JPS5819794B2 - Antifouling fabric and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stain-resistant fabric with significantly improved washing resistance.

Fabrics, especially fabrics containing synthetic fibers, have a strong lipophilic property and have the disadvantage of being easily stained.

Various improvements have been made to it. Examples include a method of grafting a hydrophilic monomer and a method of coating the fiber surface with a hydrophilic polymer.

However, the former process is complicated and costly, and there are only a few combinations of fibers and monomers that can be used.

For example, to the knowledge of the present inventors, there is no example of producing a polyester grafted with a hydrophilic monomer.

On the other hand, there are examples of nylon being grafted with acrylic acid monomers, but in this case the monomer penetrates into the fibers, changing the basic properties of the fibers themselves.

On the other hand, various methods of coating fiber surfaces with hydrophilic polymers have been investigated.

However, this method has a fatal problem of insufficient washing resistance.

In particular, synthetic fibers have strong lipophilic properties and are easily stained, but their molecules are highly crystalline and have a dense molecular structure, so the hydrophilic polymer film easily peels off, making it impossible to make significant improvements.

The present inventors have arrived at the present invention as a result of intensive studies to solve such problems.

That is, the present invention has the following configuration.

(1) Made of triazine or melamine polymer,
Through a membrane covering the fibers, a fluorine-containing polymer represented by the general formula where R1: hydrogen or a lower alkyl group R2: a group containing a perfluoroalkyl group having 2 to 21 carbon atoms, n2, is an integer from 10 to 200. Applying a treatment liquid containing a triazine-based or melamine-based compound to the surface of the bonded antifouling fabric and (2) the fabric, and drying the fabric in the presence of moisture of 25% or more of the weight of the fabric to be treated. 1. A method for producing an antifouling fabric, which comprises reacting the fabric without any heat treatment, then applying a treatment liquid containing a fluorine-containing polymer represented by the general formula CI), and then heat-treating the fabric.

The present invention will be explained in detail below.

The triazine-based or melamine-based polymers used in the present invention are particularly preferred as polymers of the following compounds.
'Roney H, -OH, -CI CONH2 'n H2H+1 (nl=1-16) -C6H.

-COOCn2H2n2+, (n2-1~16)R1~
Ra' Ht ”n3H2n 3+ 1 (n
321-16): -CH20Cn4)(2n4 +
t (n+=1-16)-CH20H,-CH2CH2
0H -CONH2, -CONHCH20H -0(-X -0+n H (X=C2H4,C3H6,C,H8゜n21~1500) In addition to what is represented by the above general formula (1) j (2), the above Ethylene urea co-condensed compounds, dimethylol urea co-condensed compounds, dimethylol thiourea co-condensed compounds, acid colloid compounds, etc. of compounds (1)>(2) can also be used.

By bringing these compounds into contact with a fabric and subjecting it to moist heat treatment or long-term treatment at room temperature, the triazine or melamine compound penetrates into the interior of the fabric and condenses to form a polymer.

The polymer condensed 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, 0.0% of the triazine-based or melamine-based compound.
01-20% (by weight, between), preferably 0.1-1
In a 0% aqueous solution or dispersion, at a temperature of 40 to 140°C1
A dipping method in which the fabric is heat-treated for a period of 1 to 90 minutes, and a triazine or melamine compound of 0.1 to 90 minutes.
A 40%, preferably 1 to 20%, aqueous solution or dispersion is applied to a fabric, and the fabric is heat treated with a heated steamer at a temperature of 40 to 140°C for 10 seconds to 60 minutes.

The amount of resin bonded to the fabric is 0.1% or more, preferably 1 to 5%.

If it is less than 0.1%, the effect is small, and if it is more than 5%, the hue of the fabric becomes dull.

Furthermore, a cold batch method in which the processing solution is deposited, batched up, and processed for a long time at room temperature is also effective.

Examples of catalysts for curing triazine-based or melamine-based compounds in the above-mentioned immersion method, steaming method, and cold batch method include the following.

Various organic carboxylic acids such as formic acid, acetic acid, and oxalic acid; their organic salts such as ammonium, sodium, and potassium; and ammonium, sodium, magnesium, and aluminum sulfuric acid, persulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid;
Examples include inorganic salts such as zinc and double salts thereof.

These catalysts are used in a range of 0.01 to 10% (based on the treated liquid).

In the present invention, if the heat treatment is performed using dry heat, the penetration of the triazine-based or melamine-based compound into the fabric becomes insufficient, reducing the effect of improving the washing resistance of the stain resistance that will be applied later.

Specifically, it is desirable that 25% or more of water based on the weight of the fabric be present during the reaction.

The effect decreases below 25%.

After applying the treatment liquid, without drying, at a humidity of 40% RH or higher and a temperature of 40 to 140°C for 30 seconds to 18
The purpose can be achieved by heat treatment for 0 minutes.

If the humidity is below 40% RH, the effect will decrease.

