JPS59130374A - Water and oil repellent fiber product and production thereof - 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 water- and oil-repellent textile product with significantly improved washing resistance and dry cleaning resistance, and a method for producing the same.

Conventionally, efforts have been made to improve the water repellency defects of textile products, whether synthetic or natural, and various proposals for improvement have been made. As a result, various types of fibers such as polyester and polyamide have been modified by applying water repellent treatments depending on the type of fiber.

For example, silicone-based water repellents and fluorine-based water repellents are applied in separate water-based and solvent-based processes, fluorine-based water repellents are applied and then protected with cross-linkable ethylene monomers, and polyurethane Techniques are known in which a water repellent agent is supported on a water repellent resin or an epoxy resin.

However, all of these techniques are ineffective in terms of washing resistance and dry cleaning resistance, and particularly cellulose fibers such as cotton and rayon have the drawback of being significantly inferior in durability. In terms of process, all of the above-mentioned conventional techniques include a process of treating with an organic solvent system, and in such a process, the treatment of dyed products causes dye elution and discoloration, which is a problem that must be avoided. There was also.

In view of these conventional drawbacks, the present invention was developed in order to stably provide high-performance water and oil repellency with excellent durability to mixed fiber products made of various fibers. By combining a film made of a compound with a functional group and a specific water/oil repellent, it simultaneously satisfies a high level of performance and durability for any fiber.
The present invention was achieved by investigating the fact that such properties can be stably imparted.

That is, the present invention has a first-order configuration.

(1) On the fiber surface, a fluorine-containing compound represented by the following general formula A water-repellent and oil-repellent fiber product characterized by containing and bonding.

R3 1 (wherein R5: hydrogen or lower alkyl group Rt: CF
Perfluoro m2m+< A group having a loalkyl group and containing at least one group selected from a hydroxyl group, an ester group, an ether group, an amino group, and an unsaturated group.

m: an integer from 2 to 21 n: an integer from 10 to 200) (2) A compound having both a monopolymerizable vinyl group and a condensable methylol group is brought into contact with the surface of the fiber f#, and reacted in the presence of moisture. 9. A method for producing a water- and oil-repellent textile product, which is then treated with a treatment liquid containing a fluorine-containing compound [■] and then heat-treated.

By adopting this technical configuration, polyester,
It is possible to modify not only synthetic fibers such as polyamide, but also various fiber products such as products made of mixed fibers such as cotton and rayon, into products that have excellent water and oil repellency regardless of their type, and are highly resistant. It dramatically improves washability and dry cleaning resistance, as well as texture (flexibility) and wrinkle resistance.

We were able to provide something extremely superior.

Furthermore, the method of the present invention may be either water-based or solvent-based, but
For example, when textile products are dyed, there is the advantage that the dyeing can be done consistently in an aqueous system.

The textile products referred to in the present invention include any fibers (including mixtures) such as natural fibers such as cotton, hemp, silk, and wool, synthetic fibers such as polyester and acrylic, and semi-synthetic fibers such as acetate and rayon. It may be a product consisting of, and the form of the product does not matter.

In the present invention, the compound having both a polymerizable vinyl group and a condensable methylol group is one in which each reaction of a double bond and a methylol group can be used separately. This is then reacted with another compound to crosslink the condensable methylol groups introduced as pendant groups.

It is a compound that can thermally cure or acid-catalyze the entire polymer. Representative compounds include N-methylol acrylamide, N-methylol methacrylamide, and N-(hydroxymethyl)methylenebisacrylamide.

In the present invention, a film made of such a compound is formed on the fiber surface, and the fluorine-containing compound of general formula C1) is bonded to the fiber by this film. The method of bonding may be such that the compound layer is bonded through the coating, the compound is contained within the coating, or a mixture of these may be used. ,
From a performance standpoint, the former two-layer structure type is preferable.

The fluorine-containing compound as used in the present invention is an acrylate compound containing a perfluoroalkyl group represented by the following general formula [1].

R.

C-Q-R.

(I) Such a compound is one type or two type represented by the above general formula.
, a polymer or copolymer consisting of the following compounds, or a copolymer with a polymerizable compound other than those listed above, such as a vinyl compound such as acrylic acid, methacrylic acid, styrene, or vinyl chloride.

The present invention provides that the fluorine-containing compound is contained in the coating formed of the compound having both the polymerizable vinyl group and the condensable methylol group and/or is contained in the coating (and is bonded to the fiber surface). In particular, when the fluorine-containing compound is bonded to the fibers through the coating, that is, when it is bonded to the coating in a two-layer structure, it has excellent water and oil repellency. It has a great effect.

When a triazine ring-containing compound is further combined with the fluorine-containing compound, the durability and resistance to misalignment are significantly improved, and the object of the present invention can be suitably achieved.

