JPH02221461A - Soil-proofing spin-dyed yarn and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject spin-dyed yarn having excellent smoothness and a little fear of adsorption of soil by attaching in surviving of specific hydrophobic smoothing oil less than specific amount on the surface of spin-dyed yarn composed of thermoplastic fiber containing spin-dyeing pigment and spin- dyeing dye. CONSTITUTION:In production of spin-dyed yarn by subjecting a thermoplastic synthetic fiber-forming polymer containing spin-dyeing pigment and spin-dyeing dye to melt-spinning, applying an oil containing hydrophobic smoothing agent of solid at normal temperature as principal ingredient and subjecting to hot- drawing and/or drawing and crimping, said oil is evaporated by heat in said process, or water is applied to the yarn before winding to de-oil so as to make attached amount of said oil to be <=0.3wt.% to fiber weight and preferably further covered with fluorine compound to afford the aimed soil-proofing spin- dyed yarn with a slight attaching of dirt and small proceeding of soil. Said yarn is suitable as spin-dyed yarn for carpet, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an antifouling dyed yarn, and more particularly to an antifouling dyed yarn that can prevent stains on woven and knitted fabrics, especially carpets. .

[Prior Art] Conventionally, inorganic pigments, organic pigments, organic dyes, etc. have been used in polyolefins such as polyamides and polypropylene,
Dye yarns blended with thermoplastic synthetic fibers such as polyester are widely used in industrial materials such as carpets, mats, car seats, artificial turf, uniforms, and general clothing. The reason for this is that the dyed yarn has excellent weather fastness and washing fastness, so it maintains the same color tone as after dyeing for a long period of time.

However, on the other hand, it has recently been discovered that products such as carpets made of dyed yarns have the disadvantage that they are easily contaminated with dirt, and stains progress quickly, resulting in darkening.

Furthermore, when a product becomes dark and dirty, even if it is washed, the dirt will soak in and be difficult to remove, and the color tone will change substantially. The benefits of threading had been halved. Conventionally, these causes have not been fully elucidated.

As a result of various studies to investigate the cause of this problem, the inventors of the present invention found that the oil adhering to the textile product adsorbs dust, oil, or water-based stains and promotes staining, resulting in stains in the fibers. It was determined that the change in color tone was caused by darkening. This is because in the case of products using spun-dyed yarn, there is generally no dyeing process, so the oil content in the oil agent is not washed away and remains in the product, and this oil content is unique to products made with spun-dyed yarn. It turned out to be a drawback.

However, in order to solve this problem, separately washing products made of spun-dyed yarn with water increases the cost and is not practical. In addition, since the spinning and drawing process of thermoplastic synthetic fibers is carried out at high speed, if no oil is added to the fibers, the fibers will become fluffy and drawn.Therefore, even if it is a spun-dyed yarn, adding an oil is not recommended. It is not possible to do so, and applying an oil agent is an essential requirement in the silk spinning process.

On the other hand, in recent years, in order to fully demonstrate the functionality of dyed yarns such as weather fastness and washing fastness, it has become necessary to have both durable water and oil repellency (so-called stain resistance). Became.

Conventionally, there have been two ways to impart stain resistance to carpets, mats, fabrics, etc., in post-processing, and in the yarn stage, but from the perspective of durability, A better method is to add (
JP-A-55-90677, JP-A-57-1717
60, JP-A-57-171761, JP-A-171762). In addition, one of the advantages of spun-dyed yarn is that the dyeing process can be omitted, but the highly durable yarn-applied antifouling agents disclosed in the above-mentioned patent application publications, etc., are available separately. Experiencing a washing, wet heating process, or dyeing process was an essential condition for developing its antifouling properties. This is due to the reasons mentioned above that if the product is made from dyed yarn without going through the washing process,
This is because hydrophilic or lipophilic oil adsorbs dirt and, due to its hydrophilicity or lipophilicity, greatly inhibits the water-repellent and oil-repellent functions of fluorine compounds.

In order to solve the above problems, the present inventor previously filed a patent application filed in 1983-29
No. 8841 and No. 63-298842 proposed controlling the oil content of spun-dyed yarn to 0.3% or less.

This has certainly greatly improved the problem of oil stains and the problem of inhibition of water and oil repellency when combined with fluorine compounds.

