JP2002088646A - Fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fiber structure having excellent soil resistance that stains adhered and then left can easily be removed by a water washing treatment. SOLUTION: This fiber structure characterized in that a resin composition comprising a fluorine-containing resin and a compound containing phosphorus and a fluoro group is adhered to the surfaces of the fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber structure having an excellent antifouling property (stain removal property), and particularly, an excellent stain removal property for a stain which has been left after being stained.

[0002]

2. Description of the Related Art Hitherto, many fiber structures having antifouling properties have been proposed. Generally, for example, a hydrophilic resin having a hydrophilic group such as polyethylene glycol is provided, or a so-called fluorinated water repellent having a polyfluoroalkyl group in a side chain is provided, or a polyfluoroalkyl group and a hydrophilic group are provided. A resin to which a fluorine-based SR agent is provided and a resin to which both of these resins are provided are known.

[0003] A resin to which a hydrophilic resin has been added has an effect of preventing re-contamination by hardly adsorbing other stains during washing. However, machine oil and the like are easily adhered to the opposite side, and the stains once adhere and dry. It is very difficult to remove even after washing.

[0004] In addition, those provided with a fluorine-based water repellent having a polyfluoroalkyl group have the effect of making it difficult to repel liquid stains, but have the opposite effect of removing stains that have been pushed in by washing. It becomes worse. In addition, those provided with a fluorine-based SR agent having a polyfluoroalkyl group and a hydrophilic group have an effect of repelling both aqueous and oily stains by the polyfluoroalkyl group,
During washing, the effect of the hydrophilic group makes it easier to remove dirt than a fluorine-based water repellent consisting of a polyfluoroalkyl group alone, but the effect is not sufficient.

Japanese Patent No. 2,836,249 discloses the use of a compound containing phosphorus and a polyfluoro group in a fiber treating agent and a processing method in which a fluorine-containing phosphoric acid derivative or a salt thereof is combined with a metal chloride. There is disclosed a method of treating with a fluorophosphate derivative or a salt thereof and a metal chloride followed by treatment with a fluorine-based water repellent. A processed article made of a fiber treating agent obtained by combining such a fluorinated phosphoric acid derivative or a salt thereof with a metal chloride has high oil repellency, but it is very difficult to remove oil stains once adhered by washing. . In addition, for processed products further treated with a fluorine-based water repellent, although the process is complicated and has the effect of repelling dirt, it is very difficult to remove oil stains and the like left after being attached by washing. It was difficult.

A method of treating the surface of a fiber cloth with a water repellent which does not inhibit the SR property after the surface of the fiber cloth is hydrophilized can be found in JP-A-64-6178. However, the water-repellent and oil-repellent effects were low, and the cleaning effect on the contaminated dirt was not sufficient.

[0007] An antifouling cloth obtained by coating a fiber surface with a melamine resin and then adding a copolymer of a perfluoro group-containing vinyl monomer and a polyoxylenalkylene-containing vinyl monomer is disclosed in JP-A-2-27787. But the effect of repelling oily dirt is not enough,
The pushed-in dirt had poor dirt-removability in washing.

[0008] All of these fiber structures have dirt attached to them, and if they are immediately washed, the dirt can be removed to some extent.
At present, if left unattended for a long time with dirt attached, it hardly falls off even after washing.

[0009]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention relates to a fiber structure having an excellent antifouling property, in which dirt that has been left behind after dirt has adhered is easily removed by washing with water. It will not be provided.

[0010]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the fiber structure of the present invention is characterized in that a resin composition composed of a compound containing phosphorus and a fluoro group and a fluorine-containing resin adheres to the fiber surface.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been studied diligently with respect to the above-mentioned problem, that is, a fibrous structure excellent in specific antifouling property that dirt is easily removed by washing with water with respect to dirt left after the dirt is attached. When a resin composition composed of a combination of a compound containing phosphorus and a fluoro group and a specific substance called a fluorine-containing resin was attached to the fiber surface, it was found that such a problem could be solved at once. .

The compound containing phosphorus and a fluoro group referred to in the present invention is preferably a compound represented by the following general formula [I]. Since such a compound has high oil repellency, by adhering to the fiber surface, the effect of repelling an oil component such as a machine oil which tends to enter the inside of the fiber bundle or the inside of the fiber is greatly improved.

[0013]

Embedded image

Among these compounds, a phosphoric acid compound having a fluoroalkyl group having 5 to 10 carbon atoms is preferably used.

The fluorine-containing resin according to the present invention is characterized in that it is composed of a polymerizable monomer of a (meth) acrylate having a terminal perfluoroalkyl group having 6 to 14 carbon atoms. And preferably contains a monomer represented by the following general formula [II].

