JPH06322663A - Water-and oil-repellent fiber structure - Google Patents

Abstract

PURPOSE:To obtain a fiber structure improved in washing and dry cleaning as well as durability of water and oil repelling properties to abrasion in wearing. CONSTITUTION:The fiber structure has cotton monofilament whose interior is cross-linked or packed by a reaction product of a processing agent (A) having >=2 reactive groups and capable of reacting with a cellulose-based fiber and a compound (B) having >=2 active hydrogen groups and capable of reacting with the processing agent (A) and whose surface is covered with a film of reaction product of water and oil repelling agent (C) and a cross-linkable compound (D) capable of reacting with the water and oil repelling agent (C). In this fiber structure, abrasion frequency on the surface until the cotton monofilament is subjected to splitting or fibrillation in carrying abrasion test is two or more times based on that of the fiber structure before processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water- and oil-repellent treated fiber structure, and more particularly to a cellulosic fiber having improved water- and oil-repellency durability against abrasion and the like during washing and dry cleaning. The present invention relates to a contained fiber structure.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting a high degree of water and oil repellency to a fiber structure such as a cloth, a water and oil repellent treatment agent made of a fluorine compound is applied to form a water and oil repellent film on the fiber surface. The way is done. However, since these processing agent films are brittle and have poor adhesion to fibers, the processing agent film is easier than the fibers due to washing and dry cleaning, and friction between cloths and cloth and other objects during wearing. There was a problem that the water repellency and the oil and oil repellency were significantly reduced by falling off.

Particularly regarding water repellency, hydrophilic fibers such as cellulosic fibers have poor durability, and the following proposals have been made to improve the durability. That is, a method in which a blocked isocyanate crosslinking agent is mixed with a fluorine-based water and oil repellent finishing agent containing an active hydrogen group (Japanese Patent Laid-Open No. 54-1334).
86), a method of forming a base layer of a blocked isocyanate compound on the fiber surface to improve the adhesiveness of a fluorine-based water / oil repellent agent (JP-A-54-139641), an aqueous fluorine-based water / oil repellent agent A method of treating with a solvent-based fluorine-based water- and oil-repellent finishing agent after treatment with an agent (JP-A-60-151)
380), a method of copolymerizing a fluorine group-containing acrylic monomer on the fiber surface (Japanese Patent Publication No. 63-14117), and the like. However, even with these methods, the durability of water repellency is not sufficient, and particularly in the case of a fibrous structure containing cellulosic fibers, water repellency is almost lost when a high durability test such as 50 times of washing is performed.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a water- and oil-repellent fiber structure having a high degree of durability, which has not been obtained by the prior art with respect to cellulose fibers.

The inventors of the present invention have earnestly studied a method for preventing a decrease in water repellency due to washing and rubbing of a cellulosic fiber cloth treated with a fluorine-based water and oil repellent finishing agent.
It has been found that it is effective not only to prevent the water-repellent finishing agent from falling off by washing and rubbing, but also to prevent the monofilaments on the fabric surface from being fibrillated by washing and rubbing.

From the above, the inventors of the present invention only prevent the water- and oil-repellent finishing agent from falling off from the fiber in order to dramatically improve the durability of the water- and oil-repellent finishing of the cellulosic fiber structure. Is not sufficient, and the present invention has been achieved in which the fibers themselves are not fibrillated by washing or friction between cloths.

That is, the present invention relates to a processing agent (A) having at least two reactive groups capable of reacting with the cellulose fiber inside the cellulosic monofilament and / or active hydrogen capable of reacting with the processing agent (A). Crosslinked or filled with the compound (B) having two or more groups, and the surface of the cellulosic single fiber is mainly a film of the water / oil repellent finishing agent (C) or the water and oil repellent finishing agent (C) and the water repellent. A fiber structure having a cellulosic single fiber coated with a film of a reaction product of a crosslinkable compound (D) capable of reacting with an oil repellent finishing agent.
When a friction test was performed with a cotton No. 3 of JIS L 0803-1986 (white cloth attached for dyeing fastness test) in a wet state with a friction tester type II according to L 0823-1971, the surface cellulose single fiber was The split fork is a water- and oil-repellent fiber structure characterized in that the number of times of friction before fibrillation is twice or more that of the fiber structure before processing.

