JP2935874B2 - Deep-colored polyester fiber fabric and method for producing the same - Google Patents

Description

The present invention relates to a deep-colored polyester fiber fabric and a method for producing the same.

[Conventional technology]

2. Description of the Related Art Conventionally, many studies have been made to enhance the deep hue, particularly the deep color of black, particularly in polyester fibers.

For example, a compound having a low refractive index on a dyed fiber fabric,
For example, a fiber is treated with a fluorine-based treating agent (JP-A-57-176275, etc.), a silicon-based treating agent (JP-A-64-45466, etc.) or a urethane-based treating agent (JP-A-57-29682). There is a method of coating the surface. Although the level of the deep color ratio can be improved by these means, with the improvement of the deep color, problems such as a decrease in the deep color due to dry cleaning washing processing and bleeding out of color due to bleed out of dyeing are likely to occur However, there was a problem in durability of the deep color effect. Another problem is that when an antistatic agent is used to prevent dust and the like from adhering, the deep-colored property is reduced.

On the other hand, there is a method in which fine irregularities are formed on the fiber surface to prevent irregular reflection of light on the fiber surface and aim at deepening the color. As this technical means, a polyester fiber internally containing a microporous forming agent is alkali-treated. (Japanese Patent Application Laid-Open No. 54-120728) and a method of forming fine irregularities by plasma etching the fiber surface (Japanese Patent Publication No. 59-11709, Japanese Patent Publication No. No. 60-37225).

Furthermore, there is also a method in which a fiber product is previously treated with a compound having a low refractive index, and then subjected to low-temperature plasma treatment (Japanese Patent Application Laid-Open No. 61-97490).

By forming fine irregularities on the fiber surface by these methods, the deep coloration is also improved, and particularly when the surface is coated with a compound having a low refractive index, the deep color degree is considerably improved, but the irregularities on the fiber surface are improved. If the fabrics are easily broken, for example, the fabrics are rubbed with each other or the fabrics are entangled in washing, the deep color effect tends to be extremely reduced, and the durability of the deep color is not always at a sufficient level in terms of the durability of the deep color.

[Problems to be solved by the invention]

The present invention relates to a dyed polyester fiber cloth which has been improved to the problem of the conventional deep-coloring technology means, in particular, the durability of the deep-color effect at a high level of deep-coloring to a practically acceptable level. It is an object of the present invention to provide a polyester fiber cloth having an antistatic effect that does not reduce the deep color effect.

[Means for solving the problem]

In the present invention, the surface of the dyed polyester fiber cloth is formed by a general formula (I) (In the formula, m is an integer of 5 to 500, n is 5 to 10, R is a hydrogen atom, a methyl group or an ethyl group, and R 'is a divalent hydrocarbon group.) An object of the present invention is to provide a deep-colored polyester fiber cloth characterized by being coated with a modified silicone and a phosphate compound, and a method for producing the same.

The present invention is directed to dyed polyester fibers. Here, the dyed polyester fiber is
Heat treated at a high temperature of 100 ° C or higher using a dye. Usually, a disperse dye is used as the dye, but a cationic dye or an acid dye may be used in the case of a modified polyester fiber. In addition, as a dyeing method, dip dyeing,
Both thermosol and printing are applicable.

The polyester fiber in the present invention is a polycondensate of a glycol component such as ethylene glycol, trimethylene glycol, 1,4-butanediol, and a dicarboxylic acid component such as terephthalic acid, isophthalic acid, malonic acid, and succinic acid, and glycol. A polyester copolymer obtained by copolymerizing another third component as a component or a part of the dicarboxylic acid component, or a fiber made of a blend of the polyester polymer and another polymer.

In addition, the polyester fiber may contain optional additives such as a catalyst, a coloring inhibitor, a heat-resistant agent, a flame retardant, an antioxidant, and inorganic fine particles as needed.

In the present invention, the polyester fiber may be used by blending, cross-knitting, weaving, or the like with natural fibers such as cotton and wool, regenerated fibers such as rayon and acetate, and synthetic fibers other than polyester, if necessary. Absent.

In the present invention, as the polyester fiber,
Even those which have been subjected to an alkali weight reduction treatment can be used, and a sufficient deep color effect can also be exhibited.

As the polyepoxide compound used in the present invention, a compound containing at least two or more epoxy groups per molecule and 0.2 g equivalent or more per 100 g of the compound is preferably used, and ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene Reaction products of polyhydric alcohols such as glycol and halogen-containing epoxides such as epichlorohydrin, resorcinol bis (4-hydroxyphenyl) dimethylmethane, phenol-formaldehyde resin, resorcinol
Reaction products of polyhydric phenols such as formaldehyde resins and the above-mentioned halogen-containing epoxides, polyepoxide compounds obtained by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, that is, 3,4-epoxycyclohexene epoxide, 3 , 4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate, and the like. Among them, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is particularly preferred because it exhibits excellent performance.