[0016]

Embedded image

The fluorine-containing resin of the present invention is selected from a polymer obtained by polymerizing such a monomer on a fiber, a polymer of such a monomer, and a copolymer obtained by polymerizing such a monomer and a third component. The fiber preferably contains at least one compound containing phosphorus and a fluoro group, from the viewpoint of durability.

In the present invention, the resin composition comprising a compound containing phosphorus and a fluoro group and a fluorine-containing resin adheres to the fiber surface, thereby greatly improving the stain removability. Among such resin compositions, the compound containing phosphorus and fluoro group is preferably 2
A composition of 0 wt% or more, more preferably 20 to 80 wt%, is preferable from the viewpoint of greatly improving oil repellency. If it is less than 20 wt%, the oil repellency is greatly reduced, and if it exceeds 80 wt%, the washing durability tends to be inferior. More preferably, in such a resin composition, the content of the fluorine-containing resin is preferably in the range of 0.5 to 2.5 times the compound containing phosphorus and fluoro group from the viewpoint of washing durability. .

In the present invention, such a resin composition may contain a hydrophilic compound, and the hydrophilic compound is preferably a polyalkylene glycol or a block copolymer of a polyalkylene glycol and a synthetic resin. To use.

As the synthetic resin constituting such a hydrophilic compound, at least one selected from polyester, urethane resin and silicone resin is preferably used.

Such a polyester block copolymer of polyalkylene glycol is obtained by block copolymerizing a polyalkylene glycol with a polyester comprising an aromatic dicarboxylic acid and an alkylene glycol.
The polyalkylene glycol referred to herein is -C in the molecule.
refers to _{n H 2n O- (n = 2~4} ) becomes one having a backbone molecular weight is preferably in the range of 300 to 40,000, more preferably in a range of 1,000 to 10,000. As such a polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol or a block polymer thereof can be used. When the molecular weight is less than 300, durability tends to be insufficient, and when the molecular weight exceeds 4000, dispersibility tends to decrease.

Next, the polyurethane block copolymer of polyalkylene glycol is a polymer or prepolymer having a polyalkylene glycol as a functional group, preferably an isocyanate group blocked with a blocking agent that dissociates by heat. A polyalkylene glycol-blocked product of a heat-reactive prepolymer is preferred. A dissociation catalyst may be used to promote dissociation, and dibutyltin thiolate, dibutyltin tearate, stearyl zinc, and organic amine compounds are preferred.

As the silicone resin block copolymer of polyalkylene glycol, those usually used as a water-absorbing softening agent for fibers are preferably used. Among them, one containing both an amino group and a polyalkylene glycol in one molecule is preferred. Aminopolyether-modified silicone containing an organopolysiloxane as a main component is preferably used. Since silicone resins are generally lipophilic, they tend to attract oil stains, and those having no hydrophilic group are very difficult to remove stains in washing. Therefore, it is preferable to use one having a hydrophilic group such as polyalkylene glycol.

In addition to the above, examples of the aromatic dicarboxylic acid for block copolymerizing a polyalkylene glycol include, for example, terephthalic acid, lower alkyl esters of terephthalic acid, isophthalic acid and lower alkyl esters of isophthalic acid. At least one kind can be preferably used. Further, as the alkylene glycol, for example, ethylene glycol, propylene glycol, butylene glycol and the like can be preferably used.

In the block copolymerization of the polyalkylene glycol, the molar ratio of the polyalkylene glycol: the aromatic dicarboxylic acid: the alkylene glycol is 1
A range of from 31: 1: 2 to 3 is preferably adopted from the viewpoint of stain removability.

In the present invention, oil repellency and dirt removal properties are simultaneously achieved only by a synergistic effect of a specific combination of a compound containing phosphorus and a fluoro group and a fluorine-containing resin. That is, the present invention has an excellent effect that it easily repels oil stains such as machine oil, and even if the apparatus is left with the stains attached, the stains can be easily removed by washing.

The compound containing phosphorus and a fluoro group of the present invention is preferably used in an amount of 0.04 to 2.5 wt%, more preferably 0.1 to 2 wt%, based on the weight of the fiber of the fibrous structure.
It is preferable that the weight% is adhered. If it is less than 0.04 wt%, sufficient oil repellency cannot be obtained, and if it is more than 2.5 wt%, the texture of the fiber structure tends to be hard.

Further, the fluorine-containing resin is preferably used in an amount of 0.08 to 3.5 wt% with respect to the fiber weight of the fibrous structure.
More preferably, 0.1 to 3 wt% is attached. If it is less than 0.08 wt%, sufficient water repellency cannot be obtained, and if it is more than 3.5 wt%, the texture of the fiber structure tends to be hard.

