JPH0258374B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a woven or knitted fabric having special fluff and a method for producing the same. Traditionally, one method of giving fluff to the surface of woven or knitted fabrics is needle cloth raising, and other methods include using emery cloth instead of cloth. We offer brushed products. All of these conventional raised products are obtained through the process of pulling out the single fibers that make up the woven or knitted fabric into a loop, and cutting the loops to make raised fibers. It has a thickness and length based on a single fiber. Also, very recently, as an improvement on the above-mentioned napping or fuzz, it has been proposed to use ultrafine fibers of 1.0 denier or less. However, even if such ultrafine fibers are used, there are still limitations on their fineness and length. That is, the ultrafine fibers can be produced by a method in which the fibers are raised using a bonded composite fiber and then the bond is separated, or by a method in which the fibers are raised using a sea-island composite fiber and the sea component is subsequently dissolved and removed. You can get it, but
Due to the conditions of the spinneret and the spinning process, it is impossible to spin infinitely thin composite fibers with stepless changes in fineness, and therefore the ultrafine fibers obtained also have a limit in thickness. However, the napped or fluff obtained from fibers having such a limit in thickness also has a limit in length. The object of the present invention is to provide a woven or knitted fabric that has extremely short fluffs, including fluffs so long that they can hardly be determined with the naked eye, rather than the conventional long fluffs, and has an excellent texture, and the production thereof. It consists in proposing laws. That is, the present invention provides fluff formed by microfibrillating the surface fibers of a woven or knitted fabric made of polyester fibers, (a) the thickness of which is within the range of 0.01 to 5μ in apparent diameter; (b) It is substantially covered with fluff that satisfies the requirement that the length is 1.0 mm or less, and the number of fluff is 1×10 ⁵ per 1 cm ² . The present invention relates to a woven or knitted fabric having a special fluff on its surface, which is characterized by having a certain amount of fluff on its surface, and a method for producing the same. The present invention will be explained in detail below. The fluff of the woven or knitted fabric of the present invention is obtained by microfibrillating the fibers that constitute the woven or knitted fabric. Therefore, the obtained fluff has various thicknesses and lengths. In the present invention, the apparent diameter indicating the thickness of the fluff means the thickness of the fluff measured as follows. Apparent Diameter Take an electron micrograph of microfibrillated fluff with a standard scale, measure the diameter of the photographed fluff with a reading microscope, and calculate the apparent diameter of the fluff from the magnification of the electron microscope and the standard scale. Depends on how you ask. Next, the term "the thickness of the fluff has various thicknesses steplessly" means that the thickness of the fluff is an integral multiple of a specific thickness, as in conventional ultrafine fibers, or It does not have a single thickness, but it refers to one that is determined naturally and at random, and has a stepless variety of thicknesses. Such unprecedented fluff can be obtained by microfibrillating the fibers as described above.
To microfibrillate fibers, the fiber polymer is blended with incompatible additives and spun to form a woven or knitted fabric.The surface of the woven or knitted fabric is lightly buffed, and then the additives are added to the fiber polymer. By extracting and removing at least a portion of the additive, or by treating the woven or knitted fabric to extract and remove at least a portion of the additive, at least cracks or micropores are formed in the fibers on the surface of the woven or knitted fabric. Seshime,
Thereafter, by lightly buffing the surface, the fibers can be microfibrillated. The additive is preferably an organic compound that is incompatible with the fiber polymer to be added. For example, regarding polyester fiber,
First, a metal salt of an organic sulfonic acid represented by the general formula R.SO ₃ M is used as the additive, and the metal salt is obtained by blending the metal salt into polyester as an additive. However, in the above general formula, R has 3 to 30 carbon atoms.
an alkyl group or an aryl group having 7 to 40 carbon atoms,
or an alkylaryl group, M represents an alkali metal or an alkaline earth metal. Moreover, when R is an alkyl group or an alkylaryl group,
It may have a linear or branched side chain. M is an alkali metal such as Na, K, Li, etc.