However, these low-oil content dyed yarns lack smoothness due to the low amount of attached oil, and have a high coefficient of friction during the post-process combing, knitting on a knitting machine, or tufting on a tufting machine. It was found that this method also had the disadvantage of poor operability.

[Problems to be Solved by the Invention] The object of the present invention is to solve the above-mentioned contradictory problems and provide a stain-resistant, spun-dyed yarn that has both excellent stain-proofing properties and processability.

[Means for Solving the Problems] The present invention provides: (1) In a dope-dyed yarn made of thermoplastic synthetic fiber containing a dope-dyed pigment and/or a dope-dyed dye, a hydrophobic substance that is solid at room temperature is provided on the surface of the fiber. Oil whose main component is a smoothing agent is
&Anti-fouling spun-dyed yarn characterized in that it is coated in an amount of 0.3% by weight or less based on miscellaneous weight; 3) When melt-spinning a thermoplastic synthetic w4N-forming polymer containing a dope-dyed pigment and/or a dope-dyed dye, applying an oil agent, and heat-stretching and/or stretching/crimping processing to produce a dope-dyed yarn, An oil agent containing a hydrophobic oil agent (smoothing agent) that is solid at room temperature is applied to the oil component, and the oil agent is volatilized and decomposed by the heat during the heating stretching and/or stretching/crimping processing, and/or is rolled up. By applying water beforehand to selectively remove oil components other than the hydrophobic smoothing agent, the oil component mainly containing the hydrophobic smoothing agent is removed.
A method for producing an antifouling dyed yarn, characterized in that the stain-resistant yarn remains in an amount of 0.3% by weight or less based on the weight of the fiber, and (4) forming a thermoplastic synthetic fiber containing a doped pigment and/or a doped dye. When producing spun-dyed yarn by melt spinning a polymer, applying an oil agent, and performing heating stretching and/or stretching/crimping processing, an oil agent containing a fluorine compound and a hydrophobic smoothing agent that is solid at room temperature is applied. , by volatilizing and decomposing the oil component except for the fluorine compound and the hydrophobic smoothing agent in the oil agent by the heat during the heating stretching and/or stretching/crimping process, and/or by adding water before winding. By selectively removing oil components other than the fluorine compounds and the hydrophobic smoothing agent in the oil agent, the oil containing the hydrophobic smoothing agent as a main component (but not containing fluorine compounds) is applied to the fiber surface. The purpose of the present invention is to provide a method for producing stain-proof dyed yarn, characterized in that the fluorine compound remains in an amount of 0.3% by weight or less and the fiber surface is coated with a fluorine compound.

The original pigments and/or the original dyes used in the original dyed yarn of the present invention include, for example, inorganic pigments such as carbon black, titanium dioxide, red iron, copper phthalocyanine green, perylene red.

Organic pigments such as polyazo red and azine yellow: Examples include organic dyes such as azo dyes, anthraquinone dyes, and perinone dyes.

The content of these dope-dyed pigments and/or dope-dyed dyes in the dope-dyed yarn is not particularly limited, but is usually an amount that provides a practically sufficient color density, such as 0.01 to 3.0. % by weight, preferably about 0.05 to 2.0% by weight.

In addition, the constituent fibers of the dope-dyed yarn or the dope-dyed pigment and/or
Or, in order to improve the weather resistance of the doped dye, in addition to the above doped components, 50 ppm of a copper compound such as copper iodide is added.
As mentioned above, it is preferable to add about 100 to 1,000 ppm.

The thermoplastic synthetic fibers constituting the dyed yarn include nylon 6, nylon 6.6. Nylon 12° Nylon 4
, 6 and other polyamides; polyethylene terephthalate,
Examples include polyesters such as polybutylene terephthalate; polyolefins such as polyethylene and polypropylene; vinyl polymers such as polyvinyl chloride and polyacrylonitrile; and copolymers or blends thereof.

The stain-resistant, dope-dyed yarn of the present invention contains such a dope-dyed pigment and/or
Or, it is a hydrophobic oil that adheres to the fiber surface of spun-dyed yarn made of thermoplastic synthetic fiber containing spun-dyed dye.
The amount of oil mainly composed of a smoothing agent that is solid at room temperature (hereinafter referred to as a hydrophobic smoothing agent) is 0.3% by weight or less, and the fiber surface is coated with the fluorine compound. There is a big feature in this.