The cellulosic fiber in the present invention means
Examples include cotton, rayon, polynosic, cupra, and tencel. In these cellulosic fibers, the inside of the single fiber is not uniform and various microstructures are formed.

For example, in the case of cotton fibers, the monofilaments are composed of a primary wall containing a large amount of wax and pectin and removed in the refining process, and a secondary wall containing cellulose as a main component. The secondary wall is
It forms a higher-order structure composed of a fine cellulose structure called lamella, fibril, microfibril, and elementary fibril, and there are minute voids between the structures. Therefore, when a large external force is applied due to friction or the like, the fibrous structure is not scraped off uniformly, but the fibrous structure is first torn between the lamellas, which are the largest microstructures, and the single fibers are fibrillated.

The fibrillation of the cotton fiber due to this friction occurs even in a dry state, but particularly when the cotton fiber swells due to water or the like and the voids between the lamellas expand.
Therefore, when the cotton cloth is swelled with water and rubbed against each other and the wall of the washing machine tub due to washing and the like, and the surface of the cloth is strongly rubbed, the single fibers on the surface of the cloth are fibrillated between the lamellae. The fibrils generated by this washing are so small that they are not visible to the naked eye, but when the surface of the cotton fabric after washing is magnified 500 times or more with a scanning electron micrograph, it is a mustache-like shape with a size of several μm or less from the surface of the single fiber. Fibrils are generated as the fiber structure turns over.

In order to prevent the decrease in water and oil repellency due to the fibrillation, the processing agent (A) having two or more reactive groups capable of reacting with the cellulosic fiber is added to the inside of the monofilament of cellulosic fiber such as cotton. It is necessary to infiltrate and improve the friction durability of the monofilament.

Here, in order to allow the processing agent to penetrate into the inside of the cotton single fiber, it is necessary that the molecular diameter or the particle size of the processing agent is such a size that the processing agent penetrates into the inside of the single fiber or that the single fiber is swollen. . Fluorine-based water and oil repellent finishing agent (C) in the present invention
Is a water-based emulsion type or solvent-soluble type, the water-based emulsion type has an emulsion particle size of about 0.05 μm.
If it is above, it does not enter the gap (0.05 μm or less) between the lamellas swollen and opened by water, and the cotton does not swell because the chlorine-based or petroleum-based solvent is used as the solvent in the solvent-soluble type. Since the gap between the lamellas remains closed, the processing agent does not penetrate into the inside of the single fiber and forms a film mainly on the surface of the single fiber. It is difficult to prevent the fibril formation of single fibers by friction only with this coating.

In order to improve the friction durability of the single fiber in order to prevent fibrillation due to friction, a processing agent (A) having two or more reactive groups capable of reacting with the active hydrogen group of the cellulosic fiber itself is used. It is necessary to crosslink the inside of the single fiber or the surface of the fiber, or to form a tough film on the surface of the fiber.

The processing agent (A) having two or more reactive groups capable of reacting with the active hydrogen group of the cellulosic fiber is N-
Methylol compounds, ketone resins, acetal resins, isocyanate compounds, epoxy resins and the like can be used.

Examples of the N-methylol compound include urea formaldehyde resins such as dimethylol urea, melamine formaldehyde resins such as trimethylol melamine and hexamethylol melamine, dimethylol ethylene urea,
Ethylene urea resins such as dimethylol dihydroxyethylene urea, alkyl carbamate resins such as dimethylol hydroxyethyl carbamate, polymers of N-methylol acrylamide and copolymers with other acrylic and methacrylic compounds can be used.

