type for obtaining a super extra fine fiber having a single fiber fineness of 0.2 dtex or less, Sea island structure type fiber yarn may be used.

  Warp yarns for woven and knitted fabrics are generally sized (glued) for the purpose of improving the knitting properties of spun yarns and multifilament yarns. For spun yarn, usually sizing is always performed for a single yarn, but in many cases it is not performed for a twisted yarn of two or more yarns. In the case of multifilament yarn, in the case of non-twisted or sweet-twisted yarn of multifilament yarn, sizing is usually performed when fuzz is expected in the weaving and weaving process and production failure is expected. is there. Sizing m / c has a spun yarn specification and a multifilament yarn specification, and conditions are set according to yarn characteristics.

  The conditions of sizing are changed according to the yarn characteristics and the knitted or knitted fabric to be knitted or woven. Sizing condition settings include selection and blending of pastes and oils, adjustment of the amount and form of glue attached to the concentration and temperature of the paste bath, and the pick-up amount by mangle, and an aqueous system containing paste-type emulsions and oils in the paste bath Alternatively, in the case of only an oil agent, there is a case of a quick-drying paste, but drying is usually performed after passing through a paste bath.

  In general, drying is generally performed by hot air and then cylinder drying. After drying the glue bath, the yarn is wet with the glue, oil and water adhering to it, and the attached state changes when it comes into contact with the guide, etc., so it is dried with hot air and then dried with a metal cylinder. Although the thermal drying section is called a chamber and is continuous, the hot air temperature setting can be changed in several sections. The specification that several cylinders are arranged is common.

  The sizing condition setting varies greatly depending on the yarn used, and the standard for setting is the optimum condition for increasing the production efficiency of the weaving and weaving. The requirement is based on the premise that it is easy to drop in the dyeing process without dropping off in the process because it is the amount of glue and adhesion. The drying condition is to evaporate the water adhering in the paste bath to an appropriate moisture content with the paste and oil. Therefore, the chamber temperature and cylinder temperature appropriate conditions are determined as drying conditions depending on the amount of pick-up from the glue bath and the m / c speed of the properties of the glue and oil. Also, due to the characteristics of the yarn used, especially the hygroscopic and hydrophobic fibers, heat shrinkage and stretchability, the yarn passes through the glue bath, and the yarn is generated or tensioned in the drying zone chamber to become the original yarn. It will be adversely affected. For this reason, the machine specification is such that the draft rate can be changed to set the tension so that it does not loosen, does not loosen, and does not become too tight when the sizing yarn is dried. Setting the sizing conditions does not change the fiber characteristics, set the conditions to stabilize the sizing tension and increase the speed by sizing drying, and set the stable conditions to suppress the occurrence of trouble by sizing, and further, the weaving process passing property The most stable condition setting is basic. That is, for the original purpose of using the above-described sizing machine, the present invention uses a conventional sizing machine to heat-draw multifilament yarns using cellulose esters at a high pressure of less than 100 ° C. This makes it possible to provide a new effect so that the raw yarn characteristics that can only be dyed can be dyed at 100 ° C. or higher under high pressure.

  Next, a technique will be described in which a multifilament yarn made of cellulose ester used in the present invention is dipped in a paste bath and then hot-drawn simultaneously with drying and used as a warp yarn.

  Conventionally, when dyeing a multifilament yarn woven or knitted fabric made of cellulose ester obtained by melt spinning, if dyed at a temperature of 100 ° C. or higher under high pressure, the fiber becomes brittle due to thermal embrittlement of the multifilament yarn and It cannot withstand wearing, and it cannot improve the decrease in strength due to fibrillation of fibers due to friction or the like, or the occurrence of dyeing fastness problems. In addition, when dyeing at a temperature of less than 100 ° C. under high pressure, the disperse dye exhaustion rate is low and sufficient high color developability cannot be obtained. There was a problem to say. As a result of diligent studies to overcome such problems, the present inventors have reached the present invention.

  A multifilament yarn made of cellulose ester is usually produced by obtaining a cellulose ester from a cellulose raw material such as wood pulp or cotton linter, and melt spinning it together with a thermoplastic agent. In the melt spinning method, a cellulose ester is discharged from a spinneret, taken up at a spinning speed of about 2,000 m / min, and wound directly on a bobbin to obtain a multifilament yarn made of cellulose ester. The obtained multifilament yarn is used for forming a knitted or knitted fabric through a gluing-drying-hot drawing process which is an embodiment of the present invention. Attach multifilament yarn to the creel and warp it as a warp yarn beam on a loom or knitting machine. The warp yarn is usually sized for a woven fabric using untwisted or sweet twist, but in the case of warp knitted fabric, it is knitted as it is without sizing. In the case of interlace yarn in which weaving is performed by twisting a warp yarn or recently interlacing a multifilament in air, weaving is often performed without sizing.