In general, the oil agent added to thermoplastic synthetic fibers such as polyamide, polyester, and polypropylene during the spinning process is usually a hydrophobic agent such as mineral oil, vegetable oil, animal oil, aliphatic hydrocarbon, or fatty acid ester to improve drawing properties. It consists of a surfactant (emulsifying component) to which hydrophilic ethylene oxide is added or has a polar terminal group, and a surfactant with an antistatic function.

These oil agents are necessary to maintain smoothness during stretching and suppress the occurrence of fuzz, and the amount of the oil applied is at least 0.3% by weight based on the weight of the fiber, preferably 0.3% by weight based on the weight of the fiber.
5% by weight or more is required.

Most of these oils are not decomposed or volatilized by the heat during heating, stretching, and crimping, but remain fixed as oil on the fiber surface. Therefore, this residual oil content exceeds at least 0.3% by weight, and usually 0.5 to 1.0% by weight.
In some cases, it reaches 1 to 2% by weight. Among these oil components, it has been found that hydrophilic surfactants adsorb water-based dirt and oil-based dirt, and when combined with dust, form extremely harmful dirt.

In addition, surfactants with large molecular weights due to long bonding of ethylene oxide groups tend to remain on the S cloth.
It has also been found that when remaining, this component adsorbs moisture and dirt, and is particularly likely to promote dirt. Also,
In the case of a hydrophobic smoothing agent, it was also found that it adsorbs oil-based stains and, as a result, adsorbs lumps, making it easy to stain.

However, a more detailed study reveals that among smoothing agents, so-called hydrophobic smoothing agents that are solid at room temperature (room temperature) remain solid even on products, so smoothing agents that are liquid It has been found that it is relatively difficult to adsorb dirt compared to other agents.

In other words, it can be inferred that a smoothing agent that is liquid in nature adsorbs surrounding dust and sticks to the fibers, whereas a solid smoothing agent is smooth, making it difficult for the dust to fall off and stick. be done.

In order to make a hydrophobic smoothing agent solid, it is generally best to increase its molecular weight to at least 500, for example, by lengthening the ethylene chain or introducing a benzene ring, but it is not possible to simply increase the molecular weight. It is meaningless, and it is important to increase the molecular weight with a hydrophobic group.

That is, if the molecular weight is increased by adding a hydrophilic group such as ethylene glycol, it tends to adsorb dirt more easily and does not satisfy the intended purpose.

By leaving a small amount of hydrophobic smoothing agent on the fiber surface in this way,
The smoothness improves, and the workability in post-processing (breakage and fluffing) improves, and the conventional drawbacks are greatly improved. Examples of such hydrophobic smoothing agents include stearyl stearate (
(molecular m = 550) and fatty acid esters having carbon number C = 18 or more.

In general, antistatic agents can be used in small amounts and have the effect of preventing dust from being attracted by static electricity.
It is preferable to have a small amount of OPU mixed in, and from the viewpoint of workability in the post-process, the minimum amount is necessary, that is, about 0.00% in OPU.
It has also been found that about 1% or less may remain in the final product.

From the above findings, the oil agent used for the spun-dyed yarn has its function until it is stretched, but after the stretching and crimping process, it decomposes and evaporates due to heat, leaving a part of the smoothing agent behind. , or require a combination of ingredients that are easily washed away with water.

For example, the heat treatment temperature for thermoplastic synthetic fibers is generally 180 to 190°C for nylon 6;
6 is 200 to 220°C, polyethylene terephthalate is 200 to 220°C, and polypropylene is 110 to 135°C, so oils other than hydrophobic smoothing agents are likely to decompose and volatilize at their respective heat treatment temperatures. It is necessary to select suitable oil components.

Among such oil agents, when the applied fiber is nylon 6, ethylene oxide adducts of caprylic alcohol ether and ethylene oxide adducts of lauryl alcohol are preferable as hydrophilic surfactants, and the number of carbon atoms in the alcohol is Those having a relatively low molecular weight of 10 to 12 and a low boiling point are suitable. In this case, if the number of carbon atoms in the alcohol is 9 or less, the emulsifying ability will be extremely low, while if it exceeds 13, it will remain on the surface of the nylon 6 fibers without volatilizing even after stretching and crimping, which is not preferable.