As the ketone resin, acetone formaldehyde resin or the like can be used.

As the acetal resin, glycol acetal, pentaerythritol bisacetal, etc. can be used.

As the isocyanate-based compound, a compound having two or more isocyanate groups obtained by blocking the isocyanate group with sodium sulfite, an oxime-based compound or the like can be used.

As the epoxy resin, glycidyl ether compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerin diglycidyl ether and trimethylolpropane triglycidyl ether can be used.

Among the processing agents (A) having two or more reactive groups capable of reacting with these cellulosic fibers, the voids between the fine structures (between the lamellas in cotton) inside the single fiber or the fiber surface can be used. In order to efficiently crosslink, those having a relatively large molecular weight are preferable. In this sense, the above-mentioned processing agent (A) having a small molecular weight, which has a large molecular weight upon crosslinking due to self-condensation, is particularly effective in the present invention. It is also effective to use a compound having another active hydrogen group in combination to lengthen the crosslinked chains to crosslink the fine structure gaps, or to form a crosslinked film crosslinked with the fibers on the fiber surface.

As the compound used in combination to lengthen the crosslinked chain or to form a crosslinked film on the fiber surface, a compound (B) having two or more active hydrogen groups capable of reacting with the above-mentioned processing agent (A). Is available. As the compound (B), a polyhydric alcohol compound, a polymer compound having two or more active hydrogen groups, and the like can be used.

Examples of the polyhydric alcohol compound include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, natural sugars such as glucose and sorbitol, and addition of ethylene oxide and / or propylene oxide. You can also use things.

Examples of the polymer compound having two or more active hydrogen groups include polyalkylene oxide compounds, polyvinyl alcohol, acrylic copolymers having a hydroxyl group in the side chain, natural polysaccharides such as starch and carboxymethyl starch, and the like. Modified compounds, cellulosic compounds such as sodium alkynate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and the like can be used.

These polyhydric alcohol compounds and polymer compounds must have a small molecular size in order to enter between the fine structures inside the swollen single fiber and play a role of a cross-linking chain between the fine structures. Is preferably tens of thousands or less. On the contrary, in order to form a crosslinked film with the above-mentioned processing agent (A) on the fiber surface, it is preferable that the molecular weight is large.

When the above-mentioned processing agent (A) and compound (B) having an active hydrogen group are applied to the fiber, if the purpose is to crosslink the inside of the fiber, the compound penetrates into the inside of the fiber. In order to do so, it is necessary to dissolve and apply with a solvent that swells the cellulosic fibers. The solvent for swelling the fibers is not particularly limited, but water is preferable.

As a method of reacting the above-mentioned processing agent (A) and a reaction product of the active hydrogen group-containing compound (B) capable of reacting with the processing agent (A) with the cellulose fiber, these processing agents are used inside the single fiber. Any method may be used as long as it is possible to carry out the reaction after permeating the cells, but the method of heating and reacting is the most convenient.

Next, as another method for forming a tough film on the fiber surface, which is another method for preventing fibrillation due to friction, a method of applying a film-forming polymer compound to the fiber surface to form a film, polymerization There is a method in which a functional compound is added and polymerized on the fiber surface to form a film.

As a method for applying a film-forming polymer compound to the fiber surface to form a film, the film-forming polymer is dissolved, dispersed or emulsified in water or various solvents, applied to the fiber surface and dried by heat or the like. A method of curing and forming a film can be used.

As the film-forming polymer, vinyl polymer, acrylic polymer, urethane polymer, polyalkyl oxide polymer, polyester polymer, polyamide polymer, epoxy polymer, cellulose polymer Molecules can be used.

At this time, for the purpose of improving the durability of the polymer compound film, a crosslinkable compound may be used in combination to crosslink the polymer film or crosslink the polymer film and the cellulose fiber. Examples of the crosslinkable compound include N-methylol compounds, ketone resins, acetal resins, isocyanate compounds,
Epoxy resin etc. can be used.

