JPH02145815A - Stain-proofing mass-colored yarn and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject yarn giving a stain-resistant carpet having excellent stain-proofing property without using a water-washing process and dyeing process by removing an oil component of a lubricant other than fluorine compounds from the surface of a fiber using a specific means. CONSTITUTION:A lubricant composed solely of a fluorine compound is applied to a yarn produced by the melt-spinning of a polymer forming a thermoplastic synthetic fiber and containing mass-coloring pigment and/or mass-coloring dye. The yarn is subjected to hot-drawing and/or drawing and crimping treatment. As an alternative method, the fiber is applied with a lubricant containing a fluorine compound and the oil components other than the fluorine compound are evaporated or decomposed by the heat of hot-drawing and/or drawing and crimping treatment and/or the oil components in the lubricant other than the fluorine compound are removed by applying water to the fiber before winding. The amount of the oil component other than the fluorine compound and attached to the surface of the fiber is <=0.3wt.% and the surface of the objective fiber produced by the above process has a coating layer of the fluorine compound.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a stain-resistant spun-dyed yarn, and more particularly to a stain-proof spong-dyed yarn that can prevent stains on woven and knitted fabrics, especially crabbed. Regarding.

[Conventional technology]

Traditionally, inorganic pigments, organic pigments, or organic dyes have been used in polyolefins such as polyamides and polypropylene,
Dye yarns blended with thermoplastic synthetic fibers such as polyester are widely used in carpets, mats, car seats, artificial turf, graduation materials such as 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 new forever.

However, on the other hand, it has been found that products such as carpets made of dyed yarns have the disadvantage of being easily contaminated with dirt (and becoming dirty and darkening quickly).

In addition, when a product becomes dark and dirty, it is difficult to remove the stain even after washing (it is difficult to remove the stain). The benefits of threading were halved.The cause of this had not been fully elucidated until now.

The present inventors investigated the cause of this problem and found that the oil adhering to textile products adsorbs dirt, oil, or water-based stains and accelerates staining, and as a result, it soaks into the fibers and causes a change in color as darkening. It was found that this caused The reason for this is that in the case of products using dyed yarns, 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 a drawback peculiar to products made with dyed yarns. It turned out that this was the case.

However, in order to solve this problem, if the product made of spun-dyed yarn is washed separately with water, the cost will increase and it is not actually economical. In addition, since the spinning and drawing process of thermoplastic synthetic fibers is carried out at high speed, the fibers will become fluffy and cannot be stretched unless an oil agent is applied to them. cannot,
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 repellency and 6 oil properties (so-called stain resistance). It became so.

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-57-171762). 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. The conditions for developing the antifouling property were to undergo a washing, wet heating process, or dyeing process. This is because if the dyed yarn is made into a product without going through the water washing process, the hydrophilic or lipophilic oil will adsorb dirt for the reasons mentioned above, and due to its hydrophilic and lipophilic properties, Water repellency due to fluorine compounds,
This is because it greatly inhibits the expression of oil repellent function.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned problems of the prior art, and has stain resistance (durable water and oil repellency) without washing with water or dyeing processes, and has fastness to weathering and washing. The purpose of the present invention is to provide a spun-dyed yarn with excellent stain resistance, which enables the production of final products such as carpets with excellent stain resistance.

[Means to solve the problem]

The present invention deals with the use of a dope-dyed yarn made of thermoplastic synthetic fibers containing dope-dyed pigments and/or dope-dyed dyes. The purpose of the present invention is to provide an antifouling spun-dyed yarn characterized in that the content of the fluorine compound is 0.3% by weight or less, and the fiber surface is coated with a fluorine compound.

In addition, the present invention involves melt-spinning a thermoplastic synthetic fiber-forming polymer containing a dope-dyed pigment and/or a dope-dyed dye, applying an oil agent, and subjecting it to heat-drawing and/or drawing/single-shrunk processing to make a dope-dyed yarn. When producing the above-mentioned heat-stretching and/or
Alternatively, the oil content other than fluorine compounds in the oil agent may be volatilized and decomposed by the heat during stretching and crimping, and/or the oil content other than fluorine compounds in the oil agent may be removed by adding water before winding. Provided is a method for producing stain-resistant spun-dyed yarn, characterized in that the oil content other than fluorine compounds in the oil adhering to the fiber surface is 0.3% by weight or less, and the fiber surface is coated with the fluorine compound. It is something to do.