Such a polyepoxide compound is usually good for use as an emulsion.

In order to prepare an emulsion or a solution, for example, a solution in which the polyepoxide compound is used as it is or in a small amount of a solvent as necessary, is added with a known emulsifier such as sodium alkylbenzene sulfonate, sodium salt of dioctyl sulfosuccinate, and addition of nonylphenol ethylene oxide. Emulsify or dissolve using a substance.

In the present invention, the amount of the polyepoxide compound is not particularly limited, but in order to impart durable deep color to the polyester fiber, 0.1 to 1 with respect to the polyester fiber.
Those used in the range of 0% by weight are exemplified.

If the amount of the polyepoxide compound is less than 0.1% by weight, a durable deep color effect cannot be obtained. On the other hand, 10
If the content is more than 10% by weight, the deep color and the durability thereof are not always improved, and the feeling and other disadvantages occur.

The processing temperature of the polyepoxide compound is 70 to 130.
C. is preferred, and a range of 80 to 100 C. is more preferred. If the treatment temperature with the polyepoxide compound is less than 70 ° C, the durability of the deep color is insufficient, while if it exceeds 130 ° C, the durability of these properties is not necessarily further improved, but may be rather reduced. Therefore, it is preferable to process in the above range.

Further, the treatment time of the polyepoxide compound is preferably 1 minute or more, and more preferably 5 to 60 minutes.

If such a condition is satisfied, the processing method may be a high-temperature continuous processing, or a so-called batch-type processing in which fibers are charged from a normal temperature, and then the temperature is raised and the processing is performed at a predetermined temperature.

Next, the amino-modified silicone oil used in the present invention is represented by the following general formula (I).

(In the formula, m is an integer of 5 to 500, n is 5 to 10, R is a hydrogen atom, a methyl group or an ethyl group, and R 'is a divalent hydrocarbon group.) General formula (I) When m is less than 5, a stable compound is difficult to synthesize, and when m is more than 500, the desired performance of the present invention is difficult to obtain, so that m is in the range of 5 to 500, preferably 100 to 200.

Further, n is suitably 1 to 50, and when n is 0, durability of the deep color effect cannot be obtained. On the other hand, when n exceeds 50, processing tends to be unstable.

In the general formula (I), R needs to be a hydrogen atom, a methyl group or an ethyl group. With other alkyl groups, the production is difficult and the durability of the deep color effect is poor.

R ′ is a divalent hydrocarbon group, for example, —CH _{2
-, - (CH 2) 2} -, - (CH 2) 3 -, - (CH 2) 4 -,
_{-CH 2 CH (CH 3) CH} 2 - alkylene groups, such as, - (CH ₂₎
An alkylene arylene group such as _2- C ₆ H ₄ — is exemplified.

 Of these, propylene groups are the most common.

These amino-modified silicons are prepared by using, for example, octamethyltetrasiloxane and gamma- (2-aminopropyl) trimethoxysilane as raw materials, and mixing these raw materials with an alkali metal catalyst, for example, sodium hydroxide or potassium hydroxide. The mixture is heated to a temperature high enough to allow the raw materials to equilibrate (siloxane unit rearrangement).
It can be easily manufactured by heating to 120 ° C.

These amino-modified silicons are dissolved in an organic solvent such as toluene, xylene, n-hexane, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, mineral terpene, and isopropyl alcohol to prepare a treatment liquid. ,spray,
Mangle, may be adhered to the polyester fiber fabric by a method such as immersion, or self-emulsifying as it is, or a suitable emulsifier, for example, a higher alcohol sulfate salt, an alkylbenzene sulfonate, a higher alcohol polyoxyalkylene adduct, It may be emulsified with a higher fatty acid polyoxyalkylene adduct or a higher fatty acid sorbitan ester and adhered to a polyester fiber cloth by a method such as spraying, mangled, or dipped.

In the present invention, the amount of the amino-modified silicone used is preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on the polyester fiber cloth. When the amount of the amino-modified silicone oil is less than 0.05% by weight, the deep color effect is insufficient. On the other hand, when the amount exceeds 1% by weight, the texture of the processed fabric becomes too soft or the dyeing fastness is insufficient. This is not preferred because of disadvantages.

Next, the phosphate ester compound is used as an antistatic agent. Examples of the phosphate ester compound include a higher alcohol phosphate ester salt obtained by phosphorylating a higher alcohol with phosphoric anhydride or an ethylene oxide adduct. Are preferred. Generally used cationic antistatic agents such as guanidine hydrochloride, zwitterionic betaine-type compounds, and nonionic polyhydric alcohol fatty acid esters are not preferable because of a marked decrease in deep color. This effect tends to be better as the refractive index of the phosphate compound is smaller.

