JPS6312189B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyester fiber woven or knitted fabric and a method for producing the same. Polyesters, particularly polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyester fibers mainly composed of these polyesters have various excellent properties and are therefore widely used in woven and knitted fabrics. However, these conventional woven and knitted fabrics made from polyester fibers lack a dry and voluminous feel, and are not hydrophilic. Efforts are being made to get closer to these without getting the same results. Recently, due to advances in production and processing technology for polyester fiber woven and knitted materials, it has become possible to obtain woven and knitted materials that are quite similar to natural fiber woven and knitted materials in terms of texture and appearance, but with a dry surface touch and a sense of volume. There is still a large difference in terms of texture, water absorption, etc., and this is one of the decisive differences in comfort between natural fiber woven and knitted fabrics and polyester fiber woven and knitted fabrics. The dry feeling mentioned here refers to the unique dry feeling that silk fiber woven and knitted fabrics have, for example, and is in contrast to the slimy feeling that polyester fiber woven and knitted fabrics have.
Quantitative measurement is difficult at present, and is generally based on the touch of the fabric manufacturer. Although it is difficult to measure, it is an extremely important element in determining the properties and comfort of woven or knitted fabrics. Moreover, the volume feeling refers to the unique volume feeling that woolen fiber woven and knitted fabrics have, for example, and is in contrast to the flat and thinness that polyester fiber woven and knitted fabrics have. This sense of volume particularly affects the properties of woven or knitted fabrics and the comfort level centered on the texture. Furthermore, water absorbency is an extremely important factor that affects the comfort of clothing. That is, when using hydrophobic fiber fabrics such as polyester fibers when sweating a lot, the sweat is not absorbed by the fabric and accumulates on the skin, and the fabric is also wet, so it sticks to the skin and becomes sticky. It had drawbacks such as clinging. Therefore, it has been a long-standing dream since the birth of synthetic fiber woven and knitted fabrics to impart water absorbency to polyester fibers and eliminate the above-mentioned drawbacks. An object of the present invention is to improve the above-mentioned drawbacks of polyester fiber woven and knitted fabrics, and to provide a polyester long fiber woven and knitted fabric that provides an excellent dry feel, rich volume feel, and excellent water absorption, and a method for producing the same. . That is, the present invention provides a mixed yarn consisting of two or more types of polyester long fibers, at least one of the polyester long fibers consisting of hollow fibers,
The hollow fiber has micropores scattered in its cross section and arranged in the fiber axis direction, the diameter of the micropores is 0.01 to 3 μm, the length is 50 times the diameter or less, and at least one of the micropores is 0.01 to 3 μm in diameter. A polyester fiber woven or knitted fabric is characterized in that it consists of a mixed fiber yarn in which hollow fibers, the hollow fibers of which are connected to the hollow portion, are arranged mainly in the outer layer of the mixed fiber yarn, and such a woven or knitted fabric is obtained. For example, the modified yarn is a yarn made by blending two or more types of polyester long fibers, and at least one of the polyester long fibers is copolymerized with an organic sulfonic acid compound represented by the following general formula (). Consisting of long fibers with a hollow cross section and blended with at least one type of micropore-forming agent selected from the group consisting of polyester, a phosphorus compound represented by the following general formula (), and a sulfonic acid compound represented by the following general formula (). , after subjecting a blended yarn consisting of long fibers in which at least one of the polyester long fibers has a heat shrinkage rate greater than the heat shrinkage rate of the polyester long fibers containing the micropore-forming agent, to a relaxing heat treatment;
1. A method for producing a polyester woven or knitted fabric, which comprises woven or knitted, or subjected to relaxation heat treatment after woven or knitted, and then treated with an alkaline solution. [Wherein, A is a trivalent aromatic group or an aliphatic hydrocarbon group, X is an ester-forming functional group, Y is an ester-forming functional group or a hydrogen atom, and M ¹ is a metal or a hydrogen atom. ] [In the formula, V is a monovalent organic group, Z is -OV', OM ⁵ or a monovalent organic group (where V' is a monovalent organic group, M ⁵ is a metal), M ² is a metal, and m is a Indicates 0 or 1. ] [Wherein, W is a hydrogen atom or an ester-forming functional group, M ³ and M ⁴ are metals, and n is 1 or 2. ] Hereinafter, the present invention will be explained in detail. The mixed fiber yarn referred to in the present invention is one in which hollow polyester fibers having micropores are arranged in the outer layer portion. In the inner layer of this mixed yarn, normal polyester fibers and polyester fibers with micropores are arranged, but like the hollow polyester fibers arranged in the outer layer, polyester fibers with a hollow cross section and micropores are used. However, in this case, it is preferable that the hollow polyester fibers disposed in the inner layer have a larger fineness than those disposed in the outer layer. The shape of the hollow polyester fiber referred to in the present invention may be any shape as long as there is a continuous polymer layer in the fiber axis direction. Those whose outer shape and hollow part are circular, those whose outer shape is polygonal with convex sides and whose hollow part has a circular hollow cross section, and those whose outer shape is circular and whose hollow part is polygonal. , those having irregularly shaped hollow portions, and those having a plurality of 2 to 4 hollow portions. Furthermore, there is no limit to the outer diameter of such hollow polyester fibers. The hollowness ratio of such hollow polyester fibers, that is, the ratio of the cross-sectional area of the hollow portion to the total apparent cross-sectional area of the fibers, is preferably in the range of 5 to 50%.
