JPS61245386A - Polyester dyed cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] fO! TECHNICAL FIELD The present invention relates to a dyed polyester fabric with high color development and excellent abrasion resistance.

←) Conventional technology Polyester fibers have excellent physical properties and have been widely used for clothing and non-clothing applications, but the color of their dyed products is inferior to that of acrylic and acetate fibers. Various improvement measures have been proposed so far.

For example, there is a method of coating the surface of polyester fibers using a low refractive index base material. Polyester fiber #1llI has a high refraction wheel among fiber materials, and the surface reflection becomes large and the dyed material has a pastel tone, giving it a so-called Chinese cabbage-like appearance.

For this purpose, a low refractive index is added to the surface of the fiber to improve this drawback, and the low refractive material is fluorine-based, silicon-based, or urethane-based.

A silica-based compound or the like is used. As treatment methods, there are methods such as padding, adsorption from bath, etc.
5485 etc.). However, these methods have poor durability when washed, reduce dyeing firmness, impair texture, and even cause unevenness during fiber processing, making them insufficient as techniques for achieving high color development. However, an alternative method is to form micropores on the fiber surface and roughen the surface. This method is known, for example, in JP-A-55-107512 and JP-A-57-139118.
In this method, inert fine particles are blended in the polymer manufacturing stage, and the surface of the obtained polyester fiber is made uneven by an alkali weight reduction process. As active fine particles, silica blocked with a silanol group or an internally precipitated particle method using particles precipitated by reacting a phosphorus compound with an alkaline earth metal have been proposed. The color development of these polyester fibers can only be improved by reducing the amount of polyester fibers, forming micropores on the surface of the fibers, and then dyeing them. Because of this, the abrasion resistance is insufficient, and there is a drawback that there are frequent scratches caused by friction with busy equipment during the processing process. As a countermeasure against this, there is a method of uniformly damaging the entire fabric with a washer etc. in advance so that it is difficult to visually tell when it is made into a product (Japanese Patent Laid-Open No. 57-101036).
However, with this method, KF1 cannot be applied to flat products (e.g., tucks, textured yarn plain fabrics) that do not pass through the washer process, and because it damages the fibers, it is difficult to apply KF1. There is a drawback that high color development is impaired. As another technical means for making the fiber surface uneven, the formation of micropores on the surface of polyester fiber by irradiation with low-temperature plasma has been proposed (Japanese Patent Publication No. 11709/1982). Although this method also improves the coloring properties of the microporous formation, the abrasion resistance of the dyed fabric obtained is poor, and the technology is still in the development stage and is very difficult to use at the current stage. Therefore, it cannot be put to practical use.

e→ Problems to be Solved by the Invention The problems to be solved by the present invention are that when polyester fibers containing a microporous forming agent are dyed after alkali weight loss as in the past, the first K, reduction washing after dyeing, Or saw
Ping makes it extremely difficult to remove the dye in the micropores, and the dye remains inside the pores, adhering to the surface.For this reason, it is difficult to make full use of the optical functions of the micropores! In addition to not being able to obtain the original color of the dye, the coloring properties are significantly reduced.Second KFi, when dyeing polyester fibers with fine holes and holes formed on the surface using a jet dyeing machine, for example. , due to the treatment in high-temperature, high-pressure water, the fabrics collide violently with each other, or the fabrics collide with the inner wall of the can,
As a result, the material becomes fibrillated, causing deformation and collapse of the pores, resulting in so-called scratching, which significantly deteriorates the quality.

2) Means for Solving the Problems As a result of intensive research to solve these problems, the present inventors have developed a method for dyeing woven and knitted fabrics made of polyester fibers containing a micropore-forming agent. Later, it was discovered that it is possible to obtain a fabric that simultaneously satisfies the two properties of high color development and improved abrasion resistance by reducing the alkali weight loss, and arrived at the present invention. The fiber surface has micropores, and the maximum frequency value of #micropores in the frequency distribution of the size is in the range of 0.1 to 0.5# in the direction KG width perpendicular to the fiber axis. , and the fiber axis direction K G 'S length ζ is 0.5 to 5 #
A fabric made of a polyester fiber car in the range of It is a polyester dyed fabric characterized by having a color density of 920 ■ or less.