The hydrophilic compound is preferably adhered to the fiber structure in an amount of preferably from 0.03 to 1.2% by weight, more preferably from 0.1 to 1% by weight, based on the fiber weight. If it is less than 0.03 wt%, there is no effect of further improving the antifouling property, and if it is more than 1.2 wt%, water repellency,
It tends to reduce oil repellency.

In the present invention, a fixing agent may be used in order to fix the resin composition to the fiber surface with high durability. As such a fixing agent, those generally used as a fixing agent for water repellent for fibers and those used as fixing agents for water repellent for paper are preferably used. Aminoplast resins and polyfunctional blocked isocyanate-containing urethane resins can be used as fixing agents for water-repellent finishing for fibers.

As the aminoplast resin, melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea and dimethylol ethylene urea, and uronic resins such as dimethylol uron resin can be used. Among such aminoplast resins, hexamethylolmelamine is preferred.

It is preferable that the aminoplast resin adheres to the fiber in an amount of 0.05 to 1.0% by weight based on the weight of the fiber. If it is less than 0.05 wt%, the durability will not be improved, and if it is more than 1.0 wt%, the feeling will be hard, which is not preferable.

Commonly used catalysts may be used together with the aminoplast resin, for example, ammonium, aluminum or zinc salts of inorganic acids such as phosphoric acid, sulfuric acid and nitric acid, formic acid, acetic acid, acrylic acid, succinic acid and the like. And the like of organic acids.

Further, a urethane resin containing a polyfunctional blocked isocyanate may be used. As such a urethane resin containing a polyfunctional blocked isocyanate, 2
There is no particular limitation as long as it is an organic compound containing two or more blocked isocyanate functional groups. For example,
A polyfunctional compound obtained by reacting tolylene diisocyanate, hexamethylene diisocyanate, diphenyl methane diisocyanate, etc. with a blockable compound capable of regenerating an active isocyanate group upon heating at 70 to 200 ° C., for example, phenol, sodium bisulfite, etc. A blocked isocyanate-containing urethane resin is preferably used.

It is preferable that the urethane resin containing the polyfunctional blocked isocyanate adheres in an amount of 0.05 to 0.8 wt% based on the weight of the fiber. If less than 0.05 wt%,
If the durability is not improved and it is 0.8 wt% or more,
It is not preferable because the texture becomes hard. Further, a dissociation catalyst may be used in order to increase the rate of thermal separation of the blocked isocyanate and promote a decrease in the thermal dissociation temperature.For example, dibutyltindiolate, dibutyltinstearate, stearylzinc, and organic amine compounds are preferably used. You.

As a fixing agent for a paper water repellent, a monomer or oligomer having at least one vinyl terminal is preferable, and a monomer or oligomer containing at least one (meth) acrylate ester is more preferable. Oligomers can be used. More preferably, those containing nitrogen in the alcohol residue of the (meth) acrylate are preferably used. Such a monomer or oligomer is present in an amount of 0.05% by weight of the fiber.
Preferably, it is attached to 0.5 wt%. 0.05
If the amount is less than 0.5 wt%, the durability will not be improved, and 0.5 wt%
% Does not improve the effect.

The method for processing the fibrous structure of the present invention is not particularly limited, and a padding method, a spraying method, a coating method and the like can be employed. A polymerizable monomer monomer of a compound and a (meth) acrylate having a perfluoroalkyl group, a dispersion of a copolymer containing such a monomer, or a hydrophilic compound further containing a polyalkylene glycol are added. After impregnating the resulting dispersion with the fiber structure, it is preferable to squeeze with a mangle at a fixed squeezing rate and heat-treat.

The heat treatment means a dry heat treatment or a wet heat treatment. The wet heat treatment includes a steam treatment. As the steam treatment, a normal pressure saturated steam treatment, a heating steam treatment, a high pressure steam treatment, or the like can be employed.

The temperature of the dry heat treatment or the wet heat treatment is 100
~ 200 ° C is preferred. When the heat treatment temperature is lower than 100 ° C, the washing durability is insufficient, and the heat treatment temperature is lower than 200 ° C.
, Yellowing of the fiber and embrittlement tend to occur.

In the present invention, a resin composition composed of a compound containing phosphorus and a fluoro group and a fluororesin may be adhered to the surface of the fiber having a hydrophilic group.

As such a fiber having a hydrophilic group, a fiber having at least one hydrophilic group among a hydroxyl group, a carboxyl group, a sulfo group, a sulfonyl group, an amino group, an amide group, an ether group and an ester group is preferably used.
In addition, as the fiber having a hydrophilic group, the fiber constituting the fiber structure may have a hydrophilic group as an intrinsic property, or may have a hydrophilic group by pretreatment for hydrophilicity.