Examples include alkaline earth metals such as Mg and Ca, among which Na and K are preferred. Note that when using the organic sulfonic acid metal salt, it is not necessary to use a single compound, and a mixture of organic sulfonic acid metal salts having various alkyl groups or alkylaryl groups may be used. Specifically, such organic sulfonic acid metal salts include sodium stearyl sulfonate, sodium octylsulfonate, sodium dodecyl sulfonate, a mixture of sodium alkyl sulfonates having an average carbon number of 14, and dodecylbenzenesulfonic acid. Examples include soda, sodium octadecylbenzenesulfonate, and sodium nonyldiphenyl ether sulfonate. In addition, as another additive, a modified polyester copolymerized with an organic sulfonic acid compound represented by the following general formula (), a phosphorus compound represented by the following general formula (), and a sulfonic acid compound represented by the general formula (). It may also contain at least one additive selected from the group. That is, 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 preferable 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 modified polyester described above, phosphorus compounds or sulfonic acid compounds represented by the following general formula () or () are also preferable as additives. where M ² is a metal, especially an alkali metal,
Alkaline earth metal, Mn1/2, Co1/2 or
Zn1/2 is preferred, especially Li, Na, K,
Particularly preferred are Ca1/2 and Mg1/2. m is 0 or 1. V is a monovalent organic group, specifically an alkyl group, an aryl group, an alkylaryl group,
Arylalkyl group or [-(-CH ₂ )- _l O]- _p R″(
However, 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. Z is -OH, -OV', ^-OM5 or a monovalent organic group, and V' is the same as the definition of V above,
V′V may be the same or different, M ⁵ is the same as the definition of M ² above, and M ⁵ and M ² may be the same or different. Further, one 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, addition of 5 moles of EO means addition of 5 moles of ethylene oxide, and hereinafter the same meaning) ,
Polyoxyethylene (EO5 mole addition) Lauryl ether phosphate magnesium salt, Polyoxyethylene (EO50 mole addition) Methyl ether phosphate sodium salt, Monoethyl dipotassium phosphite, Diphenyl monosodium phosphite, Polyoxyethylene (EO50 addition) molar addition) disodium methyl ether phosphite, monomethyl monosodium phenylphosphonate, monomethyl monopotassium nonylbenzenephosphonate, monomethyl monosodium 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 preferable, especially
Particularly preferred are Li, Na, K, Ca1/2, Mg1/2, and particularly preferred as ^M4 are alkali metals or alkaline earth metals, among which Li, Na, K,
Ca1/2, Mg1/2 are particularly preferred, M ³ and 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'' (where R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group) or -CO[-O(-
CH ₂ ) _l ] - _p OH (where l is an integer of 2 or more, p is 1
or larger integer), etc. are preferable. Preferred specific examples of such sulfonic acid compounds include sodium 3-carbomethoxybenzenesulfonate-5-sodium carboxylate and sodium 3-carbomethoxybenzenesulfonate-5.
- Potassium carboxylate, Potassium 3-carbomethoxybenzenesulfonate - Potassium 5-carboxylate, Sodium 3-hydroxyethoxycarbonyl benzenesulfonate - Sodium 5-carboxylate, Sodium 3-carboxybenzenesulfonate -5-Carboxylate acid sodium, 3-hydroxyethoxycarbonyl benzenesulfonic acid
Examples include Mg1/2 of Na-5-carboxylic acid, Na-3,5-dicarboxylic acid Na-benzenesulfonic acid, and Mg1/2 Na-3,5-dicarboxylic acid 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. The woven or knitted fabric is woven and knitted so that the polyester fibers containing such additives are disposed on at least the surface of the woven or knitted fabric, and then the woven or knitted fabric is subjected to an alkali hydrolysis treatment and a buffing treatment to remove the additives. The polyester fibers are microfibrillated. Further, the alkaline hydrolysis treatment can be performed either before or after the buffing treatment, but from the viewpoint of controlling the density and length of the fluff, it is desirable to perform it before the buffing treatment. From the viewpoint of promoting microfibrillation, it is preferable that the alkaline hydrolysis treatment is carried out at a fiber weight loss rate of 5% to 35%. The alkaline hydrolysis treatment can be performed by applying a known method, but for example, in the immersion method, the concentration is 20 to 40.