The polyester fibers used in the present invention must contain a micropore-forming agent, and the effects of the present invention cannot be obtained by twisting polyester fibers that do not contain a micropore-forming agent.

Such a micropore-forming agent can be used in alkali weight loss treatment to form micropores on the surface or inner surface of polyester fibers, thereby creating a natural fiber-like texture and hygroscopicity.

There is no need to specifically limit the material as long as it can substantially exhibit the functions of micropores such as the depth and clarity of a single water-absorbing color, but especially when the micropore-forming agent is a compound containing a metal. The effects of the present invention are significantly exhibited.

Among the above-mentioned micropore-forming agents, in order to achieve the object of the present invention, particularly desirable ones are those that (a) react with the acid component constituting the polyester at any stage until the synthesis of the polyester is completed.

0.3 to 3 mol % of a phosphorus compound represented by the following general formula (1) % formula % and (b) an alkali+7 F class metal compound are reacted in advance with (&) and (b). And by adding so that the total number of equivalents of metals (a) and cb) is 2.0 to 3.2 times the number of moles of phosphorus compound (&), polyester reaction is carried out. Examples include insoluble fine particles precipitated by the reaction between (a) and ka) inside the system.

In the above formula (,1) representing a phosphorus compound, R1 and Bt are hydrogen atoms or monovalent organic groups. Specifically, this monovalent organic group is an alkyl group, an aryl group, an aralkyl group, or a mo(
CHt)kR" (where Bm is a hydrogen atom, an alkyl group, an aralkyl group, or an aralkyl group, j is an integer of 2 or more,
is preferably an integer of 1 or more, and R' and W may be the same or different. X is a hydrogen atom, a monovalent organic group, or a metal, and examples of the monovalent organic group include the above R1, Rl
Same as the definition of organic group in K, ul, R1
Can be the same or different, and as a metal! For Li', Na+, Mgl/2. Cal/2. Srl/
2. Bal/2 is particularly preferred.

m is an integer of 0 or 1. Examples of such phosphorus compounds include sulfuric acid, trimethyl phosphate, and triethyl phosphate.

Phosphoric acid triesters such as tributyl phosphate, triphenyl phosphate, phosphoric acid hepta and diesters such as methyl acid phosphate, methyl acid phosphate, methyl acid phosphate, phosphorous acid, trimethyl phosphite.

Triethyl phosphite, tributyl phosphite.

Phosphite triesters such as triphenyl phosphite, methyl acid phosphite, methyl acid phosphite,
Phosphite mono- and diesters such as methyl acid phosphite, phosphorous compounds obtained by reacting the above-mentioned phosphorus compounds with glyfur and/or water, and further the above-mentioned phosphorus compounds in predetermined amounts of Li1Na, etc. One or more phosphorus compounds reacted with a compound of an alkali metal or a compound of an alkali-17f metal such as MgtCa+8reBa and the like can be used.

The alkaline earth metal compound to be used in combination with the above phosphorus compound is not limited to 41 as long as it reacts with the above phosphorus compound to form a salt insoluble in polyester, and alkaline earth metal acetates, salts, etc. organic carboxylates such as acid salts, benzoates, phthalates, stearates, inorganic acid groups such as borates, sulfates, silicates, carbonates, 9 bicarbonates,
halides such as chlorides, chelate compounds such as ethylenediaminetetraacetic acid complex salts, hydrates, oxides, alcoholades such as methylates, ethylates, glycolates,
Examples include phenolates. Organic carboxylic acid salts soluble in ethylene glycol, halogenated 'I & 1. *Lz-to compounds and lycolate are preferred, and organic carboxylic acid salts are particularly preferred. The above alkaline earth metal compounds may be used alone or in combination of 211 or more.

In addition to the above-mentioned micropore forming agents, silica sol, dry process silica containing aluminum oxide, dry process silica with blocked silanol groups on the particle surface, alumina sol, fine particulate alumina, ultrafine titanium oxide, and calcium carbonate sol are also available. Preferably, inert inorganic fine particles having an average primary particle diameter of 100 mm or less are made of at least one of the following: and finely particulate calcium carbonate. The content of such inert inorganic fine particles in the polyester fiber is 0.1 to 10% by weight based on the polyester fiber mK.
A range of 0.3 to 5% by weight is particularly preferred.