If the hollowness ratio is less than 5%, the water absorption performance will decrease and the woven or knitted fabric which is the object of the present invention cannot be obtained. In addition, if the hollowness ratio exceeds 50%, the hollow portion tends to collapse, and once it collapses, the water absorption performance decreases, which is not preferable. Further, the hollow polyester fiber used in the present invention has micropores scattered in the cross section and arranged in the fiber axis direction. The aforementioned micropores are
They may be scattered throughout the hollow cross section, or
It may be scattered in a certain part of the cross section, but
at least some of the micropores are in communication with each other,
As a result, the outer wall and inner wall of the hollow fiber as a whole communicate with each other continuously or intermittently through micropores. These micropores are scattered in the cross section of the fiber as described above, and whether or not at least one part of them communicates with the hollow part is determined by the cross section of the fiber.
It can be observed at a magnification of about 3000 times. Furthermore, the simplest and easiest way to check the communication state of micropores is to check the length of several centimeters (usually 5 cm).
While observing a single filament with a normal microscope at a magnification of about 100 times, if you place a drop of water (preferably dyed water) in the middle of this single filament, you can see whether the water reaches the hollow part or not. This can be easily confirmed. In the case of the hollow polyester fiber used in the present invention, it is observed that the water dropped as described above instantly reaches the hollow portion. FIG. 1 is a diagram showing a microscopic photograph of the outer shape of the hollow fiber used in the present invention. As shown in FIG. 1, the micropores are arranged in the axial direction of the fiber, and no fibrils are observed in the outer shape of the fiber, especially on the surface. As for the size of such micropores, it is desirable that the diameter is 0.01 to 3 μm and the length is 50 times or less the diameter. The diameter of this micropore is
If it is less than 0.01μm, the water absorption effect tends to decrease,
If the diameter exceeds 3 μm, sufficient fiber strength cannot be obtained. Furthermore, if the length of the micropores becomes longer than 50 times the diameter thereof, even if all other conditions are satisfied, the strength and fibrillation resistance of the fiber will decrease, which is not preferable. Fibers having such micropores can be obtained as follows. That is, it can be obtained by blending a micropore-forming agent into a polyester composition, melt-spinning the resulting polyester fiber, and treating the resulting polyester fiber with an alkaline solution to remove the additive. As the micropore-forming agent used here, a modified polyester obtained by copolymerizing an organic sulfonic acid compound represented by the following general formula () is preferably used. In the formula, A is a trivalent aromatic group or an aliphatic hydrocarbon group, with aromatic groups being particularly preferred. M ¹ is a metal or a hydrogen atom, and particularly preferably an alkali metal or an alkaline earth metal. X is an ester-forming functional group, and specific examples thereof include

【formula】 【formula】

[Formula] (-CH ₂ )- _a OH, -O(CH ₂ )- _b [-O(CH ₂ ) _b ]- _d OH,

[Formula] (However, R is a lower alkyl group or a phenyl group, a
