JPH03294522A - Production of water-repellent polyester fiber having excellent durability - Google Patents

Abstract

PURPOSE:To obtain the title fiber having excellent dark color developing properties and durability by providing specific polyester fiber with aliphatic polyepoxy compound, heating and drawing and supplying the fiber with an amino modified silicone compound. CONSTITUTION:Polyester fiber having <=0.08, preferably <=0.01 double refraction of amorphous part is provided with an aliphatic polyepoxy compound containing two or more epoxy groups in the molecule, then heated and drawn and/or heat- treated and then supplied with an amino modified silicone compound to give the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing polyester fibers having excellent durability and water repellency.

<Prior Art> Various studies have been conducted to improve the potability of polyester fibers, and various methods have been proposed. For example, a dyed polyester fiber fabric is treated with a low polarity compound such as a fluorine compound or a silicone compound,
A method of coating the surface of polyester fibers with the compound has been proposed.

It is true that by these methods, fabrics with good potability can be obtained. However, since the adhesion of these treatment agents to polyester fiber fabrics is low, there is a problem in that these treatment agents fall off due to friction during washing or use, resulting in a reduction in bowl water performance.

Also, a method has been proposed in which a fluorine compound is added to a spinning oil during fiber production, but in this method, the fluorine compound is simply present on the fiber surface.
Similarly to the above, it easily falls off due to washing, friction, etc., and therefore, the durability of water absorption performance was insufficient.

<Object of the Invention> The present invention has been made in view of the drawbacks of the above-mentioned prior art. The aim is to develop a method for producing polyester fibers that have water-repellent properties that are durable and do not deteriorate in performance due to friction during washing or wearing.

<Structure of the Invention> As a result of intensive research to achieve the above object, the present inventors surprisingly found that an epoxy compound was added to undrawn polyester yarn immediately after spinning, and an amino-modified silicone compound was added after drawing. As a result, the inventors discovered that a potable polyester fiber with extremely excellent durability could be obtained, leading to the present invention.

That is, the present invention provides a polyester fiber whose amorphous portion has a birefringence index of 0.08 or less, which is coated with an aliphatic polyepoxy compound having two or more epoxy groups in the molecule, and then subjected to hot stretching and/or heat treatment. This is a method for producing water-repellent polyester fibers with excellent durability, in which an amino-modified silicone compound is then added.

The polyester fiber in the present invention refers to a polycondensate of a glycol component such as ethylene glycol, trimethylene glycol, or tetramethylene glycol and a dicarboxylic acid component such as terephthalic acid, inphthalic acid, malonic acid, or succinic acid, a glycol component, or a dicarboxylic acid component. As part of the components, there are polyester copolymers copolymerized with another third component, or fibers made of blends of these polyester polymers and other polymers.

Incidentally, such polyester fibers may contain arbitrary additives such as catalysts, color inhibitors, heat resistant agents, flame retardants, antioxidants, inorganic fine particles, etc. as necessary.

Next, the aliphatic polyepoxy compound used in the present invention has at least two or more epoxy groups in one molecule,
Compounds containing 0.2 g equivalent or more per 100 g of the compound are preferably used, such as ethylene glycol,
glycerol, sorbitol, pentaerythritol,
Reaction products of polyhydric alcohols such as polyethylene glycol and halogen-containing epoxies such as epichlorohydrin, polyepoxy compounds obtained by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, i.e. 3,4 epoxycyclohexylethylene oxide, 34-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxy-6-
Examples include methyl-cyclohexylmethyl)adipate. Among these, it is particularly preferable to use reaction products of polyhydric alcohols and epichlorohydrin, ie, polyglycidyl ether compounds of polyhydric alcohols, because they exhibit excellent performance.

Such polyepoxy compounds are usually used as emulsions or aqueous solutions. To make an emulsion or solution, for example, the polyepoxy compound as it is or dissolved in a small amount of solvent as necessary may be mixed with a known emulsifier such as sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide. Emulsify or dissolve using adducts, etc.