The above-mentioned inert fine particles are prepared as a dispersion slurry or sol of glycol, alcohol, water, etc. For example, in the case of silica sol, (1) an aqueous silica sol obtained by removing a dialkali component such as water glass (2) aqueous silica sol as it is; Glycol and/or are mixed with alcohol (
3) It is desirable to replace the water in this aqueous silica sol with glycol and/or alcohol and add it at any stage until the polyester synthesis reaction is completed.

The polyester containing the micropore-forming agent thus obtained is made into υ fiber by a normal yarn spinning method.

The polyester used in the present invention has terephthalic acid as its main acid component and at least one type of glycol, preferably ethylene glycol.

The main target is a polyester whose main glycol component is at least 1s alkylene glycol selected from trimethylene glycol and tetramethylene glycol.

It may also be a polyester in which part of the terephthalic acid component is replaced with another difunctional carboxylic acid component, and/
Alternatively, it may be a polyester in which a part of the glycol component is replaced with the above-mentioned glycol or other diol component other than the main component.

Examples of difunctional carboxylic acids other than terephthalic acid used here include isophthalic acid 11, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, β-hydroxyethoxybenzoic acid, p-oxybenzoic acid, 5 - Aromatics such as sodium sulfoine heptatarate, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid.

Examples include aliphatic and alicyclic difunctional carboxylic acids. Examples of non-siol compounds other than the above glycols include aliphatic, alicyclic, and aromatic diol compounds such as cyclohexane-1,4-dimetatool, neopentyl glycol, bisphenol A, and bisphenol S, and polyoxyalkylene glycols. Can be done.

Such a polyester may be synthesized by any method KL. For example, polyethylene terephthalate [to explain, it is usually a direct esterification reaction between terephthalic acid and ethylene glycol, a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a transesterification reaction between terephthalic acid and ethylene glycol. The first stage reaction is to react with ethylene oxide to produce glyfur ester of terephthalic acid and/or its low polymer, and the first stage reaction product is heated under reduced pressure to reach the desired degree of polymerization. It is produced by the second stage reaction of polycondensation reaction ζ.

When melt-spinning the micropore-forming agent-containing polyester, a normal polyester fiber melt-spinning method can be arbitrarily adopted, and the spinning speed is 1000 to 8000 m/sts.
@ Tsuta stretching is preferably carried out as needed, but in that case, for example, heat stretching can be performed using a hot roller or hot pin, and if necessary, heat setting can be performed using a plate heater. good. In that case, it is preferable to select a low draw height so that the residual elongation of the drawn yarn is as high as 30 to 50%.

The drawing temperature (hot roller temperature) is preferably set to be equal to or higher than the glass transition point of polyester when the birefringence straw (Δn) of the spun and undrawn yarn is less than 0.035, and when Δn is 0.035 or more, , room temperature stretching may be used. The cross-sectional shape of the polyester fibers constituting the polyester fabric of the present invention may be round or irregular. A round cross section is suitable for k, which improves color development and drapability, and a triangular cross section is suitable when adding silky luster. The single yarn denier is preferably 1 to 3 deniers, and fibers of about 2 denier are particularly preferred to obtain a rayon-like stiff drape.

Fiber boiling water shrinkage straw contains 6.5% normal polyester fiber.
, 7.5 to 15% is preferable.

It may also be mixed with other fibers or made into so-called taslan yarn using turbulent air. Twisting the yarn during knitting or weaving will further improve the drape and coloring properties, so use neutral or untwisted yarn (0
Rather than knitting from yarns of ~300 T/m), the warp and/or weft are made from medium twisted or highly twisted yarns (500-350 T/m).
It is preferable to knit and weave using 0 T/m 2 ). Further, the polyester fiber used in the present invention may contain optional additives 1, such as a catalyst 9, a coloring inhibitor, a heat resistant agent, a fluorescent whitening agent, a matting agent, 9 a coloring agent, etc., as necessary. .