and d is an integer of 1 or more, b is an integer of 2 or more), etc. Y represents an ester-forming functional group or a hydrogen atom that is the same as or different from X, and is preferably an ester-forming functional group. Particularly preferred examples of such organic sulfonic acid compounds include sodium (or potassium) 3,5-di(carbomethoxy)benzenesulfonate, sodium (or potassium) 1,8-di(carbomethoxy)naphthalene-3-sulfonate, ), sodium (or potassium) 2,5-bis(hydroxyethoxy)benzenesulfonate, and the like. In order to produce a modified polyester obtained by copolymerizing such an organic sulfonic acid compound, the organic sulfonic acid compound is added at any stage before the synthesis of the polyester described above is completed, preferably at any stage before the first stage reaction is completed. An acid compound may be added. The amount of the organic sulfonic acid compound to be used in this case is in the range of 2 to 16 mol% based on the difunctional carboxylic acid component (excluding the organic sulfonic acid component) mainly consisting of terephthalic acid that constitutes the modified polyester. is preferred. The amount of the modified polyester to be blended with the polyester is preferably 5 to 100 parts by weight of the modified polyester per 100 parts by weight of the polyester. In addition to the above-mentioned modified polyester, phosphorus compounds or sulfonic acid compounds represented by the following general formula () or () are also preferable as the micropore-forming agent. where M ² is a metal, especially an alkali metal,
Alkaline earth metals, Mn1/2, Co1/2 or Zn1/2 are preferred, especially Li, Na, K, Ca1/2, Mg1/2
2 is particularly preferred. m is 0 or 1. V is a monovalent organic group, specifically an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, or [-(-CH ₂ )- _l O]- _p R'' (where R'' is a hydrogen atom ,
an alkyl group or a phenyl group, l is an integer of 2 or more,
p is an integer of 1 or more), etc. are preferred. Z is-OH,
-OV', -OM ⁵ or a monovalent organic group, V' is the same as the definition of V above, V' and V may be the same or different, and M ⁵ is the same as M ² above. It is the same as the definition of M ⁵ and M ² may be the same or different. Further, the monovalent organic group is the same as the definition of the organic group in V above, and may be the same as or different from V. Preferred specific examples of such phosphorus compounds include monomethyl disodium phosphate, dimethyl monosodium phosphate, monophenyl dipotassium phosphate,
Monomethyl monomagnesium phosphate, monomethylmanganese phosphate, polyoxyethylene (addition of 5 moles of EO), potassium lauryl ether phosphate (however, the addition of 5 moles of EO means the addition of 5 moles of ethylene oxide, and the same meaning shall apply hereinafter). ), polyoxyethylene (5 moles of EO added) lauryl ether phosphate magnesium salt, polyoxyethylene (50 moles of EO added) methyl ether phosphate sodium salt, monoethyl dipotassium phosphite, diphenyl monosodium phosphite, Examples include disodium polyoxyethylene (50 moles of EO added) methyl ether phosphite, monosodium monomethyl phenylphosphonate, monopotassium monomethyl nonylbenzenephosphonate, monosodium monomethyl phenylphosphinate, and the like. In the formula, M ³ and M ⁴ are metals, and M ³ particularly includes alkali metals, alkaline earth metals, Mn1/2,
Co1/2 or Zn1/2 is preferred, especially Li, Na,
Particularly preferred are K, Ca1/2, and Mg1/2; particularly preferred are alkali metals and alkaline earth metals as ^M4 ; particularly preferred are Li, Na, K, Ca1/2, and Mg1/ ² ; M ⁴ may be the same or different. n is 1 or 2. W is a hydrogen atom or an ester-forming functional group, and the ester-forming functional group is -COOR (wherein, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group)
or -CO[-O( _-CH2 ) _l ] _-pOH (where l is an integer of 2 or more, p is an integer of 1 or more), etc. are preferred. Preferred specific examples of such sulfonic acid compounds include sodium 3-carbomethoxybenzenesulfonate-5-sodium carboxylate, sodium 3-carbomethoxybenzenesulfonate-5-
Potassium carboxylate, Potassium 3-carbomethoxybenzenesulfonate-5-carboxylate, Sodium 3-hydroxyethoxycarbonyl benzenesulfonate-5-sodium carboxylate, Sodium 3-carboxybenzenesulfonate-5-carboxylic acid Sodium, 3-hydroxyethoxycarbonyl benzenesulfonic acid
Examples include Mg1/2 of Na-5-carboxylate, Na-3,5-dicarboxylate Na-benzenesulfonate, and Mg1/2 of Na-3,5-dicarboxylate benzenesulfonate. The appropriate amount of the phosphorus compound or sulfonic acid compound to be added is in the range of 0.3 to 15 mol%, based on the acid component constituting the polyester to be added, and 0.5 to 5 mol%.