As means for the pre-hydrophilization treatment, introduction of hydrophilic groups by fiber surface modification or fiber internal modification, attachment of a hydrophilic organic compound to the fiber, and (at least a part of) the fiber by a hydrophilic polymer Means such as coating can be employed.

As a fiber surface modification method, there is preferably a plasma treatment.

The term "plasma treatment" as used in the present invention means that a cloth is exposed to a plasma discharge generated by applying a high voltage. There are various forms of such discharge, such as spark discharge, corona discharge, and glow discharge. The discharge form is not particularly limited as long as it does not damage the fabric, but the glow discharge is uniform in discharge and has excellent activation action. Is particularly preferred.

The glow discharge is preferably 7000
It is generated by applying a high voltage in a gas atmosphere under reduced pressure of Pa or lower, more preferably 3000 Pa or lower, particularly preferably 1 to 1500 Pa. The processing time is selected depending on the type of fiber and the processing apparatus. , Preferably several seconds to several minutes, more preferably about one second to five minutes.

As the gas constituting the gas atmosphere of the plasma processing, for example, Ar, N ₂ , He, CO ₂ , C
O, O ₂ , CF ₄ , H ₂ O, air and the like are preferably used. Particularly preferably, a gas containing Ar, He, and an oxygen atom, for example, a gas containing CO ₂ , H ₂ O, air and the like is used. It is preferable for improving the hydrophilicity.

The fiber internal modification treatment is preferably performed by graft polymerization of a hydrophilic vinyl monomer.
Such a hydrophilic vinyl monomer refers to a compound containing at least one polymerizable unsaturated group, wherein the polymer is more hydrophilic than the polymer constituting the fiber to be treated. Any compound can be used regardless of the molecular weight. Generally, a vinyl monomer having a hydrophilic group is used. Examples of such monomers include unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid, unsaturated amides such as acrylamide and N-vinylpyrrolidone, and unsaturated sulfonic acid compounds such as vinylsulfonic acid and styrenesulfonic acid. Unsaturated compounds,
Further, derivatives of these monomers are preferably used.

For example, various substances such as polyethylene glycol monoacrylate and acrylamide ethylene oxide adduct obtained by adding ethylene oxide to the above monomers are used. Particularly preferred compounds are acrylic acid, methacrylic acid and derivatives thereof. These may be used alone or in combination of two or more.

Next, the fibers constituting the fibrous structure to which the hydrophilic organic compound is adhered are preferably fibers to which the hydrophilic organic compound containing polyalkylene is adhered.

The hydrophilic organic compound containing polyalkylene includes, for example, polyalkylene glycol-
A polyester block copolymer is exemplified. The polyalkylene glycol-polyester block copolymer is obtained by block copolymerizing a polyalkylene glycol with a polyester comprising an aromatic dicarboxylic acid and an alkylene glycol. The term -C in the molecule with polyalkylene glycol _{n H 2n O- (n = 2~4} )
Having a main chain of from 300 to 300
It is preferably in the range of 40,000, more preferably in the range of 1,000 to 10,000.

As the polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol or a block polymer thereof can be used. If the molecular weight is less than 300, durability tends to be insufficient, and if the molecular weight exceeds 4000, dispersibility tends to decrease.

The aromatic dicarboxylic acid for block copolymerizing the polyalkylene glycol is, for example, terephthalic acid, at least one of lower alkyl esters of terephthalic acid and isophthalic acid, or lower alkyl of isophthalic acid. Esters can be preferably used. Further, as the alkylene glycol, for example, ethylene glycol, propylene glycol, butylene glycol and the like can be preferably used. In the block copolymerization of such a polyalkylene glycol, the molar ratio of polyalkylene glycol: aromatic dicarboxylic acid: alkylene glycol is from 1 to 3.
Those having a ratio of 1: 1: 2 to 3 are preferred from the viewpoint of dirt removal.

[0053] Further, as a fiber structure in which at least a part of the fibers constituting the fiber structure is coated with a hydrophilic polymer,
Preferably, a fiber coated with a copolymer of a hydrophilic monomer having at least two vinyl groups can be used.

The hydrophilic monomers having at least two vinyl groups include the following general formulas (III) and (I)
Organic acid monomers having at least one compound represented by V) and an unsaturated double bond are preferably used.

[0055]

Embedded image

[0056]

Embedded image

The compound represented by the above general formula (III) or (IV) (hereinafter the former is a compound (III), and the latter is a compound (I
V)) are those having two polymerizable vinyl groups, and those having water solubility are selected and used. As the compound (III), for example, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate and the like are preferably used.
In such polyethylene glycol, if the number of polyoxyethylene segments exceeds n = 25, it is difficult to synthesize and produce the compound, which is not practical. Further, even if X is any of H, alkyl and alkoxy groups, substantially the same effect can be obtained.