In addition, lipophilic smoothing agents other than hydrophobic smoothing agents that are solid at room temperature are preferably those with relatively low molecular weights because they volatilize with heat. For example, in the case of nylon 6, it is preferable to Mineral oil, preferably 30-50 seconds mineral oil is suitable.

Furthermore, in the case of a smoothing agent made of a fatty acid ester, a component that decomposes and volatilizes at a heat treatment temperature of 180 to 190°C may be selected depending on its molecular weight, introduction of double bonds, etc. in the case of nylon 6.

For example, in the case of nylon 6, examples of this fatty acid ester include butyl stearate, isopropyl palmitate, etc., which have a molecular weight of 500 or less, preferably 250 to 350.
It is good to have something of a certain degree.

In other words, by combining a hydrophobic smoothing agent with a high molecular weight and a smoothing agent with a relatively low molecular weight that easily evaporates during processing, smoothness is maintained due to a high amount of oil coating until stretching, and after processing, after the product is made. Mainly solid smoothing agents remain at room temperature with little influence, and other oils are volatilized and their residual level is reduced to zero.
．． By controlling the amount to 3% or less, it is possible to prevent the product from staining and maintain smoothness in post-processing. However, it goes without saying that even if a hydrophobic smoothing agent is solid at room temperature, it is undesirable in terms of staining if it adheres to the product in an amount exceeding 0.3%.

Above, the case of nylon 6 has been explained using a specific example, but nylon 6.6. Regarding polyester, polypropylene, etc., the type and molecular weight of the surfactant and smoothing agent may be appropriately selected using the processing temperature as a guide.

In addition, as another method for removing the oil agent, water is applied to the yarn after heating drawing or drawing/crimping processing, and then the yarn is cooled (for example, by immersion in water or sprayed with water). The oil applied during the spinning process may be removed by washing with water, or the oil may be removed in combination with the above thermal decomposition and volatilization.

To give an example of water application conditions when the thermoplastic synthetic fiber is nylon 6, approximately half of the amount of water is added to the fiber yarn in a buckled pile state during jet pressing processing, which is crimping processing. This can be achieved by spraying on.

Hydrophobic smoothing agents or hydrophobic solid smoothing agents at room temperature are easier to wash with water than hydrophilic oil agents.

Water washing is more suitable for controlling hydrophobic oils as they tend to remain selectively.

Thus, the stain-resistant spun-dyed yarn of the present invention has an oil content of 0.3% to 0.1% by weight of the final finishing oil based on the weight of the fiber, which is mainly composed of a hydrophobic smoothing agent that is solid at room temperature. It is necessary to control it to about %.

If more than 0.3% by weight of the oil content of the oil agent remains in the dyed yarn, the staining of the final product such as a carpet will increase significantly. From the standpoint of stain prevention, it is better that no oil remains at all, but from the standpoint of preventing static electricity and requiring smoothness in post-processing, it is better that some oil remains.

Therefore, it is necessary to set a certain amount of a surfactant (antistatic agent) and a hydrophobic smoothing agent that is solid at room temperature to remain on the fiber surface of the spun-dyed yarn, and the remaining amount of the oil is as follows: Preferably it is 0.1 to 0.3% by weight.

In the present invention, it is more preferable that the surface of the fiber is coated with a fluorine compound. Examples of the fluorine compound include the following general formula (I> or (II).
) Trimellitic acid-based fluorine compounds can be mentioned. Its properties include acrylate-based fluorine compounds that retain water.

Any material that exhibits oil repellency may be used.