A mole % range is preferred. When spinning polyester fibers blended with such a micropore-forming agent, a spinneret that can yield the desired hollow fibers is used. For example, in order to obtain a hollow fiber having a circular outer shape and hollow part shape, a spinneret having a partially closed horseshoe-shaped opening is usually used as a spinneret. Next, the yarn in which polyester fibers having micropores are distributed in the outer layer of the mixed fiber yarn is either the above-mentioned polyester fiber containing a micropore-forming agent, or the polyester fiber containing the micropore-forming agent is previously treated with an alkaline solution. By doing so, the heat shrinkage rate of the polyester fibers having micropores is reduced, and the polyester fibers having a higher heat shrinkage rate than these fibers are mixed by a known method, and then heat treatment is performed such as relaxation heat treatment. It can be obtained by further shrinking polyester fibers with a high shrinkage rate, arranging the polyester fibers with a high heat shrinkage ratio mainly in the inner layer of the thread, and arranging the polyester fibers with a low heat shrinkage ratio mainly in the outer layer of the thread. . The blending with the above-mentioned micropore-forming agent-containing polyester fibers or hollow polyester fibers having micropores can be carried out by a known method, but in this case, the blending ratio is as follows: 10 to 80% by weight of fibers, preferably 20
-60% by weight, and preferably 90-20% by weight, preferably 80-40% by weight, of polyester fibers containing a micropore-forming agent or hollow polyester fibers having micropores. The above-mentioned relaxing heat treatment may be performed on the mixed yarn, or the relaxing heat treatment may be performed after the mixed yarn is knitted into various woven or knitted fabrics by known means. The temperature of this relaxation heat treatment is preferably in the range of 90 to 170°C, and may be carried out in a relaxed state in steam or hot water. When the woven or knitted fabric obtained as described above is made of polyester fibers containing a micropore-forming agent, the woven or knitted fabric is treated with an aqueous solution of an alkaline compound to remove at least a portion of the micropore-forming agent. By dissolving and removing the polyester fibers, polyester fibers having micropores can be obtained, which can be used to obtain the woven or knitted fabric of the present invention. Dissolving and removing at least a portion of the micropore-forming agent from the micropore-forming agent-containing polyester fibers with an aqueous solution of an alkaline compound can be performed before blending, but as described above A method in which the micropore-forming agent is subsequently removed is preferred from the viewpoint of operation. The thus obtained polyester fiber woven or knitted fabric of the present invention has hollow polyester fibers having micropores and in which the micropores are connected to the hollow portion distributed in the outer layer of the yarns constituting the woven or knitted fabric. It is possible. As described above, by arranging the hollow polyester fibers having micropores in the outer layer of the yarn constituting the woven or knitted fabric, sweat on the skin is quickly absorbed through the micropores when worn, and communicates with the micropores. This method allows the sweat to accumulate in the hollow part where the sweat is present, and also radiates this accumulated sweat to the side of the woven or knitted fabric that is not in contact with the skin. Such rapid sweat absorption properties can impart excellent wearing comfort to the woven or knitted fabric. In particular, the hollow cross-section fiber having micropores used in the present invention has at least a portion of the micropores scattered in its cross section communicating continuously or intermittently to the hollow portion, which enhances the above effect. be. Furthermore, since the above-mentioned micropores are obtained from a modified polyester blended with a sulfonic acid metal salt, fibrillation due to wear during wear, which occurs with polyester blended with other additives, is unlikely to occur. In particular, the micropores produced by polyester containing other additives have a diameter of 0.01 to 0.4 μm and a length of more than 200 times the diameter, which causes fibrillation, but the micropore-forming agent used in the present invention For modified polyester, the diameter is approximately 0.01 ~
A micropore with a length of 3μm or less than 50 times the diameter,
It is clearly different from the other additive-blended polyesters mentioned above in the shape of the micropores, and due to this,
It has excellent fiber strength and fibrillation resistance. Further, the woven or knitted fabric of the present invention has a strong dry feel due to the micropores of the hollow polyester fibers arranged in the outer layer of the mixed yarn forming the woven or knitted fabric. In addition, since fibers with a high heat shrinkage rate and polyester fibers containing a micropore-forming agent with a low heat shrinkage rate are mixed and subjected to relaxation heat treatment, it is possible to impart a sense of volume to the resulting woven or knitted fabric. , it is possible to provide the above-mentioned dry feeling as well as excellent texture. Examples will be explained below. Example 197 parts of dimethyl terephthalate, 124 parts of ethylene glycol, 4 parts of sodium 3-carbomethoxybenzenesulfonate-5-carboxylate (1.3 mol% based on dimethyl terephthalate), calcium acetate.
Put 0.118 parts of monohydrate into a glass flask with a rectifier,
The transesterification reaction was carried out according to a conventional method, and after the theoretical amount of methanol had been distilled off, the reaction product was placed in a polycondensation flask with a rectification column, and 0.112 parts of trimethyl phosphate as a stabilizer and trioxide as a polycondensation catalyst were added. 0.079 part of antimony was added, and the mixture was reacted at a temperature of 280° C. for 20 minutes under normal pressure, 15 minutes under reduced pressure of 30 mmHg, and then reacted for 80 minutes under high vacuum. Final internal pressure is 0.38mm
The intrinsic viscosity of the modified polymer obtained with Hg is
0.600, and the softening point was 258°C. After the reaction was completed, the modified polymer was made into chips according to a conventional method. The chips are dried in a conventional manner and used in a spinneret.