On the other hand, as examples of the compound (IV), bisphenol A polyethylene glycol diacrylate, bisphenol A polyethylene glycol dimethacrylate, bisphenol F polyethylene glycol methacrylate, bisphenol S polyethylene glycol dimethacrylate and the like are preferably used.

In the general formula, when n is less than 5, the solubility of the monomer in water is insufficient, and
If the ratio exceeds the above range, the production of the monomer may become difficult. Therefore, the range of 5 to 30 is preferable.

X represents an H, alkyl or alkoxy group, preferably H or CH ₃ . Y
_{Is, -CH 2 -, - C (} CH 3) 2 -, - SO 2 - represents a, preferably _{-CH 2 -, - C (CH} 3) 2 - a.

It is possible to use these compounds (III) and (IV) individually or in a mixture of both in an appropriate mixing ratio. Is more preferably used than that of the compound (IV).

The organic acid monomer having an unsaturated double bond used in the treatment includes aliphatic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, butenetricarboxylic acid, fumaric acid, acrylamide and methacrylamide. A system organic acid monomer is preferably used. In addition, these alkali metal salts can also be employed although their effects are inferior. These monomers can be used alone or
A mixture of more than one species can be used. Among the above organic acid monomers, acrylic acid, itaconic acid and methacrylic acid are particularly preferably used.

The method for coating the fiber surface with the polymer of such a monomer is not particularly limited.
After applying the mixed treatment liquid of the above compound to the fiber structure,
It is preferable to perform steaming heat treatment with saturated steam as it is.
The saturated steam referred to here has a steam content of preferably 9%.
The temperature is preferably 0% or more, more preferably 95% or more, and the temperature is preferably in the range of 90 to 150 ° C, more preferably 100 to 130 ° C. The processing time slightly varies depending on the processing temperature, but is preferably 10 to 90 seconds.

A catalyst may not be present in such a treatment solution, but a radical polymerization initiator is added as necessary. On the other hand, a pretreatment may be performed with a radical polymerization initiator, and then the treatment may be performed with the treatment liquid. Examples of such radical polymerization initiators include organic peroxides such as benzoyl peroxide and hydroperoxide, azobisbutyronitrile, potassium persulfate, ammonium persulfate, and hydrogen peroxide. It is not something to be done.

Further, in the present invention, a resin composition comprising a compound containing a phosphorus and a fluoro group and a fluororesin may be adhered to the fiber-coated fiber.

The resin coating is formed by coating fibers. In particular, it is preferable that at least a part of the single fiber of the fiber bundle constituting the fiber is covered. Here, "covering" means that each individual fiber is completely covered in a tubular shape, but in the present invention, the fiber may be partially covered.

For such a resin film, a resin such as a urea resin, a melamine resin, a phenol resin, an epoxy resin, an unsaturated polyester resin, an alkyd resin, or a urethane resin is used. The fiber surface is coated in a uniform film form. Melamine resin is preferably used because it is easy.

Such a resin film may be formed of a melamine resin alone. However, a dicamine derivative compound such as urea and thiourea, formaldehyde, a phenol compound, a triazine compound, an ethylene urea, a glyoxal compound, and a uron compound may be formed on the melamine resin. It may be formed by using a copolymer of these compounds or by using these compounds in combination with a melamine resin.

The melamine resin is preferably obtained by polymerizing a compound containing a triazine ring and having at least two polymerizable functional groups, that is, a compound represented by the following general formula [V]. Are preferably used.

[0070]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ each represent hydrogen, a hydroxyl group, a phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkyl ester group (an alkyl group having 1 to 2 carbon atoms)
0), an amide group and an amino group [the hydrogen bonded to each N of the amide group and the amino group is a hydroxyl group, an alkyloxide (alkoxy) group (the alkyl group having 1 to 2 carbon atoms)
0), an alkoxymethyl group (having 1 to 2 carbon atoms in the alkyl group)
0), methyl alkyl ester group (alkyl group having 1 to 20 carbon atoms), methylol group, ethylol group, N-methylolamide group, alkylene glycol group having a polymerization degree of 1 to 1500 (alkylene group having 2 to 4 carbon atoms). And the terminal hydrogen may be substituted with methyl, ethyl, or propyl).], Or a monovalent group selected from the group consisting of R ₁ , R ₂ and R ₃ may all be the same, or one or two may be different.

Among the compounds represented by the above formula [V], R
Compounds in which ₁ and R ₂ are amino groups are preferred, and compounds in which R ₃ is an amide group are preferred. Among these compounds, those in which hydrogen bonded to each N of an amino group and an amide group is substituted with any of a methylol group, an ethylol group and an N-methylolamide group are preferable.