([X(CF2)mW(CONH)nY]1)Z(C
=O))q-C>(CO2B)r(I) In the general formula (I> or (II), X is a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms, m is an integer of 2 to 26, n is O or 1, W and Y are an alkylene group, a cycloalkylene group or an alkyleneoxy group,
The total chain length consists of 2 to 26 carbon atoms, (
CF2) m and Y each contain at least 2 carbon atoms in the main chain, Z is an oxygen atom or a nitrogen atom, p is 1 when Z is an oxygen atom, and p is 2 when Z is a nitrogen atom. ,
B is cHzR', CH20H,t or CHOHCHz
Ro, where Ro is a hydrogen atom or a methyl group, or B is CH2CH(OH)CH2O, where Q is a halogen atom, a hydroxyl group or a nitrile group, and further B is CH2CH(OH) CH2OCH2CH(O)
-1) CH2O (where Q is the same as above)
, R is a hydrocarbon group having 1 to 14 carbon atoms, an aryl group or an aralkyl group, q and r are integers of at least 1, the total amount of which is 3, and X (CF2)III, W and Y are linear It is bibranched or cyclic, and the substituents in the above formula are the same or different.

Among the fluorine compounds represented by the general formula (I) or (II), trimellitic acid ester.

Pyromellitic acid ester and trimellitic acid and/or
or selected from the group of bis(diamide)/ester of pyromellitic acid, and the main chain of the fluorine compound group of the X(CFz)mW(CONH)nY group has 6 or more carbon atoms, and 4
Those containing at least 1 perfluorinated carbon atoms are preferred.

The means for applying the fluorine compound to the fibers is usually
Although it is preferable to incorporate it into a spinning oil together with oil components other than fluorine compounds, it can also be dissolved in an organic solvent such as acetone and used alone as a spinning oil. It may be applied separately with an oiling roller or the like before winding the strip. When the spinning oil contains a fluorine compound, the spinning oil may be an aqueous emulsion or a non-aqueous solvent.

Further, as a more preferable example of the present invention, the amount of the fluorine compound coated on the fiber surface is usually 0.05 to 2.0% by weight, preferably 0.1 to 2.0% by weight based on the fiber itself.
It is about 0.6% by weight, which is 50 to 2.0% in terms of fluorine atoms.
oooppm, preferably 200-1,2001) l)
It is about m.

The reason why it is preferred that fluorine compounds be attached to the fiber surface is that fluorine compounds repel water and oil and keep dirt away, which is preferable in terms of preventing stains on products. It is. However, even if a fluorine compound is attached, if the oil content conditions described above are not satisfied, the water repellency of the fluorine compound
Needless to say, the oil-repellent properties are significantly impaired and the stain-preventing effect cannot be achieved.

[Function/Effect] According to the present invention, since a hydrophobic component that is solid at room temperature is selectively attached as an oil agent to be left on the spun-dyed yarn, the concern about adsorption of dirt due to oil is greatly reduced, and at the same time, it can be easily removed in the subsequent process. Since sufficient smoothness is ensured, products of good quality can be obtained with excellent operability.

[Example] Hereinafter, the present invention will be described in more detail with reference to Examples.

The amounts of oil and fluorine compounds adhering to the fiber surface of the spun-dyed yarn, water repellency/oil repellency evaluation, and stain evaluation were measured as follows.

Oil content and fluorine Bulked contin bulky filament yarn of A material
uousFi +ament, hereinafter referred to as rBcFJ)
When producing BCF, first apply only water without applying oil and/or fluorine compound, roll it up accurately for 10 minutes, vacuum dry it to make the moisture content 0%, and let the weight of the BCF be Wo. . Next, an oil agent and/or a fluorine compound is applied, and the undrawn yarn before drawing and crimping is wound accurately for 10 minutes, and the drawn and crimped BCF is wound for 10 minutes, and each is vacuum-dried to remove moisture. After setting it to 0%, the respective weights W+ and W2 were measured, and OPU+ and 0PU2 of the undrawn yarn before drawing and crimping were determined.
is calculated using the formula below.

W+ Wa OPLI+ = X100 (%) W2 WO OPU2 = X100 (%) Next, the thread with the oil and/or fluorine compound attached (
BCF) at a constant IW3 is taken and stirred in pure water for 30 minutes to extract the oil with hot water (80°C).

Monomers and oligomers in the polymer are extracted together with this hot water, so after this extract is evaporated and dried, the residue is dissolved in cyclohexane, and the monomers are separated from the soluble (oil agent) and insoluble components. , oligomers), the cyclohexane in the cyclohexane solution is evaporated, the remaining oil W4 is measured, and the oil OPU:1 is measured using the following formula.