The amount of the phosphoric acid ester compound used is, for example, that emulsified to 20% by weight, preferably 0.1 to 1.0% by weight, more preferably 0.1 to 1.0% by weight, based on the solid content of the polyester fiber cloth.
1 to 0.2% by weight. If the amount of the phosphate compound used is less than 0.1% by weight, the antistatic effect is insufficient,
On the other hand, when the content exceeds 1.0% by weight, the decrease in deep coloration is large, and the decrease in friction firmness is large.

The deep-colored polyester fiber cloth of the present invention is obtained by heat-treating a dyed polyester fiber cloth with a treatment liquid containing a polyepoxide compound, and then subjecting the polyester fiber cloth to amino-modified silicon and phosphorus represented by the general formula (I). It is obtained by treating with an acid ester compound.

In the production method of the present invention, unless the dyed polyester fiber cloth is first pretreated with a polyepoxy compound, the effects of the invention (improvement in durability of deep color effect and improvement in friction fastness) cannot be obtained.

The treatment of the amino-modified silicon and the phosphate compound may be performed in the same bath, or the treatment with the amino-modified silicon may be performed first, and then the phosphate compound may be treated in another bath.

[Action]

The present invention is characterized in that a polyester fiber cloth is pretreated with a treatment liquid containing a polyepoxide compound in advance. By this pretreatment, it is not clear how the polyepoxide compound adheres to the polyester fiber fabric, but the durability is excellent without impairing the initial deep color effect even if washing, dry cleaning and friction treatment are performed. Estimated from that, because the polyepoxide compound is firmly attached to the polyester fiber surface, or partially penetrated into the interior of the polyester fiber,
It is considered that the amino-modified silicon and the phosphoric acid ester compound to be applied later react with the epoxy group of the polyepoxide compound to coat the polyester fiber surface with good durability.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The percentages are based on weight unless otherwise specified.

The measurement of the deep color, the washing treatment, the dry cleaning treatment, the rubbing treatment, the charging property, and the rub fastness in the examples were performed under the following conditions.

Measurement of Deep Color The deep color (K / S) was used as a scale indicating the deep color effect. This value is obtained from the following Kubelka-Munk equation, where the reflectance of the sample at 500 nm is R.

K / S = (1−R) ² / 2R The larger the value, the greater the deep color effect.

Measurements were made using the Macbeth COLOR-EYE
(Model M-2020PL).

Laundry processing Using a domestic electric washing machine (National, NA-680L)
30 g of 2 g / solution of new enzyme Zab (manufactured by Kao) was added, and a cotton cloth was added together with the sample so that the bath ratio became 1:30, and the mixture was washed in a vortex water flow at 40 ° C. for 10 minutes. Then dehydrate, warm water at 40 ° C
The sample was washed with hot water at 30 for 5 minutes, dehydrated, washed with overflow water for 10 minutes, dehydrated, and air-dried. This treatment was repeated five times, and the washing was repeated five times, and the deep color was evaluated.

Dry cleaning treatment is performed by the method specified in JIS-L-0844.
This was repeated five times to perform dry cleaning five times, and the deep color was evaluated.

Friction treatment According to the friction fastness test of LIS-L-0849, the sample was attached to the test table, and the same sample as the sample to be rubbed, which was made about 100% wet with distilled water, was attached to the contact surface of the friction element as a friction cloth. It was rubbed reciprocally 20 times with a load of 200 g, and the deep color of the friction portion of the friction cloth was evaluated.

Charging property Using a rotary static tester at a humidity of 40%, a friction cloth was measured by applying a cotton broad, a rotating speed of 400 rpm and a load of 500 g to reach a charging equilibrium when the charging equilibrium was reached. From a practical standpoint, those with a voltage of 1,500 V or more are practical.

Friction fastness was evaluated according to the test method (dry type, wet type) of JIS-L-0849-71.

Example 1 115% elongation obtained by spinning at a spinning speed of 3,200 m / min
Polyester filament yarn (115 denier / 20 filament) and 345% elongation polyester filament yarn (225 denier) obtained by spinning at a spinning speed of 1,380 m / min.
/ 72 filaments), and entanglement treatment and stretch false twisting were performed.

That is, an interlace nozzle gives an entangling degree of 60 pieces / m at an overfeed rate of 2.5% and a pneumatic pressure of 3.5 kg / cm ² , followed by a stretching ratio of 1.56 and a heater temperature of 180.
Stretching false twisting was performed at a temperature of 630 ° C., a surface speed of a friction false twist device of 630 m / min, a second delivery roller speed of 350 m / min, and a K value (untwisting tension / twisting tension) of 1.05.