Further, among the compounds represented by the above formula [V], R ₁ , R ₂ and R ₃ are amino groups, and the hydrogen bonded to N of the amino group is an alkyl oxide group. , An alkoxymethyl group (the alkyl group having 1 to 2 carbon atoms)
0), those substituted with any one of a methylol group, an ethylol group and an N-methylolamide group can sufficiently form a film by being left in a wet state at room temperature, and are suitable for energy saving measures. In addition, it has a feature that a film having excellent flexibility is formed.

The method of coating the fibers with such a resin coating is not particularly limited. For example, the method of impregnating the treatment liquid in the form of a solution or a dispersion comprising an aqueous medium containing a melamine resin and a polymerization catalyst is used. It is preferable to apply to the fiber structure by a method such as spraying, foaming, coating with a gravure roll or the like.

An important condition for forming the melamine-based resin film is not to apply the melamine-based resin but to polymerize the melamine-based resin in the presence of water. For example, the polymerization reaction is preferably performed in the presence of water at a weight of 25% or more of the fiber weight or in an atmosphere of a relative humidity of 40% or more. The reason why the film is formed in the presence of water in this manner is to cause the resin-forming component to polymerize while being held as it is, without causing migration of the resin-forming component on the fiber surface during the film formation, and to give water its holding action. It is.

As the temperature for forming such a film, a temperature range from room temperature (or 40 ° C.) to about 140 ° C. is preferably adopted.

Specifically, when the resin is formed in a separate step after the resin is applied, a film is formed in a heated steam (saturated or unsaturated) atmosphere for about 30 seconds to 180 minutes, or Any method of forming a film by a cold batch method in which the treatment liquid immersion product is sealed and allowed to escape so that moisture does not escape (one day and night) can be adopted. There is no limitation on the method as long as it can be coated with the melamine-based resin film.

The mixing ratio of the melamine resin in the treating solution is not particularly limited, but is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight. This range of the mixing ratio is selected and used from the viewpoint of film strength and coarse hardness.

As the polymerization catalyst, for example, acids such as inorganic acids and organic acids, and salts thereof are used. As such an inorganic acid, for example, sulfuric acid, sulfurous acid, persulfuric acid, phosphoric acid, nitric acid, carbonic acid, hydrochloric acid and the like are preferably used. Examples of the organic acid include compounds having a carboxyl group, for example, aliphatic carboxylic acids such as formic acid and acetic acid, acrylic acid, oxalic acid, malonic acid, malic acid, citric acid, tartaric acid, glutamic acid, aspartic acid, and maleic acid. Acids, itaconic acid, phthalic acid, isophthalic acid and the like are preferably used.

The amount of the polymerization catalyst to be added may be a usual amount, for example, preferably 0.01 to 10% by weight,
More preferably, it is used in the range of 0.01 to 3% by weight.

The weight of the melamine resin coating thus obtained is preferably 0.1% or more, more preferably 1 to 10%, based on the weight of the fiber. This range can be appropriately selected and determined from the viewpoint of uniformity and flexibility of the coating.

The fibers constituting the fibrous structure of the present invention are preferably composed of polyester fibers. Examples of such polyester fibers include polyethylene terephthalate, polybutylene terephthalate, and copolymerized polyester fibers containing these as a main component. Further, synthetic fibers other than polyester fibers, recycled fibers, and natural fibers are blended or blended. You may.

The fibrous structure referred to in the present invention includes not only fabrics such as woven fabrics, knitted fabrics or non-woven fabrics, but also strips,
As long as it is in the form of a string or a thread, that is, a product containing fibers, it can be used regardless of its structure or shape.

The fibrous structure of the present invention can easily repel oil stains such as machine oil, and can be easily removed by washing even if it is left with the stains attached. It is suitably used for such purposes.

[0085]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The following methods were used for quality evaluation in the examples. (Washing for washing durability evaluation / commercial washing 20 times) Drain the water into the drum dyeing machine, put the following detergent, 45 × 45 cm test piece and additional cloth, wash at 60 ° C. ± 2 ° C., bath ratio 1:20 and wash for 300 minutes. I do.

After draining and dehydrating, a new water rinse is performed for 60 minutes. This dehydration and rinsing operation is repeated a total of three times.

The test piece is dehydrated, air-dried and subjected to a test.

Neosat A (manufactured by Lion Corporation) 0.5 g / l Phosphor-free Double Corso (manufactured by Lion Corporation) 1.0 g / l New Bleach (manufactured by Lion Corporation) 0.7 g / l (antifouling) Evaluation / heavy oil removal evaluation)
m, placed on a glass plate with the table facing up, 0.1 ml of heavy fuel oil B was dropped on the center of the test piece, and 5 × 5
cm glass plate and put a load of 200 g
Leave for a minute.