The polyester fiber thus obtained is woven or knitted into a fabric, then subjected to a relaxing treatment in hot water, dried, and then heat-set. As the relaxing method, commonly used washer method, carrier washer method, continuous relaxing method, etc. are used, but it is important to fully develop the shrinkage force of the polyester fiber in the relaxing step. Usually, it is good to shrink it by 10-20%. X. It is desirable that the extension rate during heat setting be kept within 5%.

The fabric subjected to such treatment is then dyed. As a dyeing method, in order to maximize the effect of the present invention on 4#, it is desirable to employ a jet dyeing machine. For example, circular dyeing machine (manufactured by Nichiita Seisakusho), Uniace dyeing machine (
(manufactured by Nippon Senzo Kikai ■). A disperse dye is required as the dye to be used, and it is preferable to use a high-strength type dye. That is, the disperse dye has a molecular weight of 1.
A soft type with a molecular weight of less than 50 and a hard type with a molecular weight of 150 or more are known, and the soft type is mainly used because of its good level dyeing properties. In the dyed fabric of the present invention, it is preferable to use a hard type disperse dye, especially one having a molecular weight of 250.
It is preferable to use one having a value of about 350 to 350.

Although the hard type dye has good hardness, it has some difficulty in level dyeing, so it is preferable to use a dyeing aid or the liquid flow type dyeing machine. 1 more
The present invention is effective for products dyed with a dye immersion degree of 10% owf or higher. The fabric of the present invention is obtained by subjecting the dyed fabric to an alkaline weight loss treatment 31. In this alkali weight loss treatment KL, fine pores arranged in the axial direction of the fibers are formed, giving a fabric with excellent color development.

Examples of the alkali compound used here include sodium hydroxide, potassium hydroxide, tetramethylammoniumhydroxide, sodium carbonate, potassium carbonate, and the like. Among these, sodium hydroxide and potassium hydroxide are particularly preferred.

Alkaline weight loss accelerators such as polyester, cetyltrimethylammonium bromide, lauryldimethylbenzylammonium chloride, etc. can be used as appropriate.

The acid-alkali weight loss treatment may be carried out using a dyeing machine, a washer, etc. under high pressure or normal pressure, but it can also be carried out by a pad steam method or even a cold batch method. It is preferable to use 2% by weight or more based on heavy IIK, and usually 2 to 40% by weight.
Those within the range of are preferably used.

As for the size of the micropores obtained by the alkali weight loss treatment, the value having the maximum frequency in the frequency distribution of the micropores is 0.1 to 0 for the width in the cross-sectional direction perpendicular to the fiber axis.
．． 5 and the length in the fiber axis direction is 0.
．． Anything in the range of 5 to 5 # can achieve the object of the present invention.

If it exceeds the above range, the effects of the present invention will be significantly reduced. The size of the micropores obtained by alkali reduction needs to be larger than the above-mentioned lower limit in order to lower the coefficient of friction on the fiber surface and provide drapability. However,
When the diameter of the micropores becomes large, the problem arises that the color tone becomes pastel due to the influence of light scattering. Therefore, in order to obtain clear color development, the size of the micropores must be kept below the above upper limit value. Finishing Ceratra is performed after alkali weight loss treatment, but in this case, it is preferable to keep the widening ratio to 5% or less. . still,
The setting temperature is preferably as low as possible (160° C. to 5180° C.) in order to prevent migration of the disperse dye to the fiber surface and a decrease in sharpness.

In addition, the dyed fabric of the present invention can be subjected to @hydration processing etc. after the alkali weight loss treatment. As the processing after such alkali weight loss treatment, a method is preferably employed in which the surface of the polyester fiber is coated with a polymer having a refraction wheel lower than that of polyester, such as dimethylpolycyxane or tetrafluoro-a-ethylene-propylene copolymer. can. Examples of post-hydrophilization processing include a method of treating polyester fibers with an aqueous dispersion of a polyester polyether block copolymer consisting of terephthalic acid and/or isophthalic acid or their lower alkyl esters, lower alkylene glycols, and polyalkylene glycols. can be preferably adopted.

