JPS59163481A - Production of water and oil repellent acrylic fiber - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a water-repellent, rain-oil-repellent acrylic fiber. ” Conventionally, the method of imparting water and oil repellency to textile products is to apply a finishing agent mainly containing fluoro compounds to secondary products such as knitted fabrics or final products such as outerwear and hats by spraying or patching. It was common practice to process the product using the Ding/Drag 1 method to form a film of a processing agent on the surface of the product to lower the surface tension.

Although the products obtained by this method have excellent water and oil repellency in the initial stage, their durability is insufficient, for example, their wash resistance is poor, and their texture is poor. It was also stiff and quite rigid.

The reason for this is that in the case of a fabric treated by the above method, for example, the processing agent is attached to the surface of the fabric, but it also adheres to the inside of the threads that make up the inside of the fabric. This is one of the reasons why sufficient durability cannot be imparted.

To this end, attempts have been made to treat the raw cotton and yarn stages with such water-repellent compounds, but fibers treated with such compounds become stiff and stiff, and at the same time Adhesion between single fibers also occurs, and the smoothness between metal and fibers is extremely reduced.Furthermore, due to water repellency, static electricity is generated and the amount of charge increases, making it difficult to process spinning and knitting fabrics. At present, only products with very poor passability through the product processing process, such as 100% polyester, have been obtained and have not been put to practical use at all.

Therefore, the inventors of the present invention have conducted intensive studies to obtain an acrylic fiber product having excellent surface durability and water- and oil-repellent properties, and as a result, they have completed the present invention.

That is, the gist of the present invention is to combine a dyed acrylic fiber with a fluoroalkyl group-containing oil repellent and a polyamine-based cationic activator represented by the following general formula (with a Bl solid content ratio of A:B=1:0). .2 to 0.6. Further ((If necessary, add a polymeric cationic antistatic agent (C1 to
: 0.2-0.6: Immersion treatment at 40-80°C for at least 20 minutes or more in a solution containing 0.2-0.4 and a total solid content concentration of 0.2% or more in terms of fiber weight ratio. After.

Immediately before spinning, the acrylic fiber obtained by dry heat treatment at 100 to 130°C has a melting point of 10°C or lower and a boiling point of 28°C.
An oil agent whose main components are paraffin and a polyamine-based cation activator whose temperature is 0°C or less is 0.2 to 2.
It has water and oil repellency characterized by imparting zero weight coefficient.
This is a method for producing acrylic fiber.

In the formula, R is an alkyl group CnH,,n+1 and n is 15-2
52m is an integer from 5 to 20.

The present invention has no problems at all when passing through processing steps such as spinning, knitting, and weaving as described above.

This is a method for producing acrylic fibers having excellent water and oil repellency.
Ru.

The water- and oil-repellent film used in the present invention is a well-known fluoroalkyl film, and is not particularly limited.

For example, to give an example of the most important one, CF3 (CF2
)7(CH2)II OCOCH = CH2, CF
s (CF2,), CH2ococ(CH3)-CH
2, (CH3)2CF(CF2), O (CH2)3
0COCH=CH2.

( CFs) CF ( CF2)a CHz CH (
OCOCH3) OCOC ('-Hs)2CH2
Polymers of unsaturated esters represented by acrylates or methacrylates containing 3 to 20 carbon atoms, preferably 4 to 5 fluoroalkyl groups, or polymers containing such unsaturated esters and fluoroalkyl groups. Examples include copolymers with one or more compounds that can be used.

In this case, koge/vinylidene that does not contain a fluoroalkyl group (there are many polymerizable compounds, ethylene, vinyl acetate, vinyl fluoride, vinyl chloride, etc.) , acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, -r
y+) alkyl esters of methacrylic acid and its alkyl esters, acrylamide, methacrylamide, diacetone acrylamide, etc.