As a method for applying a polymerizable compound and polymerizing it on the fiber surface to form a film, an acrylic monomer,
A method in which a methacrylic monomer or other compound having a polymerizable unsaturated group is applied to the fiber surface and then polymerized by heat, ultraviolet rays, radiation or the like can be used. At this time, for the purpose of improving the film strength, and further improving the adhesiveness with the cellulose fiber and the water repellent agent, other polymer compounds and crosslinkable compounds may be used in combination.

In order to efficiently carry out the crosslinking reaction or the polymerization reaction of the compound used for the purpose of preventing fibrillation of the above fibers, an additive such as a catalyst or an initiator may be used according to each compound. Further, in order to reduce the friction on the fiber surface and to make the texture after processing preferable, a silicone-based or aliphatic-based smoothing agent, a softening agent and the like can be used in combination. The amount of these compounds applied to the fiber structure is preferably within a range that does not significantly impair the texture of the cloth, and the amount of the compound applied to the fiber structure is 20% or less, preferably 10% or less based on the fiber weight. is there.

In order to obtain the durable water-repellent and oil-repellent fiber structure of the present invention, the water- and oil-repellent finishing treatment is applied to the fiber which has been subjected to the above-mentioned treatment for preventing fibrillation. However, the processing for preventing fibrillation may be performed before the water- and oil-repellent processing or at the same time as the water- and oil-repellent processing.

As the water- and oil-repellent finishing agent (C) in the present invention, a generally used fluorine-based or silicon-based compound dissolved, dispersed or emulsified in a water or solvent can be used. Among these, a fluorine-based water- and oil-repellent finishing agent is preferable from the viewpoint of oil repellency. As the fluorine-based water and oil repellent finishing agent, a perfluoroalkyl group-containing compound having a reactive group is preferable, and the reactive group has a self-reactive property such as an epoxy group, a methylol group or a chlorotriazine group. Examples thereof include a reactive group capable of reacting through a crosslinkable compound such as a group, a hydroxyl group and an amino group. Furthermore, in order to improve the adhesion between the fluorine-based water and oil repellent finishing agent and the cellulose fiber or the film formed on the fiber surface to prevent fibrillation, the water and oil repellent finishing agent reacts with the finishing agent. A crosslinkable compound (D) can be used. Examples of the compound (D) include a polyisocyanate compound and a polyepoxy compound, and it is preferable to use a polyisocyanate compound, particularly a blocked isocyanate-based crosslinking agent in combination.

The processing agent for fibrillation prevention and the processing agent for water and oil repellent processing, which are used for obtaining the durable water-repellent and oil-repellent fiber structure of the present invention, are used as fibers. A dipping method, a pad method, a coating method, a spray method, or the like can be used as a method of applying the structure.
Among these, the pad method is preferable in order to uniformly apply it to the entire fiber.

The fibrillation in the present invention means that the single fibers are subdivided due to the phenomenon that the single fibers are split into two or more or the fiber structure is separated from the surface of the single fibers. As a test method for evaluating the friction durability of this fiber against fibrillation, a water-repellent and oil-repellent cloth is JIS
Using a friction tester type II according to L 0823-1971, a sample after rubbing with JIS L 0803-1986 (white cloth for dyeing fastness test) cotton No. 3 in a wet state was observed with a scanning electron microscope, and fibrils were observed. A method of measuring the number of occurrences of is available.

Here, the number of times fibrils start to occur is
The surface of the cloth sample after the friction test was photographed with a scanning electron microscope at a magnification (about 500 times) at which 10 or more single fibers can be seen.
It is the number of times that two or more out of ten monofilaments shown in the figure have fibrillated, and this is hereinafter referred to as the number of fibrillation occurrences.