The triazine ring-containing compound is a compound that contains a triazine ring and has at least two monopolymerizable functional groups, and is preferably one that has particularly excellent wetting properties with fibers. Examples of such compounds include those represented by the following general formula.

General formula: %formula% During the ceremony.

R0~R,: -H* -01(+ -CiH8
1-CnoH2nO+1 (no: '~10)
, -COOC1,lH,n+,(n,: 1~20
).

-CONR,R,, -NR,R4 However, R,,R4: -H, -OH, -0Cn3H
2n! +, I-CH20Cn3Htn5+1.

-CHt Co o Cn3H2ns + , (n,
: 1-20).

-CH,OH,-CH2CH,OH,-CON)J,.

-CONHCH,OH.

-o -4-x L-o÷ R6 X: c, n,, c, n,, C, H, (n,:1
~1500) R,: -H, -CH,, -C, Ho-C
,H.

More preferred compounds among the above general formulas are:

It is a compound in which R,, 'R, is -NJR4, and in its lifetime, R2 is -CONR, R4, -NR,R.

9- Furthermore, R,, R, is -CH,OH, -CH,CH,OH,
-CONH,.

Compounds that are -CONHCH,O)( are preferred.

In addition to those represented by the above general formula, ethylene urea cocondensation compounds, dimethylol urea cocondensation compounds, dimethylolthiourea cocondensation compounds, acid colloid compounds, etc. of the above compounds can also be used.

Since the triazine ring-containing compound has at least two or more polymerizable functional groups, the fluorine-containing compound [1] is strongly bonded to the film on the fiber surface.

This can significantly improve the durability of water and oil repellency. Moreover, it also has the effect of improving the resistance to misalignment, which is required in view of the characteristics of sewn products.

The coating of the specific compound of the present invention has a strong bond with the above-mentioned fluorine-containing compounds and the triazine ring-containing compound, and has the effect of synergistically enhancing the performance of the fluorine-containing compound. Through this action, it was able to exhibit even more durable water and oil repellency.

Next, 10- Explain the method.

First, a textile product is brought into contact with a compound having both a polymerizable vinyl group and a condensable methylol group, and subjected to moist heat treatment or long-term treatment at room temperature, so that the compound penetrates into the fabric and reacts to form a polymer. The polymer reacted under such moist heat conditions exhibits the characteristic effect of coating the fiber surface in the form of a uniform film. Here, the following method is effective as the moist heat treatment.

That is, the compound having both a monopolymerizable vinyl group and a condensable methylol group has a weight of 0.01 to 20 (heavy weight).

h) An immersion method in which the fabric is heat-treated in an aqueous solution or dispersion at a temperature of 40 to 140'C for a time of 1 to 90 minutes, preferably 0.1 to 10C; 1
An aqueous solution or dispersion of 0.05% to 40%, preferably 0.5% to 20%, is applied to the fabric, and the amount of the core cloth is 0.05% or less, but preferably 0.5% to 5%. If the ratio is less than 005, the effect is small, and if it is more than 5, the hue of the fabric becomes dull. Furthermore, the following can be mentioned using the treatment liquid as a deposited catalyst. That is, various organic carboxylic acids such as formic acid and acetic acid, their organic salts such as ammonium, sodium, and potassium, and sulfuric acid, persulfuric acid, hydrochloric acid, and phosphoric acid.

Ammonium, sodium, potassium such as nitric acid.

Examples include inorganic salts of magnesium, zinc, aluminum, iron 1, etc., double salts thereof, hydrogen peroxide, etc., but are not particularly limited to the above-mentioned compounds.

The amount of such catalyst added is 1 normal catalyst amount, for example,
O, 31 to 10, generally 0.01 to 0.000.

Any method such as dipping, spraying, coating, etc. may be used to apply the treatment liquid to the textile product, but the dipping method is simple.

Next, the treated fiber product is heat treated at a temperature above room temperature, preferably at 40-140'O.

The compound is reacted to form a resin (film).

What is important at this time is to carry out the reaction in the presence of water. This water content greatly influences the performance of the resin (film) formed, and the reaction is usually carried out in an atmosphere of 25% or more of the fiber weight or a relative humidity of 40 parts or more. Of course, the heating reaction may be carried out while immersed in the treatment liquid. When the heat treatment is performed in a separate step, heated steam (including saturated and unsaturated) or a cold batch method in which the product immersed in the treatment liquid is left sealed can be employed. The treatment time varies somewhat depending on the type of compound and temperature conditions, but generally, at low temperatures (including room temperature), 15
Heat treatment is performed for about 0.5 to 180 minutes in heated steam at a temperature of 40 to 140° C. for about 60 hours.