OPLI: ] = xlOO (%) Note that fluorine compounds do not substantially dissolve in hot water, but stick to the fiber surface, so they can be separated from oil and! 1tIf
Since the fluorine compound that is not fixed to 1 does not substantially exhibit the performance as a fluorine compound, its amount is ignored.

Further, as a simple method for removing oil, the oil may be extracted from the fibers using a Soxhlet extractor using a solvent of cyclohexane/isopropanol = 50150 (middle weight ratio) and then extracted in the same manner.

Using a 20 volume (V)% aqueous solution of urine water and isopropyl alcohol, drop one drop onto the sample and measure the time it takes for the water drop to disappear (
seconds) was measured.

According to Katsukomame AATCo 11B-1972, one drop of the following reagent was gently dropped onto the surface of a horizontally spread sample, and the state of penetration was determined after 3 minutes.

Judgment Reagent Surface tension (dyne/cm) 1st grade White mineral oil 32.8 (Nujol) 2nd grade 55v%735v% Nujol/29.
5'')-Hexane tertiary n-hexadecane 27,74th grade n
-Tetradecane 26.55th grade n-dodecane 25.46th grade n-decane
23.97 grade n-octane 21
．． 78 grade n-hebutane 20.0 Stain evaluation Stain evaluation is based on the JIS contamination gray level based on the level of dirt compared to a new product when the number of steps is 5,000 times while vacuum cleaning is performed once a day. Measurements were made according to the following five criteria using the scale as a guide.

Grade 5: No stains, no difference) Grade 4: Extremely small stains Grade 3: Medium stains: Grade 2 Large stains: Grade 1°: Extremely large stains Corminally processable 2 to 3 undyed BCFs are combined and used with an interlace nozzle. The workability of these yarns when mixed and colored and combed was evaluated using the following grades.

X: Difficult to process due to frequent thread breakage. Complete winding rate: 85% or less Δ; Although extreme yarn breakage did not occur, single yarn cracks and one fuzz occurrence were observed. The completion rate is poor at 85-95%.

O: Almost no fuzz was observed, and the completeness rate was 96% or higher, which was good.

◎: Complete turn rate of 99% or more.

Machining speed: soom/mtn Combing nozzle: The one shown in Fig. 1 of JP-A-63-152435. The thread guide hole is 2.0mmφ.

The liquid injection hole diameter is 5゜2mmφ, and the elliptical long axis of the thread guide hole is 9.3.
mn, short axis = 4.1nn Combing gle pressure crab 5. OKQ /cm2 G [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

Examples 1-2. Comparative Examples 1 to 3 A nylon 6 polymer with an intrinsic viscosity [η] = 1.34 was mixed with the following dyed pigment, and crimped by ordinary melt spinning, heating stretching, and jet pressing (Japanese Patent Publication No. 57-60
No. 45 (see Publication No. 45)) to produce a spun-dyed bulky filament yarn (bulked) made of polyamide multifilament.
Continuous Filament, hereinafter referred to as rBC
"F") was (qta.

Dissolved pigment A (white); titanium oxide - 0.5% by weight (concentration in the system), copper iodide = 500 ppm, potassium iodide =
2. oooppm Dye pigment B (brown); Red iron = 0.4 weight (6)%
(concentration in the system), copper phthalocyanine green = 0.1% by weight (concentration in the system), carbon black = 0.2% by weight (concentration in the system), copper iodide = 500ppm, potassium iodide = 2.000ppm where , the spinneret used for spinning has a trilobal cross section of 6
It consisted of 8 holes, and the discharge m was adjusted so that the final drawn BCF denier from this die was 1,250 denier, and the discharge was 300 Mm1n. The temperature of the polymer at the time of discharge was 245°C. Before stretching, various spinning oils shown in Table 1 were applied using two stages of oiling rollers, and then the polymer was stretched by 3.5 times, and then heated to zero with a hot roller at 190°C. After heating for 1 second, it was introduced into a jet indentation nozzle and crimped.

At that time, superheated steam heated to 210''C and at a pressure of 6.0 Kg/Cff12 was used as the diet fluid.

In addition, in some cases, water was sprayed on the accumulated yarn during the jet indentation process to cool it and remove the oil at the same time as the weight of the device, and the yarn was wound to obtain BCF. .