In the present invention, acrylic fibers are simply dyed with a water and oil repellent containing a fluoroalkyl group as described above, and then impregnated and dried (instead of a solution containing a certain amount of a polyamine-based cation/activator). At least 2% in a solution at 40-80°G with addition of a polymeric cationic antistatic agent.
After immersion treatment for 0 minutes or more, drying and heat treatment at a predetermined temperature, and immediately before spinning, the material has a melting point of 10°C or less and a boiling point of 28°C.
An oil agent whose main components are paraffin and a polyamine-based cationic activator that have a temperature of 0°C or lower, with a solid content of 0.2 to 2.0
Satisfactory water and oil repellency and processing process passability can only be achieved by adding a weight factor.

Acrylic fibers dyed in the present invention are immersed in a solution prepared by adding a polyamine cationic activator to the water-repellent earth-acid oil described in M, and further added with a polymer cationic yarn antistatic agent, and then subjected to a prescribed heat treatment. Kana 9 has excellent water and oil repellency. However, there is a problem in that some troubles such as static electricity occur in processing properties such as spinning, so a specific oil agent consisting of the above-mentioned main components is applied immediately before spinning.

The processability, especially the smoothness during spinning, is improved, the amount of static electricity generated is drastically reduced, and the water and oil repellency is maintained at the same time. This can be said to be a temporary method. In the present invention, the reason for treating acrylic fibers with a treatment solution containing a water and oil repellent (Al) containing a fluoroalkyl group-containing water and oil repellent (Al and a polyamine cationic activator (Bl) or a polymeric cationic yarn antistatic agent (C1) is originally The cationic group in the treatment liquid is bonded to an acidic group such as sulfonic acid or carboxylic acid, which is known as fluoroalkyl compound, and the cationic group in the treatment liquid is used to impart durability to the acrylic fiber of the fluoroalkyl compound.

As shown in formula (1) above, the polyamine cation activator used in the present invention must have a balance between hydrophobic components and hydrophilic components, and even the same polyamine cation activator cannot maintain this balance. Otherwise, the desired effect of the present invention cannot be obtained. That is, in the polyamine-based cationic activator used in the present invention, R in the above formula (1), that is, the alkyl group that is the hydrophobic component, is represented by the general formula CnH2n+1, where n is 15 to 25 and represents the amount of the hydrophilic component. m is 5
~20.

Textile products that have been treated to be water repellent generally have lower water absorption and hygroscopicity, and the amount of static electricity generated and electrostatic charge due to friction increases, resulting in poor passability through processing steps.

As a countermeasure, adding an antistatic agent containing ordinary polyethylene oxide or alkyl phosunate to the processing solution to remove static electricity may have some effect, but in many cases this is the intended purpose. Water and oil repellency properties are also often lost. Therefore, in the present invention, these problems are solved by adding a polymeric cationic antistatic agent at a certain ratio in order to simultaneously satisfy the desired properties of water and oil repellency and processability. ing. The addition ratio of water and oil repellents containing fluoroalkyl groups (AJ and polyamide/based cationic active MIJ (in the case of B+, A:B = 1:0, 2 to 0.6, and Cationic antistatic agent (when used together with C1 A:B:C=1:0.2-0.6:0.2-0.4
It is necessary that The reason is that the water and oil repellent (A
Naturally, if the addition ratio to 1 is small, the softness and smoothness or the electric shock effect will decrease, and if correspondence becomes too difficult, water and oil repellency, especially oil repellency, will decrease. Therefore, this addition ratio is important in order to obtain the desired performance and good processability.

Another important point in the treatment process of the present invention is the adhesion rate of the treatment agent to the fibers, and it is necessary to have a total solid content concentration of 0.2% or more by weight of the fibers. If this concentration is too low, the performance aimed at by the present invention cannot be obtained9, and the passability through processing steps will also be reduced.

On the other hand, if the concentration is extremely high, adhesion between single fibers will occur, resulting in a decrease in smoothness, that is, a decrease in workability, so 0.3
A range of 0.6% to 0.6% is a commonly used level. In order to carry out the above-mentioned treatment, according to the present invention, the substrate is immersed in a treatment solution at a temperature of 40 to 80° C. under suitable conditions at a bath ratio of 1:10 to 50, and treated for at least 20 minutes.