In the present invention, when the compound is subjected to dry heat treatment in the absence of moisture, not only does the texture become extremely hard, but also the effects of water repellency, oil repellency, washing resistance, dry cleaning resistance, etc. This would almost eliminate the possibility of achieving the present invention. In other words, when treated with dry heat, not only the polymerizable vinyl groups react, but also the condensable methylol groups react with other functional groups such as self-crosslinking or vinyl groups. Therefore, the methylol group is significantly reduced or.

Almost all of it disappears. Therefore, since the above-mentioned fluorine-containing compound [I] has almost no bonding reactive group (methylol group), the bonding force to the fiber fabric is significantly reduced.

Next, in order to achieve the objects and objectives of the present invention, padding was performed with a treatment solution containing the above-mentioned fluorine-containing compound [I] and a triazine ring-containing compound, deliquified and dried, and then heated at a temperature in the range of 120220'O for 10 seconds. ~15 minutes, preferably 140 ~
Heat treatment at 190°C for 30 seconds to 5 minutes.

Preferably, dry heat treatment is performed. In addition to Nokurado, the treatment liquid can also be applied by a spraying method or the like. [Fluorine-containing compound CI] is not limited to a homopolymer, but the effects of the present invention can be exerted even if it is a copolymer of different monomers produced as a by-product during monomer synthesis, or a copolymer of these and other monomers. be done.

Furthermore, fluorine-containing compound [■] and triazine ring-containing compound 14
- A processing solution containing a compound [, if necessary, a condensable group (-OH
, -0CR, -NH, etc.) and inorganic salts can be present together. Water repellency, oil repellency, and antistatic properties can be improved by using antistatic agents and inorganic salts in combination.
-It is something that can be avoided.

In addition to chemicals for removing flakes, the present invention can also use agents for controlling the texture of fabrics, etc., within a range that does not impair the effects of the present invention.

The present invention can be applied to all kinds of fabrics, but in view of its effectiveness, it is desirable to apply it to fabrics made of synthetic wire or fabrics containing synthetic fibers.

However, even if the form of the fabric is knitted fabric, woven fabric, non-woven fabric, or any intermediate thereof, this does not essentially affect the effects of the present invention.

For example, synthetic fibers such as polyester and polyamide, as well as other different types of synthetic fibers. Or, the number of washings and dry cleaning treatments required to achieve the same level of water and oil repellency reduction is several times to several tens of times that of synthetic fibers and mixed fibers such as natural fibers such as cotton, rayon, and wool. In practical terms, it exhibits high water and oil repellency semi-permanently. Moreover, the textile product of the present invention has the advantage of being extremely excellent in feel (flexibility), wrinkle resistance, and shear resistance.

The present invention will be described below with reference to eight examples.

The water repellency and shear resistance are measured according to JIS-T,
-1079.

The oil repellency measurement, washing conditions, and dry cleaning conditions are shown below.

◎Measurement of oil repellency Place three test pieces of 8 cm x 8 cm on the top of a flat sample stand, and place a drop (approx. .05g).

After 15 minutes, the test piece was removed from the sample stage and evaluated according to the following criteria.

Grade 1: When machine oil is dropped on the sample surface, it is absorbed within a few seconds.

Grade 2: Machine oil droplets are crushed but some liquid remains on the surface.

Grade 6: The contact angle between the machine oil and the sample is 90 or less.

Grade 4: The contact angle between the machine oil and the sample is 90 or more.
After leaving it for 5 minutes and sucking up the machine oil.

Items with slight adhesion observed.

Grade 5: 15 when the contact angle between the machine oil and the sample interface is 90 or more.
After leaving it for several minutes and absorbing all the machine oil, no adhesion is observed.

◎Washing conditions (1) Ordinary laundry commercial detergent “ZABU” (manufactured by Kako Soap) 3g/l (bath ratio 1)
:40) After washing on strong rotation in an electric washing machine for 5 minutes at 40°C,
Rinse with overflow water for 2 minutes.

Centrifugal dehydration, overflow washing for 2 minutes, and air drying after centrifugal dehydration.

(2) Dry Cleaning Using perchloroethylene, treat with a dry cleaning cylinder at room temperature for 15 minutes and then air dry.

Example 1 Polyamide 100 coefficient length fiber fabric (basis weight 68 g/m'
17- Thin taffeta) and polyester 100 coefficient length fiber fabric (
Fabric weight: 72 g/m" (thin taffeta) by conventional method.

Scouring, heat setting, and dyeing were performed, and in the first step, N-methylolacrylamide was used as a compound containing both a polymerizable vinyl group and a condensable methylol group to form a film uniformly on the fiber surface.

・Processing liquid composition: N-methylolacrylamide 4, OL? Catalyst:
Ammonium persulfate 0.3 and penetrant: CB-01 (manufactured by Koshe Chemical) 0.1 Width meter
100 Pad this processing liquid with the pickup 40.