In the cold batch method, after the treatment liquid has been applied, the treatment liquid is batched up and treated at room temperature, preferably 25 to 40°C, for a long period of time, preferably 15 to 30 hours.

The fluorine-containing polymer CI'l as used in the present invention is not particularly limited, but may generally include various polymers containing a perfluoroalkyl group having 2 to 21 carbon atoms in the side chain.

Specifically, for example, Rf: carbon number 2 to 21
Perfluoroalkyl group R: hydrogen or alkyl group having 1 to 10 carbon atoms R' double alkylene group having 11 to 10 carbon atoms R'': hydrogen or methyl group n: to an integer from 10 to 200: an integer from 1 to 10 Homopolymerization, mutual copolymerization, or mutual copolymerization of monomers having a perfluoroalkyl group having 2 to 21 carbon atoms at one end and a carbon-carbon double bond at the other end, as represented by A polymer obtained by copolymerization with a polymerizable heptamer is preferred.

Next, in order to achieve the object of the present invention, it is padded with a treatment solution containing the fluorine-containing polymer (I), deliquified and dried, and then heated at a temperature in the range of 120 to 220°C for 10 seconds to 15 minutes.
Preferably, heat treatment is performed at 140 to 190°C for 30 seconds to 5 minutes, preferably dry heat treatment.

In addition to the pad, the aqueous solution can also be applied by a spraying method or the like.

The fluorine-containing polymer CI'l is not limited to a homopolymer, but even if it is a copolymer of different monomers produced as a by-product during the synthesis of monomers, or a copolymer of these and other monomers, the effects of the present invention will not be affected. Demonstrated.

Furthermore, if necessary, a condensable group (-0H, =-oc) (3,-NH2f
An antistatic agent or an inorganic salt having i.e.) can coexist.

Water and oil repellency and antistatic properties can be improved by using an antistatic agent or an inorganic salt in combination.

In addition to these auxiliaries, the present invention can also use fabric hand control agents 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 from the viewpoint of its effectiveness, it is desirable to apply it to fabrics made of synthetic fibers or fabrics containing synthetic fibers.

The form of the fabric, whether knitted fabric, woven fabric, non-woven fabric, or something intermediate thereof, does not essentially affect the effects of the present invention.

In the present invention, bonding means adhesion or chemical bonding.

Whether the bonding is adhesive or chemical bonding does not directly determine whether the present invention is effective or not.

The fabric of the present invention can be manufactured by the above method.

In other words, it is possible to produce a stain-resistant fabric to which the fluorine-containing polymer CI) is bonded via a triazine-based or melamine-based polymer.

If a triazine-based or melamine-based polymer is present, the durability of the antifouling effect of the fluorine-containing polymer [I] is surprisingly improved.

For example, the effect is several times to several tens of times the number of washes required to reduce the stain resistance to the same degree.

In other words, in practical terms, semi-permanent stain-proofing is achieved.

This effect seems to be due to the fact that the bonding force between the fluorine-containing polymer [I] and the triazine-based polymer or the melamine-based polymer is much greater than the bonding force between the fluorine-containing polymer (I) and the fibers.

It is a great advance that stain resistance with markedly excellent washing resistance as in the present invention can be obtained by processing a fabric.

This is because antifouling agents generally have a very low affinity with the polymer that forms the fibers, or are more hydrophilic than the fibers, so they gradually fall off when subjected to water, solvents, or mechanical action during washing. This is because it cannot be avoided.

On the other hand, experts in the field are well aware of how difficult the process is to improve stain resistance by using kneaded spinning or copolymer fibers to improve wash resistance. It is a fact.

In addition, in the present invention, a secondary but excellent effect of low melting property also occurs.

This is because the fibers constituting the fabric of the present invention are covered with a film of triazine or melamine polymer.

In the above step, the fluorine-containing polymer C is first applied to the fabric.
The effects of the present invention cannot be achieved when the treatment with I) is followed by treatment with a triazine or melamine compound.

In other words, since the fluorine-containing polymer opening is directly bonded to the fibers, it easily falls off during washing.

The present invention will be explained in detail below.
In accordance with S-L 1079.

The oil repellency measurement and washing conditions are shown below.

◎ Oil repellency measurement method Place three test pieces of 8Cr/L x 86rIL on a flat sample stand, and put machine oil (J Is-K 22
Drop a drop (approximately 0.05 g) of No. 14) with a micro spoon.

After 15 minutes, the test piece was removed from the sample stage and judged 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 3: The contact angle between the machine oil and the sample is 90° or less.

Grade 4: 15 when the contact angle between the machine oil and the sample interface is 90° or more
Items with slight adhesion observed after soaking up machine oil after being left for a few minutes.

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 Normal laundry Commercially available detergent "ZABU" (manufactured by Kao Sekiken) 3g, #5 at 40℃
After washing in an electric washing machine for 1 minute, wash with water, dehydrate, and dry (100℃)
x 3 minutes).