In order to accurately determine the number of occurrences of fibrillation, the part of the fabric sample observed after the friction test is important. In the friction test, the portion where the yarn is most raised on the surface of the fabric, that is, the central portion of the warp weave in the woven fabric and the uppermost portion of the yarn loop in the knitted fabric are rubbed most strongly, so that fibrillation occurs from this portion. Therefore, it is necessary to observe this portion when determining fibrillation by observation with a scanning electron microscope.

The degree of fibrillation prevention of the fiber structure according to the present invention requires that the ratio of the number of fibrillation occurrences of the fiber structure after processing to the number of fibrillation occurrences of the fiber structure before processing is twice or more, It is preferably 4 times or more, more preferably 8 times or more.

The fiber structure containing cellulosic fibers referred to in the present invention means cotton, rayon, polynosic, cupra,
Fibers including cellulosic fibers such as TENCEL, yarns, woven fabrics, knitted fabrics, non-woven fabrics and the like, which may be a mixture with other fibers such as synthetic fibers, natural fibers and regenerated fibers.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

1. Synthesis example of processing agent (a) Fluorine-based water and oil repellent processing agent Perfluorooctylethyl acrylate: 80 parts, 2-
Ethylhexyl methacrylate: 8 parts, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid: 7
Part, methyl methacrylate: 5 parts were emulsion-polymerized in water to give a fluorine-based water and oil repellent finishing agent (active ingredient: 20%, dispersed particle diameter 0.1 μm, hereinafter abbreviated as FWP). (B) Blocked isocyanate cross-linking agent After adding 3 moles of diphenylmethane diisocyanate to trimethylolpropane, the remaining 3 moles of blocked isocyanate compound blocked with methyl ethyl ketoxime are dispersed in water (active ingredient: 30%, Dispersed particle diameter 0.5 μm, hereinafter abbreviated as BNCO), and blocked isocyanate crosslinking agent.

2. Water- and oil-repellent finishing method Examples 1 and 2 Refined, bleached, mercerized cotton twill fabric (80/2 x
80 / 2-185 x 95 lines / inch) and after pad treatment (squeeze ratio: 60%) with a pretreatment bath consisting of the following water-soluble polymer, crosslinkable compound, and catalyst, 110 ° C for 3 minutes Dried
Further, curing treatment was performed at 160 ° C. for 3 minutes. After that, a water- and oil-repellent treatment bath consisting of a fluorine-based water- and oil-repellent finishing agent and a blocked isocyanate cross-linking agent was pad-treated (squeeze ratio: 6
0%) and then dried at 110 ° C for 3 minutes and then at 160 ° C for 3 minutes.
Curing treatment was performed for a minute. (Pretreatment agent formulation) (Example 1) Polyvinyl alcohol (molecular weight 100,000) 2 parts Methylol urea highly condensed resin (active ingredient: 85%) 3 parts 2-methyl-2-aminopropanol hydrochloride (active ingredient: 20) %) 1 part Ion-exchanged water 94 parts (Example 2) Polyvinyl alcohol (molecular weight 15,000) 2 parts Dimethylol dihydroxyethylene urea (active ingredient: 50%) 7 parts Magnesium chloride (active ingredient: 20%) 1 part Ion-exchanged water 90 parts (Water- and oil-repellent finishing agent formulation of Examples 1 and 2) FWP 5 parts BNCO 2 parts Ion-exchanged water 93 parts

Comparative Example 1 Using the same cotton woven fabric as in Examples 1 and 2, a pad treatment (squeezing ratio: 60%) was performed with the water and oil repellent treatment formulation shown below, followed by drying at 110 ° C. for 3 minutes, and further. Curing treatment was performed at 160 ° C. for 3 minutes. (Prescription of water- and oil-repellent finishing agent of comparative example) FWP 5 parts BNCO 2 parts ion-exchanged water 93 parts