The two spun-dyed BCFs of white and brown made of 1,250 denier/68 filaments thus obtained were mixed and blended using an interlace nozzle, and a 2,500 denier/136 filament colloid was produced. ~ Mingle yarn is used to create a tufted carpet with a basis weight of 600M using a 1/1゜gauge tufting machine, and it is laid on the floor without washing with water or dyeing to remove dirt caused by walking. The degree of

Examples 3-4. Comparative Examples 4 to 6 A fluorine compound was added to Example 1 to see its effect. As the fluorine compound, a mixture of pyromellitic acid esters (III) (IV) (V) shown below was used.

*1) The following pyromellitic acid ester (■).

Mixture of (IV) and (V) 0zRf 0zRf O2Rf From the results in Tables 1 and 2 above, in Examples 1 and 2 using the smoothing agent stearyl stearate, which is solid at room temperature, there was no erosion effect. When machining a certain combing gle, it was smooth, the generation of static electricity was fair, and there was little fuzz generation due to friction, showing fair machining stability.

In addition, since it is a solid smoothing agent, the quality of stains and the like was less compared to liquid smoothing agents.

On the other hand, even with the same oil agent, in Comparative Example 1, in which a large amount of oil agent was applied without washing with water during the crimping process, staining was not good. In addition, in Comparative Examples 2 and 3 using butyl stearate, which is liquid at room temperature and has a small molecular weight, the oil agent volatilized during the crimping process and fell off when washed with water, resulting in a low oil content, and the film strength of the oil agent itself was Because the material was weak, the smoothness during combing processing was poor, fuzzing was likely to occur due to friction, and processing stability was not improved.

On the other hand, as shown in Table 2, adding a fluorine compound to the grains added water and oil repellency, making it more difficult to get dirty, which was a favorable direction. Only the one using the smoothing agent stearyl stearate was able to be stably processed by combing, and the one using butyl stearate, which is liquid at room temperature, had poor combing processability. Furthermore, even when using stearyl stearate, if a large amount of oil content of 0.4% or more is applied, the water and oil repellency decreases, and the effect of the fluorine agent cannot be exhibited, and at the same time, there is a lot of staining.

Claims (4)

[Claims] (1) In a dope-dyed yarn made of thermoplastic synthetic fiber containing dope-dyed pigments and/or dope-dyed dyes, an oil component whose main component is a hydrophobic smoothing agent that is solid at room temperature is present on the fiber surface relative to the weight of the fiber. An antifouling, dope-dyed yarn characterized by having less than 0.3% by weight of . (2) The antifouling dyed yarn according to claim 1, wherein the fiber surface is further coated with a fluorine compound. (3) Melt-spinning a thermoplastic synthetic fiber-forming polymer containing a dope-dyed pigment and/or a dope-dyed dye, applying an oil agent, and heat-drawing and/or stretching/crimping processing to produce a dope-dyed yarn. , an oil agent containing a hydrophobic oil agent (smoothing agent) that is solid at room temperature is applied as the oil component, and the oil agent is volatilized by the heat during the heating stretching and/or stretching/crimping process.
By selectively removing oil components other than the hydrophobic smoothing agent by decomposing and/or applying water before winding, the oil component mainly composed of the hydrophobic smoothing agent is reduced by weight relative to the fiber. A method for producing stain-resistant dyed yarn, characterized in that it remains in an amount of 0.3% by weight or less. (4) Melt-spinning a thermoplastic synthetic fiber-forming polymer containing a dope-dyed pigment and/or a dope-dyed dye, applying an oil agent, and heat-drawing and/or stretching/crimping processing to produce a dope-dyed yarn. , an oil containing a fluorine compound and a hydrophobic smoothing agent that is solid at room temperature is applied, and the fluorine compound and the hydrophobic smoothing agent in the oil are removed by the heat during the heating stretching and/or stretching/crimping processing. By volatilizing and decomposing the components and/or adding water before winding, the fluorine compounds in the oil agent and the oil components other than the hydrophobic smoothing agent are selectively removed, and the hydrophobic smoothing agent is applied to the fiber surface. An antifouling material characterized in that an oil component whose main component is a smoothing agent (but does not contain a fluorine compound) remains in an amount of 0.3% by weight or less based on the weight of the fiber, and the surface of the fiber is coated with a fluorine compound. Method of manufacturing yarn.