The glass plate having a load of 5 × 5 cm was sequentially removed, and the test piece was transferred onto filter paper. Cover the portion of the test piece with heavy oil with tissue paper, apply a roller over it with an address printing roller, and change the filter paper or tissue paper to a place where there is no dirt attached. Repeat until no more.
This test piece is placed in a thermostatic dryer and left at 70 ° C. × 1 hour.

The test pieces are stitched together with an overlock sewing machine.

Then, 25 liters of hot water at 60 ° C. ± 2 ° C. was put into a washing tub of an automatic reversing spiral electric washing machine (having the same performance as the VH-1150 type of Toshiba Corp.), and a test was conducted with the following detergent. Add 1250 g of the piece and the additional cloth, and wash for 15 minutes under strong conditions.

(Detergent) Neosat A (manufactured by Lion Corporation) 0.5 g / l Phosphor-free double corso (manufactured by Lion Corporation) 1.0 g / l New bleach (manufactured by Lion Corporation) 0.7 g / l Next, the test piece and the additional cloth are transferred to a centrifugal dehydrator attached to the washing machine. After dehydration for about 30 seconds, the test piece and the additional cloth are again transferred to a washing tub containing 25 liters of room-temperature water, and rinsing is performed for 3 minutes. This dehydration,
Repeat the rinsing operation a total of three times.

The test piece is dehydrated and air-dried.

The lightness (L value) of the contaminant-adhered portion of the test piece after washing was measured using a multi-source spectrophotometer (c) manufactured by Minolta Co., Ltd.
m-3700d).

The larger the L value, the higher the cleaning property and the better the antifouling property. (Oil repellency) Measured by AATCC method.

The larger the numerical value, the higher the oil repellency. (Test cloth) The cloth to be scoured, bleached, mercerized, and fluorescently dyed under the usual conditions is used as a test cloth. Warp yarn; Polyester 167dtex / 2-48f Weft yarn; Polyester 167dtex-30f Density: 102 × 64 yarns / in. However, in the examples, those obtained by refining the above cloth under ordinary conditions were used.

(Example 1) A dispersion comprising A and B shown in Table 1, hexamethylolmelamine as a fixing agent, and ammonium persulfate as a catalyst was prepared.
A is drawn at 0%, and the solid content based on the fiber weight is A: 1.92 wt.
%, B: 1.28 wt%, fixing agent: 0.42 wt%, and then dried at 130 ° C. in a pin tenter.
A dry heat treatment was performed at 0 ° C for 40 seconds.

The stain resistance and oil repellency were evaluated for the finished test cloth and after 20 times of commercial washing.
Table 2 shows the results.

After finishing the processing, it exhibited excellent oil repellency and stain removal properties even after 20 times of commercial washing.

(Example 2) A dispersion of A, B, and C shown in Table 1, hexamethylolmelamine as a fixing agent, and ammonium persulfate as a catalyst was prepared, squeezed with a 80% pickup, and solidified with respect to the fiber weight. Minute A: 0.
96 wt%, B: 0.64 wt%, C: 0.85 wt
%, Fixing agent: 0.42 wt%, then dried at 130 ° C. in a pin tenter, and then subjected to a dry heat treatment at 180 ° C. × 40 seconds.

The stain resistance and oil repellency of the finished test cloth were evaluated after 20 times of commercial washing.
Table 2 shows the results.

After finishing the processing, it showed excellent oil repellency and stain removal property even after 20 times of commercial washing.

(Example 3) A dispersion of A, B, D shown in Table 1, hexamethylolmelamine as a fixing agent, and ammonium persulfate as a catalyst was prepared, squeezed with a 80% pickup, and based on the fiber weight. A:
0.96 wt%, B: 0.64 wt%, D: 0.92 w
t%, fixing agent: 0.42% by weight, dried at 130 ° C. in a pin tenter, and then 180 ° C. × 40
A second dry heat treatment was performed.

The stain resistance and the oil repellency were evaluated for the finished test cloth and after 20 times of commercial washing.
Table 2 shows the results.

After finishing the processing, it exhibited excellent oil repellency and stain removal properties even after 20 times of commercial washing.

(Example 4) A dispersion liquid comprising A, B, and E shown in Table 1, hexamethylolmelamine as a fixing agent, and ammonium persulfate as a catalyst was prepared. A:
0.96 wt%, B: 0.64 wt%, E: 0.83 w
t%, fixing agent: 0.42% by weight, then dried at 130 ° C. in a pin tenter, and then 180 ° C. × 4
A dry heat treatment was performed for 0 seconds. An antifouling property evaluation and an oil repellency evaluation were performed on the finished test cloth and after 20 times of commercial washing. Table 2 shows the results.