The fibers to which these epoxy compounds have been applied are then subjected to processes such as hot drawing and/or heat treatment, so in order to improve the stability of passing through the process, the epoxy treatment liquid contains a smoothing agent, a control agent, etc. It is desirable to use commonly used textile oils such as Jing, etc. The combination ratio of the epoxy component and the oil component is as follows:
There is no particular limitation as long as it does not impair the purpose of the present invention, and it may be set appropriately based on the relationship between process stability and epoxy compound adhesion.However, if the oil component is too small, the process The stability does not improve, and on the other hand, if the amount is too large, the adhesion of the epoxy compound is impaired, so the weight ratio of oil component/'epoxy compound is usually 10. '90-7
0/30 is preferably used. In the present invention, the above-mentioned epoxy compound is added to the polyester fiber, and the amorphous birefringence index (Δna) of the polyester fiber is 0.08 or less, preferably 0.06.
Hereinafter, it is particularly important to set the value to 0.01 or less. If this value is exceeded, the adhesion of the epoxy compound decreases, presumably due to a decrease in the diffusion and adsorption of the epoxy compound into the fiber, and the durability of the water repellency of the obtained fiber becomes poor.

Further, the amount of the epoxy compound applied to the fiber is preferably 0.1 to 0.5% by weight based on the weight of the fiber.
．． If the amount is 1% by weight without grooves, the durability of the water repellent performance of the obtained fiber will be insufficient, and conversely, even if it exceeds 0.5% by weight, the durability of the water repellent performance will not necessarily improve; ,
This is not preferable because it causes other defects such as a decrease in texture.

The fibers to which the epoxy compound has been applied are subjected to hot drawing and/or heat treatment in order to strengthen the adhesion of the epoxy compound. It is presumed that if this temperature is too low, the epoxy compound will not diffuse into the fibers, but the adhesion of the epoxy compound will decrease and the durability of the water resistance performance will decrease.On the other hand, if this temperature is too high, the epoxy compound will not diffuse into the fiber. This is not preferable because the texture of the obtained fibers becomes hard as well as the quality changes.

Usually, a temperature of 70 to 250°C is preferably employed.

Next, the amino-modified silicone compound used in the present invention is
Amino modified group is -RNH2 or -RNHCH2CH
2NH2 (R is a divalent alkylene group) and has an amino equivalent of 3.000 or less.

When the amino equivalent exceeds 3.000, it tends to be difficult to obtain the watery effect.

Such an amino-modified silicone compound is applied to the fiber after hot drawing and/or heat treatment, but if the viscosity is too high at this time, uneven adhesion to the fiber will occur, so it may be used as a diluent or as a post-mobilization agent for the resulting fiber. It is desirable to use a low viscosity lubricant as a compatible diluted lubricant to improve the lubricity at the culm. Such low viscosity lubricants include:
There is no particular restriction as long as it is compatible with the amino-modified silicone compound and is non-reactive, such as mineral oil or imbutyl oleate having a viscosity of 200 seconds or less redwood.

Monobasic acid esters such as inoctyl palmitate are preferably used. The mixing ratio of the amino-modified silicone compound and the low-viscosity lubricant is also not particularly limited, as long as the liquid viscosity after dilution does not cause adhesion spots and does not pose a problem in handling. Preferably, the viscosity at 30° C. after dilution is 60 cst or less.

Further, other additives may be dissolved in these solutions for purposes such as improving antistatic properties and heat resistance. However, in this case, it goes without saying that it is necessary to be non-reactive with the amino-modified silicone compound and not increase the viscosity.

Next, in order to improve the adhesion of the compound to the fiber surface, the amount of the amino-modified silicone compound to be applied is adjusted so that the ratio with the epoxy compound is within a specific range, that is, epoxy compound/amino-modified silicone compound (weight ratio). It is desirable to set the ratio to 50/50 to 5/95. By doing so, the silicone compound can be extremely firmly adhered to the fiber surface, and as a result, the durability of the water performance is extremely improved. .