  The fiber properties of cellulose ester fibers obtained by melt spinning are often low in strength and low in heat shrinkage compared to polyester fibers and nylon fibers.

  When producing multi-filament yarns made of cellulose ester as warp yarns under normal common sense conditions and producing woven fabrics, the temperature is set to 100 ° C. using a sealed high-pressure dyeing machine used for dyeing synthetic fibers. When dyeing is performed, the actual measured temperature is increased to 97 to 105 ° C. due to the hunting phenomenon of temperature control, and the maximum actually measured temperature rises to 105 ° C. regardless of the setting of 100 ° C. Although it is good, the strength of the multifilament yarn made of cellulose ester is deteriorated, and a phenomenon of ragging occurs.

  On the other hand, when the dyeing is carried out with the same hermetically sealed high-pressure dyeing machine as above and dyeing is set at the 90 ° C. level in consideration of the hunting phenomenon of temperature control so that the maximum measured temperature does not exceed 100 ° C., the dye formulation does not exhaust the dye. Therefore, a phenomenon in which the target hue and density cannot be obtained occurs. In order to dye at a temperature of 100 ° C. or higher under this high pressure, it is necessary to improve the heat resistance of the fiber.

  Therefore, the fiber characteristics of the melt-spun cellulose ester multifilament yarn were confirmed, and it was noted that the glass transition point (Tg) was around 110 ° C., and the hot drawing set was used during sizing (gluing) in the weaving process. Considered to do. As a result, in order to improve the heat resistance of multifilament yarn, which enables dyeing of multifilament yarn made of cellulose ester at a temperature of 100 ° C or higher under high pressure, the following sizing (gluing) setting conditions are important: I found out that That is, in the drying zone between the chamber and the cylinder after the multifilament yarn is immersed in the paste bath and the paste is adhered, the multifilament yarn is preferably subjected to a draft of 1.02 to 1.15 times, preferably 80 ° C. Heat treatment is performed simultaneously with stretching at a drying temperature of ˜150 ° C. In this invention, a more preferable heat draw ratio is 1.05-1.1 times, and a more preferable drying temperature is 90 to 140 degreeC.

  The reason why heat resistance is imparted to the multifilament yarn made of cellulose ester is that the glass transition point (Tg) is around 110 ° C., and therefore, crystallization and orientation of molecules are performed by stretching heat treatment. Presumed.

  For sizing, you can use equipment such as a slasher sizing machine that has been used for filaments as a pasting machine or a warper sizing machine that performs sizing at the same time as warping. In the subsequent drying, it is assumed that heat treatment, that is, so-called drying can be performed simultaneously with stretching. A partial gluing machine and a roller sizing machine can also be used as long as stretching and drying can be performed simultaneously.

  In this way, by preparing warp yarn sized by stretching and simultaneous drying, weaving by a conventional loom loom, water jet, air jet, rapier, or the like is possible.

  In the present invention, as the yarn that can be used for the warp yarn, a multifilament single yarn made of cellulose ester obtained by melt spinning, and a composite yarn with other fiber yarn can be used. Examples of other fiber yarns include yarns made of viscose rayon, cupra, acetate, nylon and polyester, and polyurethane elastic yarns, and filament yarns are particularly preferably used. More preferably, in order to give a drawing effect to the multifilament yarn made of cellulose ester, the other fibers to be combined need to be drawn at the same time or simultaneously stretchable, and have low Young's modulus and low stress elongation. Polyester fibers such as thick ansin yarn and false twisted yarns having crimpability are more preferable, and polyurethane fibers having high elasticity are preferably used as other fibers combined.

  In addition, when the other fibers to be combined are cellulosic fibers such as viscose rayon, cupra and acetate, the fibers themselves have the property of stretching in the wet state. In order to stretch and loosen, it is necessary to adjust the tension by drafting. Therefore, in the sizing process of the multifilament yarn composed of these fibers and cellulose ester, it is a preferable embodiment because it can be easily hot-drawn.