The thus obtained dyed fabric of the present invention has a dye extraction amount of 20 ql or less per 1 g of fiber at room temperature. This means that the amount of dye attached to the surface of the fibers constituting the dyed fabric is small. 4
? K. The dyed fabric of the present invention has micropores formed by the alkali reduction treatment in which the polyester fibers constituting it are formed after the dyeing process, and the micropores are formed without attaching dye to the surface, unlike the conventional dyed fabric process. This is what is being done.

The amount of pattern dye extracted is 1. If it exceeds OV, the coloring properties will deteriorate, which is not preferable.

B) Effect of the Invention The present invention is characterized by the fact that the polyester fibers constituting the dyed fabric have micropores, and in spite of the presence of one micropore, the dye adheres to the surface of the fabric to a small extent. It has good bathochromic properties. When dyed fabrics made of fibers with micropores formed on the fiber surface are dyed using conventional methods, a large amount of Ka-collecting dye remains on the surface of the micropores, and the optical function of the micropores cannot be fully utilized, resulting in poor color development. It has decreased significantly.

Since the residual agglomerated dye exists in the micropores, it cannot be removed by the usual reduction cleaning method that is carried out immediately after dyeing, and it adversely affects one color. The fabric of the present invention is obtained by a method of dyeing with a disperse dye under high temperature and high pressure and then reducing the weight with alkali. It forms a hole. Therefore, the deep coloring function of micropores is fully demonstrated,
Compared to the conventional pre-weight reduction method, it is possible to greatly reduce the amount of alkaline weight loss straw with high color development and the degree of deep coloring equivalent to that of potassium.

The improvement in color development in the present invention refers to Kubelka-Mu
It can be evaluated by the /S value calculated from the formula of nk, and compared with the unreduced product without alkali weight loss treatment.
A good bathochromic effect is indicated when the K/S value difference is 1 or more.

Furthermore, the fabric according to the present invention does not have micropores formed yet during dyeing, so it is susceptible to friction that occurs during the dyeing process, and the M fibers do not fibrillate due to the micropores. will not deform or collapse. If micropores are formed during dyeing, fibrillation and collapse of the micropores, so-called threading, will occur, resulting in a decrease in quality, but the fabric of the present invention has improved these problems. Ru.

(F) Examples (Examples 1 to 3) 100 parts of dimethyl terephthalate, ethylene glyph-/l
/60IL Calcium acetate 1 tJ [0.06 parts (0.066 mol% based on dimethyl terephthalate) of calcium acetate was charged into a transesterification tank and 1 tJ of calcium acetate was added over 14 hours in a nitrogen gas atmosphere.
The temperature was raised from 40"C to 230°C, and the resulting methanol was distilled out of the system while the transesterification reaction was carried out. Subsequently, 0.5 parts of trimethyl phosphate (terephthalate) was added to the resulting reaction product. 0.693 mol% based on dimethyl acid)
and 0.31 parts of calcium acetate monohydrate (1 part, 2 times the mole relative to trimethyl phosphate) were reacted in 8.5 parts of ethylene glycol at a temperature of 120°C under total reflux for 60 minutes to purify it. Diester calcium phosphate salt obtained by dissolving 0.57 parts of calcium acetate monohydrate (0.9 times mole relative to trimethyl phosphate) at room temperature in 9.31 parts of a clear solution of diester calcium phosphate salt. 9.88 s of a mixed clear solution with calcium acetate was added, followed by 0.04 part of antiseptane trioxide and transferred to a polymerization vessel. Then, over 1 hour, from 760 mm1ljF to 1a+
Reduce the pressure to al19, and simultaneously reduce the pressure to 230℃ over 1 hour and 30 minutes.
The temperature was raised from 'Q to 285°C a 1 Under reduced pressure of less than wmH9, the polymerization temperature was 285°C for an additional 3 hours, for a total of 4 hours 3
Polymerization was carried out for 0 minutes to obtain a polymer having an intrinsic viscosity of 0.640 and a softening point of 259°C. After completion of the reaction, the polymer was made into chips according to a conventional method.