Dry Cleaning Using perchloroethylene, it was treated with a dry cleaning cylinder at room temperature for 15 minutes, air-dried, and lightly ironed at 140°C.

Example 1 A polyester long fiber knitted fabric (basis weight 250 g/cIit) was subjected to relaxing scouring, heat setting, and dyeing using a conventional method, and as the first step, a film was uniformly formed on the fiber surface using a melamine resin under the following conditions. I let it happen.

O treatment liquid composition: Melamine resin "Sumitex Resin M-3" 7.0% (manufactured by Sumitomo Chemical) Ammonium persulfate 0.3% Anionic dispersant "Ravanol D" (manufactured by Matsumoto Yushi) 0.1% water
92.6% total 100.
0% This resin liquid is picked up and padded at 80%, and immediately heated to 100% RH using a hanging steamer.

Steam treatment was performed at a temperature of 105° C. for 3 minutes.

Then soaped, washed with water and dried.

As a second step, antifouling processing was performed using a fluororesin and a weak water-repellent antistatic agent under the following conditions.

0 Treatment liquid composition: Compound below: Cationic antistatic agent “Fcol As 100” 1.0% (Matsumoto oil film) Water: 97.0% Total: 100
．． 0% The emulsified dispersion having the above composition was padded with a pickup of 80% and dried at 130° C. for 2 minutes.

Thereafter, dry heat treatment was performed at 180° C. for 1 minute using a pin tenter.

Comparative example 1 Same as Example 1.

However, the first step is omitted. The water-repellent and oil-repellent effects and washing resistance of Example 1 and Comparative Example 1 are shown in Tables 1 and 2.

Even after washing 30 times, Example 1 shows better water and oil repellency than Comparative Example 1 after washing 5 times.

Example 2 A polyamide long fiber fabric (fabric weight: 200 g/m) was dyed in the same manner as in Example 1 and treated with a triazine compound as the first step.

O treatment liquid composition Triazine compound 4.0% (compound (
In 1), R8 is C2H5, and R1-R4 are all -
CH20H) ammonium persulfate 0.2% Ravanol DO, 2% water
95.6% total 100.0% This aqueous solution was padded with a pickup of 70% and steamed for 2 minutes at 100% RH and 103°C using a hanging steamer.

Next, it was soaped and washed with water.

As a second step, antifouling treatment was performed under the following conditions.

○ Treatment liquid composition The following compounds "Fcol As-100" 0.7% 6 Sumitetsu Resin M-3" 0.2% Organic amine "Sumitex Accelerator ACX" (manufactured by Sumitomo Chemical) 0.1% Water 97.5% Total ioo
, o% The emulsified dispersion having the above composition was padded with a pickup of 70%, dried at 120° C. for 2 minutes, and then subjected to dry heat treatment at 180° C. for 1 minute using a pin tenter.

As a result of measuring the durability of stain resistance after washing, the same results as in Example 1 were obtained.

Comparative example 2 According to Example 2.

However, the first step is omitted. Washing resistance of antifouling effect is Comparative Example 1
It was the same.

Comparative Example 3 The same treatment as in Example 1 was performed except that the treatment conditions of the first and second steps were each changed to dry heat treatment.

The water repellency and oil repellency of the obtained treated fabric were measured after dry cleaning 30 times using the same evaluation method as in Example 1.
Furthermore, the fiber cross section of the treated fabric was observed using a scanning electron microscope (xsoo), and the film morphology was compared with that of Example 1.

Water repellency Oil repellency Coating form Examples 180 to 90 4 Uniform coating Comparative Examples 310 to 60 2 Resin is partially attached in lumps In the above coating form, each fiber of the treated fabric of the present invention is almost completely coated. While the fibers of the comparative example were covered with a resin film, the resin was scattered in the form of clusters attached only in areas where the fibers were close to each other.

For further confirmation, the treated fabric after the first step was also observed using a scanning electron microscope.
In the case of the invention example, a film covering the fibers was formed, whereas in the comparative example, the resin was scattered in lumps and no film was formed covering the fibers.

Claims (1)

[Scope of Claims] 1. Through a membrane covering the fibers made of a triazine-based or melamine-based polymer, a compound of the general formula where R1: hydrogen or a lower alkyl group R2: a group containing a perfluoroalkyl group having 2 to 21 carbon atoms An antifouling fabric bonded with a fluorine-containing polymer represented by n: an integer of 10 to 200. 2 A treatment liquid containing a triazine-based or melamine-based compound is applied to the surface of the fabric, and the reaction is carried out in the presence of moisture of 25% or more of the weight of the fabric to be treated without drying the fabric, and then the general formula proviso R1 : Hydrogen or lower alkyl group R2: Perfluoroalkyl group having 2 to 21 carbon atoms n: An antifouling agent characterized by applying a treatment liquid containing a fluorine-containing polymer represented by an integer of 10 to 200 and then heat-treating. Fabric manufacturing method.