The reason for this is that in order to increase the affinity between fibers and the treatment agent, it is more advantageous to increase the temperature of the treatment bath and lengthen the treatment time than to immerse the fibers in a low-temperature bath for a short time.

However, if the temperature is too high, the emulsification stability of the treatment agent will decrease, so for industrial moxibustion, treatment at 40 to 80℃ for about 20 minutes is most preferable, and in order to obtain a uniform treatment effect, it is usually forced using a circulation bonder etc. Stirring etc. are carried out separately.

After the treatment, dehydration is performed, followed by drying and heat treatment at 100 to 130°C to complete the water and oil repellent treatment that has the level of performance required by the present invention, but if this temperature is low, a long treatment is required, and At high temperatures, problems such as yellowing occur.2 Usually, 5 to 10 minutes at 130°C is required.

The most important point of the present invention is to apply a specific oil agent to the water- and oil-repellent acrylic fiber treated by the method described above immediately before spinning.

This specific oil treatment method will be explained below.

Conventionally, in the case of wool spinning or semi-worsting methods in spinning, even the collection of ordinary acrylic fibers is sometimes treated with an oil spray (hereinafter referred to as lubricant) immediately before spinning in order to improve process passability.

However, such fibers that have been given water and oil repellency cannot be subjected to the conventional spinning and oil addition method as they are.

Tsume 9 Since it is endowed with water and oil repellency, it is difficult to apply it uniformly like with conventional fibers, and most of the oil repellents commonly used in the past are water repellent. Since the oil repellency is reduced, it is not possible to obtain a final product with the desired performance. Therefore, the present inventors conducted intensive studies to improve process passability, mainly spinnability, without reducing water and oil repellency, and found that paraffin, which has a melting point of 10°C or less and a boiling point of 280°C or less, has a carbon number of 15. It may contain the above-mentioned rough-in, but mainly has 10 to 15 carbon atoms, such as decane or pentadeca.
The amount of oil refueling agent mainly composed of Nogurafuin and polyamine cation activator is 0.2 to 2.0% in solid content.
We have found a way to give zero weight. The main components of the refueling agent used in the present invention are paraffin with a melting point of 10°C or lower and a boiling point of 280°C or lower, and a polyamine-based cationic activator. 9. It falls into the category of liquid paraffin. It is necessary to arbitrarily change the ratio of paraffin, polyamine-based cationic activator, etc. depending on the fibrillation properties, smoothness, etc. of the treated fibers.

Usually, a material with a high paraffin ratio of 7:3 is often used, with emphasis on smoothness.

Next, the adhesion amount of this refueling agent is 0.2 to 2.0 in terms of solid content.
It must be adhered within a weight percent range, but if the amount is too small, the spinnability cannot be expected to improve, and if it is too large, the water and oil repellency performance will be reduced, so it is preferably 0.4 to 0.6.
It is necessary to regulate the amount by weight%.

In Figure 1 (representative fluoroalkyl compounds), the aforementioned polyamine-based cationic activator (Bl) is added to Asahi Guard AG-310 (Kaisei Kagaku) at a ratio of A:B=1:
Approximately 0.3% of the oil additive that can be used in the present invention adheres to fibers that have been subjected to a prescribed heat treatment, and is attached to 10 d of acrylic fibers after dyeing with a treatment solution of 0.4%. Figure 2 also shows the smoothness between the fibers, which is a characteristic value for passability through the processing process, in terms of the drawing strength of the sliver of about 101'/m2. be. The adhesion rate of oil repellent has an extremely important effect on water and oil repellency and smoothness, and Figures 1 and 2 show improvements in smoothness within a range that does not reduce the desired water and oil repellency. In other words, in order to reduce the pulling force, 0
．． This indicates that a deposition rate of 2 to 2.0% is required.

In the present invention, oil is added just before spinning, so the form of the acrylic fiber is raw cotton or tow.

Although it is assumed that the top etc. are used, there is no problem in treating this oil replenisher in the form of spun yarn or a product.