3. Evaluation method (a) Ratio of occurrence frequency of fibrillation A woven fabric is cut into a length x width-27 x 250 mm length, and JIS L so that the warp threads are perpendicular to the friction direction.
Set in a friction tester type II according to 0823-1971, dipped in water, and then lightly squeezed to JIS L 080 in a wet state.
3-1986 (Additional white cloth for dyeing fastness test) A cotton 3 No. 3 friction test (load: 200 g) was performed by changing the number of times of rubbing 10 times, and the warp portion of the woven fabric after rubbing was observed by a scanning electron microscope. Images were taken at three places at a magnification of 500 times, and the number of frictions when the number of fibrils of 10 or more single fibers on the surfaces of all three places began to be examined, and this was taken as the number of fibrillation occurrences.
The unwoven fabric and the water-repellent treated fabric were subjected to the above-mentioned test to determine the number of fibrillation occurrences, and the fibrillation occurrence ratio was calculated by the equation 1. The larger the fibrillation frequency ratio, the more difficult it is for fibrillation due to friction.

[Equation 1]

(B) Washing test The processed cloths of Examples 1 to 3 and Comparative Example 1 after the water- and oil-repellent finishing are J
According to IS L0217-1976 method 103, after 9 consecutive washing treatments (45 minutes for washing → 1 minute for dehydration → 36 minutes for rinsing →
Dehydration 1 minute) One more washing process (5 minutes for washing → 1 minute for dehydration →
After performing rinsing for 2 minutes → dehydration → rinsing for 2 minutes → dehydration for 1 minute), high temperature tumble drying was performed for 30 minutes by the I-2 method of JIS L 1042-1986 to obtain HL-10. Thereafter, this operation was repeated 3 and 5 times to obtain HL-30 and 5
It was set to 0.

(C) Water repellency evaluation method By the spray test of JIS L 1092-1986, the initial and the HL-10, 30 and 50 after the water-repellent and oil-repellent processed cloths of Examples 1 to 3 and Comparative Example 1 were used. The water repellency was evaluated. The water repellency was evaluated based on Table 1.

[0048]

[Table 1]

[0049]

[Table 2]

In Table 2, the fibrillation occurrence frequency ratios of Examples 1 and 2 and Comparative Example 1 and the initial stage, HL-10, 30 and 50.
Shows water repellency after. Therefore, compared with Comparative Example 1, the samples according to Examples 1 and 2 of the present invention are water-repellent by the washing test even when the same fluorine-based water- and oil-repellent finishing agent and the blocked isocyanate crosslinking agent are used. It can be seen that the durability is greatly improved. In addition, there is a high correlation between the washing durability and the fibrillation occurrence ratio, and even if the same water-repellent oil-repellent finishing agent is used for water repellent treatment, the greater the fibrillation occurrence ratio, the greater the water repellency durability. You can see that it is getting better.

[0051]

EFFECTS OF THE INVENTION The water- and oil-repellent cellulosic fiber structure of the present invention, which prevents fibrils from occurring, is more resistant to friction during washing and wearing than the conventional water- and oil-repellent cellulosic fiber structure. Durability of water and oil repellency is remarkably excellent.

Claims (1)

[Claims] 1. A processing agent (A) having two or more reactive groups capable of reacting with the cellulose fiber inside the cellulosic monofilament and / or 2 active hydrogen groups capable of reacting with the processing agent (A). Crosslinked or filled with the compound (B) having one or more compounds, and the surface of the cellulosic single fiber is mainly a film of the water / oil repellent finishing agent (C) or the water and oil repellent finishing agent (C) and the water / oil repellent finish. A fiber structure having cellulosic single fibers coated with a film of a reaction product of a crosslinking compound (D) capable of reacting with an agent, wherein the fiber structure is defined by JIS L 0823.
-1971 Friction Tester Type II in wet condition JIS L
0803-1986 (white cloth applied for dyeing fastness test) cotton 3
When the friction test is carried out with No. 1, the number of frictions before the surface cellulose single fiber starts to split or fibril is more than twice that of the unprocessed fiber structure. Oily fiber structure.