This chip was dried by a conventional method, melt-spun at 290°C using a spinneret with 36 circular spinning holes with a hole diameter of 0.3 mm, wound at 1300 m/si1, and then stretched to 75 denier. A drawn yarn of /36 filaments/t was obtained.

Kono drawn yarn KSm2800'l'/M and 2 twists 2800
T/M strong twist is applied, followed by patterned high twist yarn at 70℃ for 30 minutes.
Steam for a minute and apply one coat.

This yarn was used as a weft. Similarly, the yarn which was twisted with 8 twists of 300 T/M and coated and set was used as a warp. The coated high-twist yarn has a warp density of 64 threads/country and a weft density of 32 threads/
In step 3, two S and Z@ yarns were arranged alternately to weave a weft strong twist palace fabric.

The obtained gray fabric is heated to boiling temperature in a rotary washer for 2 hours.
After 0 minutes of relaxing treatment, grain raising, and presetting in the usual way, Dianix Black HG
FS (Mitsubishi Chemical Corporation ■ product) After dyeing with a staining solution containing 2g/'l of diethylenetriaminopentaacetic acid 5Na salt at 15% owf for 60 minutes at 13''oC, dyeing with sodium hydroxide 2
g/l, in an aqueous solution containing 1 g/l of hydrosulfite and 1 g/l of ethylenethominepentaacetic acid 5Nm salt.
A black dyed cloth was obtained by light washing at 0° C. for 20 minutes. Sara K, 3.
Treated with 5% aqueous sodium hydroxide solution at boiling temperature,
A black fabric having an excellent color development property with a reduced straw content of 5.10% and 20% was obtained.

(Comparative Example 1) A black dyed cloth obtained by scouring and dyeing the gray cloth obtained in the same manner as in Examples 1 to 3 was finished without being treated with alkali. This product was inferior in bathochromic properties as an example.

(Comparative Examples 2 to 3) The gray fabric obtained in the same manner as in Examples 1 to 3 was
After mmL, I re-set it in the usual way, then did alkaline weight loss treatment (weight loss 10.20%), and then gave him the same prescription as in the example! 55 parts of black dyed cloth obtained by reduction washing,
Fibril I.

A significant deterioration in the quality of the product was observed.

1st! ! Examples 1 to 3. The results of Comparative Examples 1 to 3 are shown.

Table 1 In addition, the measured value is obtained by the following measuring method.

Measure the reflection IER (%) of the dyed fabric using a self-recording spectrophotometer RC-330 manufactured by Chromogenic Takashi Seisakusho (wavelength 500 m).
g) L., Kubelkm-Munk below.

Color development (K/8) was calculated from the formula.

K/S=(1-R)Kura/2R Acetone extraction (removal of dye from microporous holes) The dyed cloth was extracted with acetone at room temperature for 20 minutes.

Determine the amount of dye extracted per fiber weight (■/g).

The level of hit determination was visually determined and ranked as follows.

(I can't see this) ◎>0>Δ>X (This 9 is extremely large)
Fabrics dyed by the method of the present invention (reduced weight after dyeing) show no change in color development even after extraction with acetone, and no staining is observed at all. On the other hand, as shown in Comparative Examples 2 and 3, those dyed after weight loss had extremely poor color development due to the dye accumulated in the micro pores, and when this dye was extracted by acetone extraction, the optical Demonstrates its functionality and improves color development, and the hit level is extremely low.
It cannot be put to practical use.

As described above, by dyeing polyester fibers containing a micropore-forming agent and reducing the amount of alkali to impart micropore irregularities to the surface, a polyester fabric that satisfies color development and abrasion resistance at the same time was obtained. .

Claims (1)

[Claims] At least the fiber surface has micropores, and the micropores have a maximum frequency value in the frequency distribution of the size in the range of 0.1 to 0.5μ in the width along the direction perpendicular to the fiber axis; And the length along the fiber axis direction is 0.5~
A fabric made of polyester fibers in the range of 5μ, the fabric is dyed with a disperse dye at a dye concentration of 10% OWF or more, and the amount of dye extracted from the dyed fabric by room temperature acetone is per gram of fiber weight. A polyester dyed fabric characterized by having a content of 20 mg or less.