Using g/L caustic soda, temperature 90-100℃,
It can be carried out for 30 to 60 minutes, and the alkali hydrolysis treatment can be carried out on the surface fibers by coating the surface of the woven or knitted fabric with an alkali paste. It is also possible to place only the fibers on the surface of the woven or knitted material in a state where fibrillation is likely to occur. Note that the buffing treatment described above may be performed by rubbing the surface of the woven or knitted fabric with sandpaper or the like, and it is not preferable to use needle cloth raising or the like because the length of the fluff becomes large. The sandpaper used in the buffing process has a roughness of, for example, a particle size of #100 to #300, and in the buffing process, the sandpaper is applied to the surface of a roller rotating at high speed. The degree of buffing treatment varies depending on the particle size of the sandpaper, the amount of additive used in the woven or knitted fabric to be treated, etc., but it is sufficient that the roller contacts the surface to be treated 1 to 20 times. The thus obtained woven or knitted fabric becomes a novel woven or knitted fabric having special fuzz. That is, the woven or knitted fabric of the present invention has an apparent diameter of 0.01 to
1×10 5 short, thin fluffs per 1 cm ² that are ^within the range of 5μ and have various thicknesses within this range, and whose length is 1.0 mm or less The entire surface of the woven or knitted fabric due to the above-mentioned fuzz, or
Part of it is covered. In addition, when a part of the fluff is covered with such fluff, it is desirable that the ratio of the fluff to the whole of the fluff be 20% or more in terms of the appearance of the raised woven or knitted fabric. In the present invention, since a woven or knitted fabric is manufactured using fibers made of polyester made of an organic compound and in which additives that are incompatible with polyester are dispersed, the additives are removed by alkaline hydrolysis treatment. By eluting and removing a portion of the agent from the polyester, the surface of the polyester fiber can be brought into a state where it is extremely easy to fibrillate. In particular, when alkaline hydrolysis treatment is applied to such an extent that part of the additive is eluted and removed from the polyester and excessively striated micropores are formed on the surface of the polyester fiber, buffing occurs because fibrillation is extremely likely. It is necessary to do it to a mild degree. In addition, the above-mentioned limitations on the apparent diameter and fluff length were set because fluff with an apparent diameter of less than 0.01μ cannot function as fluff for woven or knitted fabrics in terms of appearance or texture. , the apparent diameter is 5μ
If the fluff exceeds 100 mL, the surface of the fluff will become rough and hard, as in conventional fluff knitted fabrics, and the object of the present invention cannot be achieved. Also, if there is a lot of fluff with a length exceeding 1.0 mm,
This is undesirable because it causes fluff spots, which impairs the appearance of the surface and causes pilling. In order to further lengthen the fluff, it is necessary to promote microfibrillation by increasing the amount of additives or by strengthening the removal and treatment of additives, but as microfibrillation progresses, This is not preferable because the fibers become brittle and the strength decreases significantly. In addition, in the woven or knitted fabric of the present invention, it is necessary that the apparent diameter and length of the fluff be in the above-mentioned range, and the number of fluffs is 1×10 ⁵ or more per ¹ cm 2 .
When the number is less than ⁵ ×10, the fluff on the surface of the woven fabric is thin and short, and the texture and appearance of a woven or knitted fabric with fluff cannot be obtained. As described above, the fluff covering the surface of the woven or knitted fabric of the present invention is a special type of fluff that is difficult to discern with the naked eye due to microfibrillation of the fibers, so it does not seem to be a fluffy knitted fabric. With a plain,
In addition, it has a smooth surface and a fluff layer with a thickness of 1.0 mm or less, giving a warm feel. In addition, although the length of the fluff is short at 1.0 mm or less, the apparent diameter is 0.01 to 5 μ, and it changes steplessly within this range, and the number of fluff is 1 × 10 ⁵ per 1 cm ² . By doing so, it is possible to obtain a woven or knitted fabric in which the fluff is soft and pliable, has a so-called lighting effect that flutters in the direction of pressure, and has the appearance of nubuck-like suede. That is, the polyester fiber used in the present invention is one in which an additive that is incompatible with the polyester is dispersed, and the dispersed state is such that the additive is incompatible with the polyester. They are not uniformly dispersed, but are dispersed in various sizes. In addition, since the additive is made of an organic compound, when the fiber is spun and drawn, the additive is also influenced by it and oriented in the fiber axis direction. Such polyester fibers have a highly fibrillating property due to their dispersed and oriented additives. In fabrics woven and knitted using such additive-containing polyester fibers arranged on the surface of woven or knitted fabrics, fibrils are generated by a simple buffing process. Moreover, in this fibril, the additive is dispersed on the molecular order, and furthermore, it is non-uniformly dispersed, so the fuzz generated by the fibril has various thicknesses, and its apparent diameter also falls within the above range. Become.