  Multi-filament yarns made of cellulose ester and other fiber yarns can be combined as a method of twisting together multi-filament yarns made of cellulose ester and other fiber yarns, and a method of air entanglement such as interlace and taslan. Existing composite technologies such as covering and false twisting can be applied. In addition, a sizing yarn of a multifilament yarn in which the warp yarn is made of cellulose ester may be used, and weaving or knitting using the other fiber yarn described above as the weft yarn may be used.

  When sizing composite yarn and viscose rayon, cupra and acetate filament yarns are used as characteristics of other fiber yarns, the fibers are stretched and tensioned during wet heat treatment like sizing because of cellulose fibers. Therefore, it is preferable to add a draft to the melt-spun cellulose ester fiber yarn and the composite yarn because the conditions for stabilizing the take-up property are necessary.

  Nylon fiber and polyester fiber raw yarns are tensioned by shrinkage, so overfeed conditions are suitable. However, yarns combined with warp yarns are yarns with low Young's modulus and low stress elongation, such as thick and thin yarns. Or a crimped yarn that has been false twisted. In addition, a yarn having a high stretch property such as a polyurethane elastic yarn can be preferably used as a composite yarn.

  Furthermore, when the multifilament yarn made of cellulose ester oriented and crystallized by simultaneous drying heat treatment with sizing drawing is heat resistant at a dyeing temperature of 105 ° C. to 120 ° C. under high pressure, as a polyester fiber yarn to be combined, a normal high pressure Under normal pressure dyeable polyester fiber yarn, cationic dyeable polyester fiber yarn, copolymerized high shrinkage polyester fiber yarn and polytrimethylene terephthalate fiber, rather than regular polyester fiber yarn dyeable with disperse dye at a temperature of 130 ° C A composite with a fiber yarn in which the dyeing temperature is lower than the temperature of 130 ° C. under high pressure, such as yarn, is suitable.

  Examples of the polyester fiber yarn that can be dyed under a high temperature condition of 100 ° C. or more and 130 ° C. or less include the normal pressure dyeable polyester fiber yarn, the cationic dyeable polyester fiber yarn, and the copolymerized high shrinkage polyester fiber. Yarns, polytrimethylene terephthalate-polyethylene terephthalate conjugate fiber polyester yarns, spun blends and shrinking composite blend yarns for higher-order blends, spontaneous stretch blend composite yarns, thick and thin composite blend yarns, etc. It does not matter. Furthermore, since the multifilament yarn made of cellulose ester used in the present invention contributes to the touch and draping effect of the woven or knitted fabric, a yarn having a twisted yarn of about 500 t / m to 3,000 t / m may be used. It doesn't matter.

  As the paste, commonly used starch, polyvinyl alcohol (PVA), acrylic paste, and the like can be used.

  Moreover, the oil agent, wax, antistatic agent, etc. as the smoothing agent can be appropriately determined in consideration of the process operability of weaving and knitting.

  The concentration and temperature of the paste bath can be determined based on conventional knowledge within the know-how of the sizing factory.

  The sizing speed varies depending on the yarn used for setting the basic conditions for drawing and drying. Therefore, the sizing speed may be determined by measuring the running tension and judging the operational stability.

  When the multifilament yarn made of cellulose ester according to the present invention is dyed at a temperature of 100 ° C. or higher under high pressure, a phenomenon in which the strength of the fiber deteriorates and becomes fragile occurs. It becomes easy to break by hooking on sharp parts or excessive tension when worn, and the necessary characteristics as clothing cannot be cleared. Therefore, as an index of the ease of tearing in the actual wearing state, the state of strength deterioration was evaluated by indexing with the tear strength determined in JISL1096. The tear strength here is more difficult to tear as the number is higher, and is easier to tear as the number is lower.

  As a method for dyeing the woven or knitted fabric obtained in the present invention, techniques such as liquid flow dyeing and zicker dyeing can be employed. As the dye, a disperse dye for acetate and polyester can be suitably used. In the dyeing step, first, the plasticizer contained in the multifilament yarn made of cellulose ester is removed with water alone or warm water. Therefore, a multi-tank open soaper or a softer machine having a temperature of 40 ° C. to 90 ° C. can be used. Then, it is dried, pressed with dry heat before dyeing, and dyed with a dyeing machine.