The spun yarn of acrylic fiber obtained by imparting water and oil repellency by the method of the present invention has antifouling properties. It is possible to obtain differentiated parts such as carpets and sweaters that have water-repellent properties.

The present invention will be explained below with reference to Examples.

Example 1 Bonnel (acrylic fiber manufactured by Mitsubishi Rayon Co., Ltd.) Prite 10d 102 to about 15! ,,Ordinary package dyeing was carried out under the following conditions.

Staining conditions C6I Ba5ic Blue -691, 5% owf
Acetic acid (40%) 1.0 Cateogen AN Super 1.5 (Daiichi Kogyo Seiyaku Co., Ltd.)
Cation/system active explosion 0 temperature x time 100℃
x 60 minutes Bath ratio 1:10 The above dyed raw cotton was washed and dehydrated, and the adhesion rate to the fibers was approximately 0.3 per fiber weight under each condition as shown in Table 1.
-%.

* Processing agent A: Asahi Guard AG-310 (Kaisei Chemical Co., Ltd.)
(manufactured by Sanyo Kasei Co., Ltd., fluoroalkyl group-containing water and oil repellent) B: A polyamine-based cationic activator in which the alkyl group rRJ in general formula (1) in the text has 18 carbon atoms and m is 8 (manufactured by Sanyo Kasei Co., Ltd. Finishing agent) *** Processing bath conditions Bath ratio...1:101k
! -Type package dyeing machine → dealkyl phosphate ester = 50/30/'201) Workability Card passing properties = (Good) ◎ - 〇 - △ - x - xx (Poor) Sliver drawing strength Crab card sliver - Approx. 10. The drawing strength of P/7n was measured using a 70-ton tensile strength for 20 pieces, and the average value was shown.

(Test length - 1,1 x fiber length 9 2) Appearance performance Water repellency: Conforms to DuPont method water repellency performance measurement requirements (Good) 5th grade to 1st grade (Poor) Oil repellency: 'AATCC method oil repellency performance measurement Conforms to conditions (good) Grade 8 to Grade 1 (poor) Based on the method of the present invention from Table 1 < Nu 5 and East 140
Under the conditions, good results were obtained in both processability and water and oil repellency. However, the conditions of N1111 to 4 are comparative examples where the content of water and oil repellent is very high or when treated alone, and although the water and oil repellency is excellent, the processability is poor and practical application is difficult. .

(2) Comparative Examples 6 to 13 had good workability, almost close to the current oil conditions of Slow 15, but only poor water and oil repellency, especially oil repellency, was obtained.

Example 2 A 480,000 total denier tow of 7K 7 Nellfly) 3d was package dyed under the following conditions.

C,I Ba5ic Red-232%Ow facetic acid (
40%) 1 Cationogen AN Super 2 Temperature x Time
100'CX60 minute bath ratio
1:10 The dyed tow was washed and dehydrated and treated in the same manner as in Example 1 under the conditions shown in Table 2 below. The temperature of the treatment bath at this time was 70'C.
Heat treatment after dehydration for 20 minutes at a bath ratio of 1 to 0.
It was carried out for 30'CX10 minutes.

Then, this treated tow was canted to a fiber length of 64 nm, added oil immediately before spinning, and spun into yarn with a count of 30 meters using a wool spinning method. Next, the results of making moquettes for chair upholstery using this woolen yarn are shown in Table 2. 1IvL3 and N7 made by the method of the present invention had good processability, and the resulting products were water and oil repellent. Performance has a high standard to aim for,
In addition, a moquette for chair upholstery with a good texture could be obtained. Furthermore, compared to N3, N7 had improved workability due to the addition of an antistatic agent, but its oil repellency was slightly lower. In addition, Arashi 1, a comparative example, had a low adhesion rate and poor workability, and the performance of the inferior product was also low, while NQ2 and %6 had good product performance but poor workability. Furthermore, Na4. Arashi 5+
and Qi 8 had excellent processability equivalent to that under the current conditions described in 9, but the water and oil repellency of the product was considerably inferior.