Furthermore, the generation of such fibrils is not only caused by the separation of the free tips of the fibers, but also from the sides of the central part of the fibers, and the length and number density can be within the above range. This makes it possible to obtain the appearance of a nubuck-style fabric with a lighting effect. Examples will be explained below. Example 1 197 parts of dimethyl terephthalate, 124 parts of ethylene glycol, and 0.118 parts of calcium acetate were placed in a polycondensation flask equipped with a rectifying column, and a transesterification reaction was carried out according to a conventional method. After distilling off a theoretical amount of methanol, the reaction was carried out. The product was transferred to a polycondensation flask with a rectification column, and 0.112% of trimethyl phosphate was added as a stabilizer.
1 part, 0.079 part of antimony oxide as a polycondensation catalyst was added, and the reaction was carried out at a temperature of 280°C and normal pressure for 30 minutes, and then
After reacting for 15 minutes under a reduced pressure of 30 mmHg, the pressure was returned to normal, and after adding 2 parts of a mixture of sodium alkylsulfonate having 8 to 20 carbon atoms and an average carbon number of 14 as an additive, the system was drained. Gradually reduce pressure and stir
The reaction was allowed to proceed for 80 minutes. The final internal temperature was 280°C, the final internal pressure was 0.32 mmHg, and the obtained polymer had an intrinsic viscosity of 0.65. After the reaction, the polymer is chipped according to a conventional method, dried, the dried chips are melt-spun according to a conventional method, and the resulting undrawn yarn is stretched 3.0 times,
It was rolled up at a drawing speed of 800 m/min. Using the additive-blended polyester filament yarn (50 denier/36 filaments) obtained in this way, S300T/M for the warp, S, 3000T/MZ for the weft,
A plain weave (pulse) was woven with a twist of 3000T/M. The fabric is scoured → dried → heat set →
Through each process of alkali weight loss treatment → buffing process → dyeing → final heat setting, fluff is generated on the surface of the woven or knitted fabric to create a fluffy fabric. By varying the degree of buffing, the number of fluffs with a length of 1.0 mm or less and an apparent diameter of 0.01 to 5 μm was obtained as shown in Table 1.

[Table] ◎...Very good △...Somewhat poor ○...Good ×...Poor If the number of fluffs is ^less than 1×10, the texture is poor and the writing effect cannot be obtained, but 1×10 In the case of ⁵ or more, it was possible to obtain an excellent surface like nubuck-like suede.

Claims (1)

[Scope of Claims] 1. Fluff formed by microfibrillating the surface fibers of a woven or knitted fabric made of polyester fibers, which (a) has an apparent diameter in the range of 0.01 to 5 μ; (b) It is substantially covered with fluff whose length is 1.0 mm or less, and the number of fluff is ¹ per 1 cm2.
×10 A woven or knitted fabric having special fluff, characterized by having a surface portion with ⁵ or more fluffs. 2. When manufacturing a woven or knitted fabric using a polyester fiber containing an organic compound and dispersed with an additive that is incompatible with polyester, the surface of the woven or knitted fabric is mainly affected by the polyester fiber containing the additive. The additive-containing polyester used in the woven or knitted fabric is covered with a woven or knitted fabric, subjected to an alkali hydrolysis treatment, and then subjected to a buffing treatment, or subjected to a buffing treatment and then subjected to an alkali hydrolysis treatment. A method for producing a woven or knitted fabric having special fluff, characterized by forming fluff in which fibers are microfibrillated.