<Actions and Effects of the Invention> According to the production method of the present invention, since the epoxy compound is applied in a state where the birefringence of the amorphous portion is low, the epoxy compound is added to the polyester fiber during subsequent hot stretching or heat treatment. The amino-modified silicone compound that is then applied is diffused and adsorbed onto the surface of the polyester fiber, resulting in strong adhesion.The amino groups of the amino-modified silicone compound react with the above-mentioned epoxy compound to form a chemical bond. It will be firmly fixed. As a result, the water-resistant performance based on silicone compounds exhibits extremely excellent durability against washing, dry cleaning, and other treatments that involve various frictional effects.

On the other hand, if a normal drawn yarn with a high birefringence in the amorphous part, that is, a high degree of orientation in the amorphous part, is used, it is presumed that the fixation of the epoxy compound is insufficient.
The durability of the bowl water performance described above cannot be achieved.

In addition, the polyester fiber thus obtained has excellent bathochromic properties since the silicone compound generally has a low refractive index, and the durability of the effect is also excellent.

<Example> Hereinafter, the present invention will be explained in detail by way of examples.

In addition, the amorphous birefringence index (Δna) of polyester fiber
, R water resistance, evaluation of durability against washing, dry cleaning, and abrasion treatment, and evaluation of bathochromic property were conducted under the following conditions.

(1) Δna (birefringence of amorphous region) A parameter indicating the orientation of molecular chains in an amorphous region, and the degree of crystallinity Xρ determined from specific gravity.

Birefringence △n, crystal orientation function fc (JP-A-50-595
Calculated using the following formula (described in Publication No. 26).

△n -0,212f c-Xp o, 7491- (1/ρ) However, Xρ 0.06178 Δn==n,, -n↓ Here, the birefringence (△n) is It is expressed as the difference between the refractive index (n) for polarized light and the refractive index (nll) for light polarized parallel to the fiber axis (Δn ” n11 n↓). Measurement was performed using an attached polarizing microscope using a conventional method.

However, tricresyl phosphate was used as the immersion liquid.

(2) Measurement of water repellency According to the spray test of JIS L-1092-77, the sample was mounted on a 45-degree inclined table, and after spraying distilled water from above, water repellency was determined based on the state of water remaining on the sample. was evaluated.

+a Laundry treatment Using a household electric washing machine II (National, NA-6801), add 30 L of New Enzyme Sub (manufactured by Kao ■) 2 g/L solution, and wash it with the sample so that the bath ratio is 1 = 30. In addition, it was washed with 30 L of warm water at 40° C. for 5 minutes, dehydrated, washed with overflow water for 10 minutes, dehydrated, and air-dried. This treatment was repeated 5 times and washed 5 times to evaluate water repellency and deep color.

(Dry cleaning treatment) This was carried out according to the method specified in JIS-L-0844, and this was repeated 5 times to obtain 5 dry cleaning treatments, and the water resistance and bathochromic properties were evaluated.

(5) Friction treatment In accordance with the friction fastness test of JIS-1-0849, the sample was mounted on a test stand and the same sample as the sample to be rubbed was kept approximately 100% wet with distilled water as a friction cloth. The cloth was attached to the contact surface and rubbed back and forth 20 times under a load of 200 g to evaluate the water repellency and deep color of the friction portion of the skewer rubbing cloth.

+61 Measurement of bathochromicity Bathochromicity (ni/S) was used as a measure of bathochromic effect. This value can be obtained from the following equation (Kuber's force-Munk equation), where R is the reflectance of the sample at 500 nm.

/S = (1-R)2 /2R The larger the value, the greater the bathochromic effect.The measurement was performed using Macbeth Color Eye Modelt 2020PL.