1) Water and oil repellent treatment conditions (a) Treatment agent A: Asahi Guard AG740 (manufactured by Meisei Chemical, water and oil repellent containing fluoroalkyl group) B: Polyamine-based cationic activator (same product as Example 1) C: High Molecular cationic antistatic agent *Taflon 320A: Dai-Kogyo Seiyaku Co., Ltd. Cationic softener (b) Adhesion rate: Bath concentration before and after treatment (60°C under reduced pressure
Calculate the adhesion rate from the solid content 9 difference after 4 hours drying vx (c and knee (y, □0゜■ = total amount of treatment bath < 1) - = 01: Rice temperature concentration of treatment bath (P/l) C2 : Bath concentration after treatment (P/l) F; Treated fiber Fuki (i) 2) Addition treatment conditions (a) Addition agent: Same product as addition oil agent C in Example 1 (b) Supply Amount: The amount supplied by one spray method is expressed as the solid content concentration (%) of 1 fiber.3) Workability Antistatic property: Antistatic effect during processing process (good 90-〇 - 1 × (Poor) Spinability: Wool spinning process stability (Good ◎ - 0 - 1 × (Poor weavability: Moquette greige weaving process stability (Good ◎ - 0 - 1 × (Poor 4) product Water and oil repellency is based on Example 1 Texture: Flexibility (Good) ◎-〇-△-× (Poor)

[Brief explanation of drawings]

Figure 1 shows 10 acrylic fibers after dyeing at a ratio A:B=1:0.4 of the polyamine-based cationic activator tBl, which is described in detail in the text, to the fluoroalkyl group-containing water and oil repellent + AJ.
d shows the relationship between the amount of oil repellent applied in the present invention and water repellency and oil repellency on raw cotton with approximately 0.3% adhesion. The water repellency was measured using the DuPont method, and the oil repellency was measured based on the AATCC method. Figure 2 also shows the relationship between the interfiber smoothness and the amount of lubricant applied to a card sliver (approximately 1017 m).
This is shown in terms of the pull-out strength. Procedural amendment 1゜July 1983/G) 12゜3゜Special J-I “Chief of the Agency Mr. Kazuhiro Wakasugi 4゜1, Patent Application No. 58-35549 showing the case 2, name of the invention Process for producing acrylic fibers with water and oil repellency 3, relationship with the case of the person making the amendment Patent applicant: Kyobashi 2-cho, Chuo-ku, Tokyo "l 3 Total 1.95:: (60
3) Mitsubishi Rayon Co., Ltd. ji'ZFH12L:', i Mi Kawasaki Kodai 4, Agent Kyo + 1G 2-chome, Chuo-ku, Tokyo [-13-19''; Specification subject to voluntary amendment 7, Contents of amendment 4th line, 7th line] Oil repellent” → “Water and oil repellent” 17th line 1 line “Meiho Kagaku” → 1 Asahi Glass” 20th page, 12th line “8th wa” → 4th line 8th”

Claims (2)

[Claims] (1) Dyed acrylic fibers are coated with a fluoroalkyl group-containing water and oil repellent (A+) and a polyamine-based cationic activator represented by formula (1) (Bl in terms of solid content ratio of A:B=l:0.
2 to 0.6 and the total solid concentration! Immediately before spinning the acrylic fiber obtained by soaking it at 40 to 80°C for at least 20 minutes in a solution containing 0.2% or more of aKr41 by weight and heat-treating it with dry heat at 100 to 130°C, the melting point A water repellent characterized by applying an oil agent whose main components are paraffin having a temperature of 10'C or less and a boiling point of 280C or less and a polyamine cation activator in an amount of 0.2 to 2.0% by weight in terms of solid content. A method for producing oil-repellent acrylic fiber. In the formula, R is an alkyl group CnH21+1 and n is 15 to 25
2m is an integer from 5 to 2o. (2) Fluoroalkyl group-containing water and oil repellent (A),
Polyamine-based cationic activator (Bl-containing solution containing polymeric cationic antistatic agent (C1 in solid content equivalent ratio A)
:B:C=1:0.2~0.6:0
．． 2. The method according to claim 1, wherein the amount is added to be 2 to 0.4.