Using a circular slit with a diameter of 0.005 mm and a diameter of 0.6 mm, which has arc-shaped openings closed at two places, the yarn is spun according to a conventional method to obtain hollow fibers with an outer diameter to inner diameter ratio of 2:1 ( The hollow rate was 25%). This raw yarn is 300 denier/24 filaments, and is drawn to 75 denier/24 filaments using a conventional method at a draw ratio of 4.0 times.
A multifilament of 24 filaments was obtained. The boiling water shrinkage rate of this multifilament was 8%. This modified polyester multifilament containing a micropore forming agent is blended with normal polyester multifilament yarn with a boiling water shrinkage rate of 14% and a circular cross-section of bright 50/12 filaments, and the warp is 120T/M.
The warp density is 28 threads/cm and the weft density is 25 threads/cm.
Plain weave is woven according to the plain weave standard and boiled off (96
After scouring and relaxing at 170°C for 12 minutes and overfeeding and presetting at 170°C for 30 seconds, alkali weight loss (98°C, alkali concentration 20g/
15% weight loss was achieved by 30 minutes treatment in the bath.
For comparison purposes, a conventional polyester plain woven fabric subjected to alkali weight reduction processing was prepared and compared with this, as shown in Table 1. As can be seen from Table 1, the dry feel of the fabric of this example is that the difference between the coefficient of static friction and the coefficient of dynamic friction μs - μd is much larger than that of conventional polyester fabrics, giving a dry feel to the surface of the fabric. There is. This is because the arrangement of the single fibers is disrupted by mixing two types of yarns with different shrinkage rates, and the difference in shrinkage between the two types of fibers becomes apparent when they are heat-treated after being made into a woven fabric.
This is due to the fact that the single fibers are more disturbed and the hollow fibers having micropores are arranged in the outer layer. Also, the feeling of volume is expressed by the bulkiness of the fabric,
This is because the yarn of the present invention has a large interfiber space due to the yarn structure of a mixed yarn of two types of yarns with different shrinkage rates and the alkali weight loss treatment. Water absorption is expressed in terms of water absorption rate and water absorption rate, but since hollow fibers with micropores are arranged mainly in the outer layer of the mixed fiber yarn, water absorbed through the micropores by capillary action is absorbed into the hollow fibers by the communicating pores. Move to section. Therefore, as is clear from Table 1, it has a much faster water absorption rate and larger water absorption rate than conventional polyester fabrics, and at the same time has fullness and dry touch.

[Table] Dry sample weight

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph showing an example of the surface condition of polyester fibers having micropores used in the woven or knitted fabric of the present invention.

Claims (1)

[Scope of Claims] 1. A mixed yarn consisting of two or more types of polyester long fibers, at least one of the polyester long fibers is a hollow fiber, and the hollow fiber is
It has fine pores scattered in its cross section and arranged in the fiber axis direction, and the diameter of the fine pores is 0.01 to
3μm, the length is 50 times or less the diameter, and at least a part of the hollow fiber is connected to the hollow part,
A polyester fiber woven or knitted fabric characterized by comprising yarns mainly arranged in the outer layer of the mixed yarn. 2 A yarn that is a mixture of two or more types of polyester long fibers, in which at least one type of the polyester long fibers is a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (), The polyester-based polyester is made of long fibers with a hollow cross section and is blended with at least one kind of micropore-forming agent selected from the group consisting of a phosphorus compound represented by the formula () and a sulfonic acid compound represented by the following general formula (). At least one other type of long fibers is subjected to a relaxing heat treatment on a mixed yarn consisting of long fibers having a heat shrinkage rate higher than that of the polyester long fibers containing the micropore-forming agent, and then woven or knitted; Alternatively, a method for producing a polyester woven or knitted material, which comprises woven and knitted, subjected to a relaxation heat treatment, and then treated with an alkaline solution. [Wherein, A is a trivalent aromatic group or an aliphatic hydrocarbon group, X is an ester-forming functional group, Y is an ester-forming functional group or a hydrogen atom, and M ¹ is a metal or a hydrogen atom. ] [In the formula, V is a monovalent organic group, Z is -OV', OM ⁵ or a monovalent organic group (where V' is a monovalent organic group, M ⁵ is a metal), M ² is a metal, and m is a Indicates 0 or 1. ] [Wherein, W is a hydrogen atom or an ester-forming functional group, M ³ and M ⁴ are metals, and n is 1 or 2. ]