The resulting processed yarn has an average of 8 / 10mm wrapped parts,
There was a gap between the filaments, and the whole had a moderately convergent wound portion at an average of two places / 10 mm.

Using the false-twisted two-layer structure yarn thus obtained, a satin georgette fabric was woven in the following manner.

The obtained woven fabric was subjected to ordinary crimping, heat setting, and alkali weight reduction (weight loss rate of 20%), and then washed and reduced under the following conditions.

Thereafter, it was washed with water and dried.

Then, it was immersed in a treatment solution prepared according to the following formulation (A) (bath ratio 1:20), and was heated from normal temperature at a rate of 2 ° C./min.
The mixture was treated at 100 ° C. for 30 minutes, washed with water and dried.

Subsequently, the woven fabric was impregnated in a padding bath prepared according to the following formulation (B), and then squeezed at a squeezing ratio of 100%.
And heat-treated at a temperature of 160 ° C. for 1 minute.

After the treatment, the fabric was evaluated for its deep colorability and its durability,
Table 1 shows the results.

[Prescription (A)]

Sorbitol polyglycidyl ether 5% owf (Trade name, Denacol EX-611, manufactured by Nagase Kasei Co., Ltd.) In addition, this sorbitol polyglycidyl ether (Denacol EX-611) was previously emulsified (trade name, Neocol SW, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). What was emulsified (use ratio Denacol EX-611 / Neocol SW = 5/4) was used.

[Prescription (B)]

In the general formula (I), m = 100, n = 10, R = −C
Amino-modified silicone in which amino acid silicon of H ₃ , R ′ =-CH ₂ CH ₂ CH _2- is produced by a conventional method, and the obtained amino-modified silicon is added with a usual emulsifier and emulsified to 30% by an emulsifying machine. 0.6% silicon and lauryl alcohol phosphate compound (Kyoeisha Yushi Co., Ltd., Destat FN10
A mixed solution containing 0.2% of 0).

Comparative Example 1 The same woven fabric as in Example 1 was dyed black, and then a non-processed product not subjected to the prescription (A) and the prescription (B) was evaluated. The results are shown in Table 1.

Comparative Example 2 Example 1 was repeated except that the same woven fabric as in Example 1 was used, and only the prescription (B) was performed without performing the treatment by the prescription (A).
Processing and evaluation were performed in the same manner as described above.

The results are shown in Table 1. As is clear from Table 1, it can be seen that the durability of the deep color is insufficient.

Comparative Example 3 Using the same woven fabric as in Example 1, after the treatment of the prescription (A), at the time of the prescription (B), an antistatic agent (phosphate ester compound)
Except not containing, was treated and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 Using the same woven fabric as in Example 1, after the treatment of the prescription (A), the guanidine hydrochloride (manufactured by Meisei Chemical Co., Ltd., Parlex, Inc.) was used instead of the phosphate compound during the processing of the prescription (B).
600), except for using
evaluated.

 The results are shown in Table 1.

Comparative Example 5 Using the same woven fabric as in Example 1, after processing the formulation (A), when processing the formulation (B), a betaine-type compound (manufactured by Meisei Chemical Co., Ltd .;
BL) was treated and evaluated in the same manner as in Example 1 except that BL) was used.

 The results are shown in Table 1.

Comparative Example 6 Using the same woven fabric as in Example 1, after the treatment of the prescription (A), in the processing of the prescription (B), instead of the phosphate ester compound, a fatty acid ester of a polyhydric alcohol (Meisei Chemical Co., Ltd.)
And Derektor RL) were used and evaluated in the same manner as in Example 1.

 The results are shown in Table 1.

[Effects of the Invention] According to the present invention, a polyester fiber cloth having a high level of deep color and excellent durability can be obtained, and a cloth having antistatic performance can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) D06M 15/00-15/715 D06M 13/00-13/535

Claims (2)

(57) [Claims] 1. A deep-color dyed surface of a dyed polyester fiber cloth, which is coated with an amino-modified silicone and a phosphate compound represented by the following general formula (I) via a polyepoxide compound. Polyester fiber cloth. (In the formula, m represents an integer of 5 to 500, n represents 5 to 10, R represents a hydrogen atom, a methyl group or an ethyl group, and R ′ represents a divalent hydrocarbon group.) 2. A dyed polyester fiber cloth is heat-treated with a treatment liquid containing a polyepoxide compound, and then the polyester fiber cloth is treated with the amino-modified silicon and phosphate compound according to claim 1. A method for producing a deep-colored polyester fiber fabric.