The weaving and dyeing processes performed here were carried out in the following manner.

■ Weaving; Structure - Plain weave Warp twist number - 3007/m Weft twist number - Untwisted warp density -
120 threads/in Weft density - 115 threads/in (1) Dyeing process: After scouring and heat setting in the usual manner, the following dyeing and reduction cleaning were performed.

(Dyeing) Acetic acid...0.2 g/L (Reduction washing) 8°0H...1 g/L After that, the fabric was washed with water, dried at a temperature of 120°C for 1 minute, and then dried at a temperature of 160°C for 1 minute. Heat treated.

Actual example 1 260de/36 spun at a spinning speed of 1000m/m
The fiber bundle of f i I is mixed with an oil component containing dioleyl adipate as a main component and bunacol E as an epoxy compound.
A treatment agent containing X512 (manufactured by Nagase Kasei) at a ratio of 20780 was applied as a 10% emulsion. The amount of treatment agent applied at this time was 0.3% as an active ingredient amount based on the weight of the fibers. Also, the Δna of the fiber at this time is 0.
It was 003.

This fiber was further hot-stretched at 120°C to 75 de/
A drawn yarn of 36 fil was obtained. A processing agent (viscosity: 30°C
20C3t) was applied to the fiber in an amount of 0.5% based on the weight of the fiber, and the fiber was rolled up.

This fiber was further left as a wound package in an atmosphere at 60° C. for 2 days to complete the reaction between the epoxy compound and the amino-modified silicone compound.

The fibers thus obtained were subjected to the above-described weaving and dyeing process to obtain a black dyed fabric. The water resistance durability of this fabric was evaluated.

Comparative Example 1 In Example 1, no epoxy component was used as a treatment agent for the spun yarn, and only an oil component was added to the fiber weight.
．． The water repellency of the dyed fabric was evaluated in the same manner as in Example 1, except that 5% of the dyed fabric was applied and then rolled up without applying anything after stretching.

Comparative Example 2 Drawn yarn obtained in Comparative Example 1 (Δna=0.14)
Bunacol EX512 was added as an epoxy compound in an amount of 0.25% based on the fiber weight, and then an amino-modified silicone compound was added in the same manner as in Example 1 to evaluate the water resistance and durability of the dyed fabric.

Example 2 In Example 1, the spinning speed was changed to 4500 m/l 1 inch (undrawn)
A black dyed repair product was prepared in the same manner as in Example 1 except that Δn a =0.042, 98 de/36 fil).

Comparative Example 3 In Example 2, a comparative black-dyed fabric was obtained by the same treatment as in Comparative Example 1.

Comparative Example 4 The drawn yarn (Δn a = 0.93) obtained in Comparative Example 3 was
After applying the epoxy component and the amino silicone component under the conditions of Comparative Example 2, weaving and dyeing were performed to obtain a black dyed fiber.

The water challenge performance evaluation results of the polyester fibers obtained as described above are summarized in Machine 1 below.

Table 1 From this table, it can be seen that the yarn treated with epoxy at a low Δna has extremely high water resistance and durability;
It is clear that treatment systems for yarns with 0.08 or higher have some initial water resistance, but are inferior in durability.

Next, the /S value of the black dyed fabrics obtained in Example 1 and Comparative Example 1.2 was measured, and the results of evaluating the bathochromic properties are shown in Table 2.
Shown below.

It should be noted that the dyed product of Comparative Example 1 is expressed as an index, with /S being 100.

Table 2 From these results, it is clear that the fibers obtained according to the present invention not only have excellent durable water-resistant properties, but also excellent deep color development and durability.

Claims (1)

[Claims] An aliphatic polyepoxy compound having two or more epoxy groups in the molecule is added to a polyester fiber whose amorphous part has a birefringence index of 0.08 or less, and then hot-stretched and/or heat-treated,
A method for producing water-repellent polyester fibers with excellent durability, in which an amino-modified silicone compound is then added.