Immediately use a hanging steamer to bring the humidity to 100 RH.

Steam treatment was performed at a temperature of 105°C for 6 minutes. Then soaped, washed with water and dried. As a second step, water and oil repellency was performed using a resin made of a fluorine-containing compound, a triazine ring-containing compound, and a weak aqueous antistatic agent under the following conditions.

Mouth treatment fluid composition: Fluorine-containing compounds: ?・ 0 0H triazine ring-containing compound: Sumitex Resin M-30, 6 (manufactured by Sumitomo Chemical Co., Ltd.) Catalyst: Sumitex Accelerator-ACX (manufactured by Sumitomo Chemical Co., Ltd.) 0.1 group cationic antistatic agent: Perman Kusu PMX-560, 3ql) water
940chi total
A treatment solution having the above composition was padded with a 40-chip pickup and dried at 120° C. for 2 minutes. Thereafter, it was subjected to dry heat treatment at 170''C for 1 minute using a pin tenter.

Comparative example 1 Same as Example 1. However, the first step was omitted.

Comparative Example 2 The same treatment as in Example 1 was performed except that the triazine ring-containing compound in the second step was omitted.

Comparative Example In Example 1, the treatment liquid compositions in the first step and the second step were all the same treatment liquid, and the treatment was performed in only one step.

Example 1 and Comparative Example 1. The results of the water and oil repellent effects, wash resistance, and shear resistance of Comparative Examples 2 and 3 are shown in Tables 1, 2, and 6.

In Example 1, even after washing 50 times for both the polyamide 100a long edge twill fabric and the 100% polyester long fiber fabric, compared to Comparative Examples 1 to B after washing 5 to 10 times,
Shows exceptional water and oil repellency. The misalignment resistance has also been improved.

Table 2 (Second class oil repellency) Table 6 Example 2 N7C fabric, i.e. 65% polyamide, 35% cotton blended fabric (fabric weight 170 g/m”, Tussar) and T
After scouring, heat setting, and dyeing the /C fabric, i.e., polyester (65 ql), cotton 35 qi (basis weight: 200 g/m", twill) by a conventional method, a polymerizable vinyl group was added as the first step in the same manner as in Example 1. N-methylol methacrylamide was used as a compound having both a condensable methylol group and a condensable methylol group.

O treatment liquid composition: N-methylolmethacrylamide 2.0% catalyst: potassium persulfate 0.2% immersion: C, B-
01 (manufactured by Cosmo Chemical) 0.1 Width meter 10
0 % Apply this processing solution to the pick-up section 80.

Immediately place the humidity at 100% RH in a banking type stager.
, and steamed at a temperature of 105° C. for 3 minutes. Then, it was washed with soap and water and dried. As a second step, water and oil repellent finishing was performed using a resin made of a fluorine-containing compound, a triazine ring-containing compound, and a weak water-based antistatic agent under the following conditions.

O treatment liquid composition: Fluorine-containing compounds CH.

0 0H Triazine ring-containing compound: Sumitex Resin M -30,4tI) (manufactured by Sumitomo Chemical Co., Ltd.) 24- Catalyst: Sumitex Accelerator ACX (manufactured by Sumitomo Chemical Co., Ltd.) 0.1 cationic antistatic Agent: Fcol As-1000, 3% (manufactured by Matsumoto Yushi) Total of 100% A treatment liquid with the above composition was padded at 80% pick-up, and 1
After drying at 30°C for 2 minutes, use a pin tenter.

Heat treatment was performed at 180°C for 1 minute.

Comparative example 4 According to Example 2. However, the first step was omitted.

The washing resistance and scratch resistance of the water and oil repellent effects of Example 2 and Comparative Example 4 are as shown in Tables 4, 5, and 6.
Similar results to Example 1 were obtained.

Table 5 (Oil repellency grade 2) Table 6 (misalignment resistance 2g) 28-

Claims (2)

[Claims] (1) A fluorine-containing compound represented by the following general formula (11) is coated on the fiber surface with a coating made of a compound having both a 9-polymerizable vinyl group and a condensable methylol group, or/
and a water-repellent/oil-repellent fiber product characterized by being contained in and bonded to the film. R1 (wherein R6: hydrogen or lower alkyl group Rf: Cm
It has a perfluoroalkyl group represented by 2m+1,
and a hydroxyl group, an ester group, an ether group, or an amino group. Group containing at least one group selected from unsaturated groups) 1-m: 2-21'? Integer n in r: integer from 10 to 200 (2) A compound having both a monopolymerizable vinyl group and a condensable methylol group is brought into contact with the fiber surface, and reacted in the presence of water, followed by treatment with a treatment liquid containing a fluorine-containing compound CTE and a triazine ring-containing compound. A method for producing water-repellent and oil-repellent textile products, which is characterized by heat treatment after treatment.