  The dyeing temperature can be dyed not only under a temperature condition of less than 100 ° C. under a high pressure of a conventional woven or knitted fabric made of cellulose ester but also under a temperature condition of 100 ° C. or more under a high pressure.

  In the case of a woven or knitted fabric made of the above-described composite yarn, it can be dyed with a dye corresponding to the composite fiber yarn. For example, it is possible to obtain a woven or knitted fabric excellent in texture such as high color development and swell in a dyeable fiber having a high pressure of 100 ° C. or higher such as polyester fiber yarn. In this way, it becomes possible to obtain a woven or knitted fabric in combination with yarns that require high-pressure dyeing such as polyester fiber yarn, which has been impossible in the past.

  In the present invention, a spectrocolorimeter is used for the evaluation of dyeability, and the L value is a value indicating lightness as an index of the colorimetric value. The higher the L value, the lighter the color, and the lower the L value, the more the color. It is an index that can be evaluated as being dark.

  Hereinafter, the method for producing the woven or knitted fabric of the present invention will be described in more detail with reference to Examples. Each characteristic value in the examples is obtained by the following method.

A. Tensile test of multifilament yarn under the conditions of temperature 20 ° C, humidity 65%, Shimadzu Autograph AG-50NISMS type, sample length 20cm, tensile speed 20cm / min. The value obtained by dividing the stress (cN) at the point indicated by the load by the fineness (dtex) was defined as the strength (cN / dtex) of the multifilament yarn, and the elongation at break was defined as the elongation (%) of the multifilament yarn.

B. Boiling water shrinkage of multifilament yarn After taking up the sample (multifilament yarn) and measuring the sample length L0 under a load of 0.09 cN / dtex, it was treated in boiling water for 15 minutes under no load. It was. After the treatment, the sample was air-dried, the sample length L1 was measured under a load of 0.09 cN / dtex, and calculated using the following formula. The number of measurements was 5, and the average value was defined as the boiling water shrinkage.
Boiling water shrinkage rate (%) = {(L0−L1) / L0} × 100.

C. Tear strength of woven or knitted fabric Measured by the pendulum method in JIS L 1096 (General Textile Test Method).

D. Lightness: D65, field of view: Minolta Co., Ltd. multi-light source spectrocolorimeter CM-3700d
The lightness L value was measured at 10 ° under the condition of removing regular reflection light.

Example 1
A multifilament yarn made of cellulose fatty acid mixed ester was prepared by melt spinning as follows.

  82% by weight of cellulose acetate propionate, 17.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol as a phosphite colorant Diphosphite 0.1% by weight was mixed, kneaded at a temperature of 230 ° C. using a biaxial extruder, and cut to about 5 mm to prepare pellets of cellulose fatty acid mixed ester composition (Mw 16.00,000). The obtained pellets were spun at a spinning temperature of 260 ° C. by a direct spinning method, taken up at a speed of a take-up roller of 1500 m / min, and a single filament was a multifilament yarn (raw yarn) having a total fineness of 100 dtex-72 filaments with a round cross section. Created.

  The properties of the obtained multifilament yarn (raw yarn) had a strength of 1.1 cN / dtex, an elongation of 22.5%, a boiling water shrinkage of 3.1%, and an entanglement of 57 pieces / m.

A single filament used in the warp yarn has a round cross section with a total fineness of 100 dtex-72 filaments, and 500 pieces of warper sizer creel are placed on the multifilament yarn. In order to divide it into books, a twisting machine for filaments, Murata Machinery Co., Ltd. double twister was used, and the rotational speed was 9,000 r. p. The twisted yarn was split at m. The twisted yarn was stopped at 30 ° C. for 30 minutes using a vacuum twist set machine. Subsequently, a multifilament yarn twisted on a creel of a warper sizing machine was placed, and sizing was performed under the following conditions.
・ Paste tank temperature: 40 ℃
Drying chamber (chamber 2 section) temperature: 90 ° C / 100 ° C
・ Cylinder: 5 (each temperature 90 ℃)
・ Draft ratio of the drying zone (stretching ratio): 5% (1.05 times) stretching and simultaneous heat treatment (thermal stretching)
Sizing speed: 200 m / min Paste PVA205: 5% by weight
-Formulated with CITEX A280: 1.8 wt% and CITEX A518: 2.2 wt% as oil agents-Glue adhesion target: 5.5 wt%.