Examples of the dope-dyed pigments and/or dope-dyed dyes used in the dope-dyed yarn of the present invention include inorganic pigments such as carbon black, titanium dioxide, and red iron; copper phthalocyanine green, perylene red, polyazo red, azine yellow, etc. Organic pigments 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 in an amount that provides a practically sufficient color density, for example, 0.01-3. O
%, preferably about 0.605 to 2.0% by weight.

In addition, in order to improve the weather resistance of the fiber itself of the spun-dyed yarn or the spun-dyed pigment and/or spun-dyed dye, a copper compound such as copper iodide is added in an amount of 50 ppm or more, preferably 100 to 1, in addition to the spun-dyed components. It is preferable to add about .000 ppm.

In addition, the thermoplastic synthetic fibers constituting the dyed yarn include nylon 6, nylon 6.6, nylon 12, and nylon 4.
．． Polyamide such as 6; 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, the content of oil other than fluorine compounds in the oil adhering to the fiber surface of a spun-dyed yarn made of thermoplastic synthetic fibers containing a spongy dye is 0.3% by weight or less, and the fluorine compound A major feature is that it is coated with

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 or crimping, but remain fixed as oil on the fiber surface. Therefore, this residual oil content exceeds at least 0.3% by weight, and usually 0.5-1. It reaches 0% by weight, and in some cases reaches 1 to 2% by weight.

Among these oil components, hydrophilic surfactants are
It has been found that water-based stains and oil-based stains are adsorbed, and when combined with dust, they form extremely harmful stains. In addition, surfactants with large molecular weights due to long bonding of ethylene oxide groups tend to remain in fibers, and if they remain, these components will absorb water and dust, especially dirt. It was also found that it is easy to encourage In addition, in the case of hydrophobic smoothing agents, they can absorb oil-based stains,
As a result, it was found that it was easy to get dirty by adsorbing lumps.

This tendency shows that the larger the molecular weight, the easier it is to stain.

Furthermore, antistatic agents can be used in small quantities and have the effect of preventing dust from being attracted by static electricity.
It has been found that it is preferable that a small amount of it be present, and that it may remain in the final product to the minimum extent necessary from the viewpoint of workability in subsequent steps.

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, or easily flows out when washed with water. It requires a combination of ingredients that results in

For example, the heat treatment temperature for thermoplastic synthetic fibers is generally 180 to 190°C for nylon 6;
．． In the case of No. 6, the temperature is 200 to 220°C, in the case of polyethylene terephthalate, the temperature is 200 to 220°C, and in the case of polypropylene, it is 110 to 135°C. need to be selected.

As such an oil agent, one containing a hydrophilic surfactant and a lipophilic smoothing agent is preferable.

As this hydrophilic surfactant, for example, when the fiber to be applied is nylon 6, an ethylene oxide adduct of caprylic alcohol ether or an ethylene oxide adduct of lauryl alcohol is preferable, and a comparative example where the alcohol has 10 to 12 carbon atoms is preferred. Those with low molecular weight and 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, the nylon 6
It is undesirable because it remains on the surface of the fiber without volatilizing even after stretching and crimping.

Furthermore, the lipophilic smoothing agent preferably has a relatively low molecular weight in order to be volatilized by heat. For example, in the case of nylon 6, mineral oil,
Preferably mineral oil for 30-50 seconds is suitable. If the viscosity of the mineral oil exceeds 60 seconds, it will not volatilize during drawing or crimping and will remain in the fibers, which is undesirable, and if it is less than 30 seconds, the smoothness will decrease, which is undesirable.

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.

As the fatty acid ester, for example, in the case of nylon 6, butyl stearate, isopropyl palmitate, etc. have a molecular weight of 500 or less, preferably 250 to 350.
Moderately good.

Above, a specific example was given for nylon 6, but for nylon 6.6, polyester, polypropylene, etc., the type and molecular weight of the surfactant and smoothing agent may be selected as appropriate, using the above 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, for example, immersing it in water or cooling it by spraying water. The oil applied in the process may be removed by washing with water, or the oil may be removed in combination with the thermal decomposition and volatilization.