  After gluing, it was beamed, pulled through the ridges and ridges, and then set in an air jet room made by Tsudakoma. For the weft, a multifilament non-twisted hot-drawn yarn used for warp yarn is used, and 500 r. p. A plain structure was woven at a weaving speed of m. The weaving density of the weaving was set at 152 vertical / inch and 93 horizontal / inch.

  The woven weaving machine was put into the dyeing process. First, the deplasticizer treatment was carried out by spreading with 50 ° C. warm water using three tanks of open soaper. The deplasticizer treatment was carried out at a treatment speed of about 2 minutes, and the amount of the deplasticizer was confirmed by the weight ratio of the raw machine and the weight after treatment / drying, and it was 17% by weight. Subsequently, sodium carbonate was added to the liquid dyeing machine at a concentration of 0.5% by weight, and the temperature was raised to 90 ° C. for scouring and relaxation. Subsequently, using a high-pressure liquid flow dyeing machine, dyeing was performed under a pressure of 0.06 Mpa. Disperse dye Cibacet Black EL-FGL 7% owf (manufactured by Huntsman Japan Co., Ltd.) was used as the dye, and dyed black with a bath ratio of 1: 100. After dyeing was completed, an antistatic agent and a finishing agent were applied, and tumbler drying was performed at a temperature of 170 ° C. The finished woven fabric had a warp yarn density of 164 yarns / inch and a weft yarn density of 72 yarns. Table 1 shows the results of measurement and evaluation of the tear strength of the finished fabric and the coloring property of the dyed fabric.

(Example 2)
The fabric obtained in Example 1 was treated in the same manner as in Example 1 except that it was dyed at a temperature of 105 ° C. under a pressure of 0.07 MPa using a high-pressure liquid flow dyeing machine. A woven fabric having the same density was obtained, and the tearing strength and the coloring property of the dyed fabric were evaluated. The results are shown in Table 1.

(Example 3)
The draw ratio at the time of warp yarn sizing in Example 1 was 1.10 times, and the weft yarn was treated in the same manner as in Example 1 except that a multifilament yarn not subjected to heat drawing treatment was used. The finished fabric had a warp yarn density of 165 / inch and a weft yarn density of 72. The tear strength of the finished fabric and the color development of the dyed fabric were evaluated. The results are shown in Table 1.

Example 4
The fabric obtained in Example 3 was treated in the same manner as in Example 3 except that the fabric was dyed at a temperature of 105 ° C. under a pressure of 0.07 MPa using a high-pressure liquid dyeing machine. A woven fabric was obtained, and the tearing strength and the coloring property of the dyed fabric were evaluated. The results are shown in Table 1.

(Example 5)
A multifilament yarn made of cellulose fatty acid mixed ester was prepared by melt spinning as follows.

  82% by weight of cellulose acetate propionate, 17.9% by weight of polyethylene glycol (PEG 600) having an average molecular weight of 600, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol as a phosphite colorant Diphosphite 0.1% by weight was mixed, kneaded at a temperature of 230 ° C. using a biaxial extruder, and cut to about 5 mm to prepare pellets of cellulose fatty acid mixed ester composition (Mw 16.00,000). The obtained pellets were spun at a spinning temperature of 260 ° C. by a direct spinning method, taken up at a speed of a take-up roller of 1500 m / min, and a single filament was a multifilament yarn (raw yarn) having a total fineness of 100 dtex-36 filaments in the Y section. Created.

  The properties of the obtained multifilament yarn (raw yarn) had properties of strength 1.1 cN / dtex, elongation 21.5%, boiling water shrinkage 2.8%, and entanglement 30 / m.

  In order to use this multifilament yarn as a woven warp yarn, additional twisting and sizing were carried out under the same conditions as in Example 1, and the rapier loom was set. A polyester different shrinkage composite fiber yarn that can be dyed at a temperature of 110 ° C. was used for the weft to obtain a plain woven fabric (raw machine) having a raw machine density of 111 warp yarns / inch × 87 warp yarns / inch. Polyester hetero-shrink composite fiber yarn includes filament yarn having a boiling water shrinkage of 20% (total fineness 33 dtex-12 filament) obtained by spinning and stretching a polymer obtained by copolymerizing 15 mol of isophthalic acid to polyester, and spinning speed. POY hot-drawn spun at 3,700 m / min, combined with a spontaneously stretchable filament yarn (total fineness 33 dtex-24 filament) with a boiling water shrinkage of ± 0%, interlaced, and a boiling water shrinkage of 17% A multifilament yarn having a total fineness of 66 dtex-36 filaments having characteristics was twisted in the S direction with a twist number of 1,600 T / M using a double twister. The raw machine obtained above was subjected to a deplasticizer treatment, scouring relaxation, drying, presetting, and a high-pressure liquid flow dyeing machine under the same conditions as in Example 1 at a temperature of 100 ° C. under a pressure of 0.06 Mpa. Stained. As the dye, disperse dye Cibacet Black EL-FGL 10% owf (manufactured by Huntsman Japan Co., Ltd.) was used and dyed black. After dyeing was completed, an antistatic agent and a finishing agent were applied, and tumbler drying was performed at a temperature of 170 ° C. The evaluation results of the fabric after dyeing are shown in Table 1.