To give an example of water application conditions when the thermoplastic synthetic fiber is nylon 6, approximately the same amount of water as the fiber is blown onto the fiber yarn in a buckled pile state during jet pressing processing, which is crimping processing. This can be achieved by attaching.

Thus, in the soil-resistant spun-dyed yarn of the present invention, the oil content of the final finishing oil must be 0.3% by weight or less, preferably 0.1% by weight or less, based on the weight of the fiber. For undyed yarn,
If the oil content of the oil agent remains in excess of 0.3% by weight, 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 preferable to set a certain amount of a surfactant (antistatic agent) and a hydrophobic smoothing agent so that they remain on the fiber surface of the spun-dyed yarn, and the remaining amount of the oil is preferably 0.1% by weight. % or less.

In the present invention, the fiber surface is further coated with a fluorine compound, and examples of the fluorine compound include fluorine compounds represented by the following general formula ('I) or (II).

・ ・ ・ ・ (1) ・ ・ ・ ・ (If) [In the general formula (1,) or (If), X is a fluorine atom or a perfluoroalkoxy group having 1 to 6 carbon atoms, and m is an integer of 2 to 26 , n is 0 or 1, W and Y are alkylene groups, cycloalkylene groups, or alkyleneoxy groups, the total chain length of which consists of 2 to 26 carbon atoms, (CF2), and Y are each in the main chain. contains at least 2 carbon atoms, Z is an oxygen atom or a nitrogen atom, p is 1 when Z is an oxygen atom, P is 2 when Z is a nitrogen atom, and B is CH2R' CHOH, or CH2R 'Cl
-10) 1cI(2R' CHOH, where R' is a hydrogen atom or a methyl group, or B is CH2C1((O
f()CH2O, where Q is a halogen atom, hydroxyl group or nitrile group, and B is C)12C)I (
OH)CH2QC)12CF((OH)CH2O, where Q is within the above range, R is a hydrocarbon group having 1 to 14 carbon atoms, an aryl group or an aralkyl group, q and r are an integer of at least 1, The total amount is 3, and X(CF
2), , W and Y are straight chain rods, branched or cyclic, and the substituents in the above formulas are the same or different. ]Among the fluorine compounds represented by the general formula (1) or , x(ct'
2) The main chain of the fluorine compound group of W(CONH) and Y group preferably has 6 or more carbon atoms and contains 4 or more perfluorinated carbon atoms in the group.

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 up the strip. When the spinning oil contains a fluorine compound, the spinning oil may be an aqueous emulsion or a non-aqueous solvent.

In addition, in the present invention, it is sufficient that at least the surface of the fibers constituting the spun-dyed yarn is coated with a fluorine compound, but the amount of the fluorine compound attached is usually 0.05 to 2.0 with respect to the fiber itself.
% by weight, preferably about 0.1 to 0.6% by weight,
The amount is about 50 to 2,000 ppm, preferably about 200 to 1,200 ppm in terms of fluorine yarn.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

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

and Bulked Contin bulky filament yarn.
When manufacturing a bulk filament (hereinafter referred to as rBCF), first apply only water without applying an oil agent and/or a fluorine compound, roll it up accurately for 10 minutes, vacuum dry it to make the moisture content 0%, and then Let the weight of 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. is set to 0%, and from the measured values of the respective weights W, , and W, the OPU and OPU of the undrawn yarn before drawing and crimping are calculated from the following formula.

Next, threads with oil and/or fluorine compounds attached (
Take a certain amount W of BCF), stir in pure water for 30 minutes, and extract the oil with hot water (80°C).

Monomers and oligomers in the polymer are extracted together with this hot water, so after evaporating and drying this extract, the residue is dissolved in cyclohexane and the soluble components (oil agent) are extracted.
and insoluble components (monomers, oligomers, etc.), volatilize the cyclohexane in the cyclohexane solution, weigh the remaining oil w4, and calculate the oil 0PU3 using the following formula.

Note that fluorine compounds do not substantially dissolve in hot water.
．． Since the fluorine compound is fixed to the fiber surface, it can be separated from the oil, and since the fluorine compound that is not fixed to the fiber does not substantially exhibit its performance as a fluorine compound, its amount is ignored.

■Using a 20 volume (V)% aqueous solution of isopropyl alcohol, drop one drop onto the sample and time (seconds) until the water drop disappears.
was measured.