(Example 6)
The fabric obtained in Example 5 was treated in the same manner as in Example 5 except that the fabric was dyed at a temperature of 110 ° C. under a pressure of 0.12 MPa using a high-pressure liquid flow dyeing machine. The tearing strength and color development of the dyed fabric were evaluated. The results are shown in Table 1.

(Comparative Example 1)
In order to divide a multifilament yarn made of cellulose ester having a total fineness of 100 decitex-72 filaments with a round cross section of the single fiber used in Example 1 into 500 pieces necessary for warp for non-glue weaving, a twist of 1,000 t / m at the same time as the filament twister Murata Machine Co., Ltd. Double Twister p. The twisted yarn was split at m. The twisted yarn was stopped with a vacuum twist set machine at 70 ° C. for 30 minutes. 500 warp creels were placed on the warping machine, and a warp yarn beam was placed on the loom by beaming after rough winding. The beam is applied to a rapier loom, and the weft yarn is a multifilament untwisted yarn used for warp yarn. p. A plain structure was woven at a weaving speed of m. The weaving density of the weaving was set at 152 vertical / inch and 93 horizontal / inch.

  The obtained raw machine was processed under the same conditions as in Example 1, and dyed at a temperature of 100 ° C. under a pressure of 0.06 Mpa using a high-pressure liquid flow dyeing machine. Disperse dye Cibacet Black EL-FGL 10% owf (Huntsman Japan K.K.) was used as the dye, and dyed black. The finished fabric was 165 / inch and the weft density was 72. Table 1 shows the results of measurement and evaluation of the tear strength of the finished fabric and the coloring property of the dyed fabric.

(Comparative Example 2)
The fabric obtained in Comparative Example 1 was treated under the same conditions as in Comparative Example 1, and an attempt was made to dye at 110 ° C. under a pressure of 0.12 MPa using a high-pressure liquid flow dyeing machine. Cutting occurred and could not be dyed. The results are shown in Table 1.

  From the above results, in the present invention, dyeing was possible without causing a decrease in strength even under dyeing conditions at a temperature of 100 ° C. or higher under high pressure.

Claims (7)

  Cellulose characterized by using, as warp yarn, multifilament yarn obtained by hot drawing during the time of production when weaving and knitting using multifilament yarn made of cellulose ester obtained by melt spinning as warp yarn Manufacturing method of ester fiber woven or knitted fabric.   The method for producing a woven or knitted cellulose ester fiber according to claim 1, wherein the draw ratio is 1.02 to 1.15 times in the step of hot drawing.   A multifilament yarn made of cellulose ester obtained by melt spinning is immersed in a paste bath, and then hot-drawn simultaneously with drying, and the resulting multifilament yarn is used for warp yarn to be knitted and woven. A method for producing a cellulose ester fiber woven or knitted fabric.   4. The method for producing a woven or knitted cellulose ester fiber according to claim 3, wherein in the step of heat drawing simultaneously with drying, the draw ratio is 1.02 to 1.15 times and the drying temperature is 90 to 150 ° C.   The cellulose ester fiber according to any one of claims 1 to 4, wherein the warp yarn is a yarn formed by combining a multifilament yarn made of cellulose ester and a polyester fiber that can be drawn or stretched simultaneously. Manufacturing method of woven or knitted fabric.   The method for producing a cellulose ester fiber woven or knitted fabric according to any one of claims 1 to 5, wherein at least a part of the acyl group of the cellulose ester is an acyl group having 3 to 18 carbon atoms.   The method for producing a cellulose ester fiber woven fabric according to any one of claims 1 to 5, wherein the cellulose ester is cellulose acetate propionate or cellulose acetate butyrate.