(1) In accordance with AATCC11B-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/c
111 grade white mineral oil 32.8 (Nujol) 2nd grade 55V%/35v% Nujol/29.5
n-hexane tertiary n-hexadecane 27.74th grade n-
Tetradecane 26,55 class n-dodecane
25.46 class n-decane
23.97 grade n-octane 21.78
Class n-hebutane 20.0 Soil Standard pressure 5 stain evaluation is based on the JIS contamination rating based on the degree of contamination when the number of steps is 5,000 times compared to a new product while vacuum cleaning is performed once a day. Measurements were made using the gray scale as a guide and the following five criteria.

Grade 5: No stains, no difference) Grade 4: Extremely small stains Grade 3; Medium stains Grade 2; Large stains Grade 1; Extremely large stains Examples 1 to 4, Comparative Example 1 Intrinsic viscosity [η) = 1.34 nylon 6 polymer, 0.7% by weight of copper phthalocyanine green and 0.1% by weight of carbon black (total content in the system is 0.8% by weight)
, and 0.1% by weight of copper iodide were mixed and subjected to the usual melt spinning, heating stretching, and jet pressing crimping process (see Japanese Patent Publication No. 57-6045) to obtain a spun-dyed bulky material made of polyamide multifilament. Filament thread (B
ulkedContinuous Filament
SBCF) was obtained.

Here, the spinneret used for spinning had a trilobal cross section of 6
It consisted of 8 holes, and the discharge amount was adjusted so that the final drawn BCF denier from this die was 1,250 denier. The temperature of the polymer at the time of discharge was 245°C, and before stretching, various spinning oils shown in Table 1 were applied using two stages of oiling rollers, and then the polymer was stretched 3.5 times to 190°C.
After heating with a hot roller at °C for 0.1 seconds, it was introduced into a jet pressing nozzle and crimped.

At that time, the jet gas was heated to 210°C.
, superheated steam at a pressure of 0 kgloil G was used.

Table 2 shows the results of the water repellency, oil repellency, and stain evaluation of the fabric woven using the spun-dyed BCF composed of 1,250 denier/68 filaments thus obtained.

As is clear from Tables 1 and 2, oil agents ■ and ■ containing only fluorine compounds or hydrophobic components are
Even untreated gray fabric that does not go through the washing or moist heating process does not absorb dirt and exhibits clear water and oil repellency. Although they are hydrophilic components, oils ■ and ■ containing caprylic alcohol polyethylene oxide adducts or lauryl alcohol polyethylene oxide adducts, which are volatile at low temperatures, are both slightly inferior to oils I and ■, but untreated. It exhibits sufficient water and oil properties even on gray fabric. However, in oil agent V containing hydrophilic components, the residual oil content (BC
It can be seen that the oil adhesion amount of F exceeds 0.3% by weight, indicating that the untreated gray fabric is inferior in clear water and oil repellency.

Table 1 *1) The following pyromellitic acid esters (II[), (I
Mixture of V) and (V) [Effects of the Invention] According to the present invention, a highly functional spun-dyed yarn with excellent weather fastness and washing fastness, as well as durable water and oil repellency is obtained. , it can be produced without washing or dyeing processes, and its industrial significance is extremely large.

Claims (2)

[Claims] (1) In a dope-dyed yarn made of thermoplastic synthetic fiber containing dope-dyed pigments and/or dope-dyed dyes, the oil content of the oil agent excluding fluorine compounds attached to the fiber surface is 0.3% by weight.
An antifouling spun-dyed yarn having the following properties and having a fiber surface coated with a fluorine compound. (2) 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-stretching and/or stretching/crimping processing to produce a dope-dyed yarn. In the case where an oil agent consisting only of a fluorine compound is used as the oil agent, or an oil agent containing a fluorine compound is used, the above-mentioned heating stretching and/or stretching/stretching is performed.
The heat during the crimping process causes the oil content in the oil agent other than fluorine compounds to volatize and decompose, and/or by adding water before winding, the oil content other than fluorine compounds in the oil agent falls off, thus forming a fiber surface. A method for producing stain-resistant spun-dyed yarn, which comprises controlling the oil content other than the fluorine compound in the attached oil agent to 0.3% by weight or less, and coating the fiber surface with the fluorine compound.