[0107] Even after finishing the processing and after 20 times of commercial washing, it exhibited excellent oil repellency and stain removability.

(Example 5) As a first step, a carboxyl group, a hydroxyl group, and an amino group were introduced into the fiber surface of the sample cloth under the following plasma conditions to obtain a fiber cloth whose fiber surface was modified. <Low-temperature plasma treatment conditions> Gas: Ar 30 ml / min Decompression degree: 80 Pa Applied voltage: 3 kV Processing speed: 20 cm / min Next, the same treatment as in Example 1 was performed on the above treated cloth as a second step.

The antifouling property evaluation and the oil repellency evaluation were performed on the obtained test cloth after washing 0 times and after 20 times of commercial washing.
Table 2 shows the results.

Even after washing 0 times and after 20 times of commercial washing, excellent oil repellency and stain removal properties were exhibited.

(Example 6) In the first step, a fiber cloth in which a carboxyl group was introduced into the interior of the fiber to modify the interior of the fiber was obtained as follows. <Graft Polymerization of Hydrophilic Monomer> As a graft polymerization initiator, an organic peroxide (manufactured by NOF Corporation, Niiper-MT-
80) 1 g, 30 g of methacrylic acid as a hydrophilic vinyl monomer, and 5 g of a quaternary ammonium salt type surfactant (Daiichi Kogyo Kachiogen AN Super) diluted with water,
100 g of an aqueous mixed solution was prepared.

The sample cloth was immersed in the above aqueous mixture, squeezed with a mangle, wound up on a roll, and sealed with a vinylidene chloride film. This sealed sample is put into a microwave processing device (Apollopet manufactured by Ichikin Co., Ltd.),
After heating and irradiation with steam and microwave at 100 ° C for 10 minutes,
After washing with hot water and drying, the weight increase rate with respect to the initial dry cloth weight was determined, and it was found that the weight increase was 15.5%.

Next, a dry heat treatment machine (Nosei Dyeing Industry Co., Ltd.)
(Hot air test pin tenter) at 180 ° C. for 30 seconds.

As a second step, the same processing as in Example 1 was performed.

The antifouling property evaluation and the oil repellency evaluation were performed on the obtained test cloth after 0 times of washing and after 20 times of commercial washing.
Table 2 shows the results.

Excellent oil repellency and stain removability were exhibited after 0 washes and 20 washes after commercial washing.

(Example 7) As a first step, an organic compound having a hydroxyl group was adhered to the fiber surface as follows to obtain a fiber cloth having a hydrophilic group.

In dyeing the sample cloth with a jet dyeing machine, a block copolymer of terephthalic acid-isophthalic acid-ethylene glycol-polyethylene glycol (terephthalate unit: isophthalate unit: polyethylene glycol unit = 2.1: 0.9: A 10% aqueous dispersion of 7.0 (weight ratio: polyethylene glycol molecular weight: 1400) was added to the material to be treated in an amount equivalent to 10% by weight in a dye bath, and dyeing was simultaneously performed at 130 ° C for 20 minutes. .

As a second step, the same processing as in Example 1 was performed.

The antifouling property evaluation and the oil repellency evaluation were performed on the test cloth obtained after washing 0 times and after commercial washing 20 times.
Table 2 shows the results.

Excellent oil repellency and stain removability were exhibited even after 0 times of washing and 20 times of commercial washing.

(Example 8) In the first step, a fiber surface was coated with a polymer having a hydroxyl group to obtain a fiber cloth coated with a hydrophilic polymer. <Saturated steam treatment of hydrophilic divinyl monomer> First, 15 g of compound III, 5 g of compound IV, and 10 g of acrylic acid
g of an aqueous solution containing 5 g of ammonium persulfate was adjusted to 1 liter. Compounds III and IV are shown below.

Compound (III) CH ₂ ＣC (CH ₃ ) —COO— (C ₂ H ₄ O) ₂₃ —CO—
C (CH ₃₎ = CH ₂ Compound _{(IV) CH 2 = C (} CH 3) -COO- (C 2 H 4 O) 15 -C 6 H 4
_{-C (CH 3) 2 - C} 6 H 4 - (C 2 H 4 O) 15 -CO-C (CH 3) = a CH ₂ trial cloth wrung homogeneous immersion mangle the treatment liquid described above.

This was placed in a steamer filled with saturated steam at 100 ° C. in a wet state and treated for 2 minutes. After the heat treatment, the product was washed with hot and cold water to remove unreacted monomers and dried.

As the second step, the same processing as in Example 1 was performed.

The antifouling property evaluation and the oil repellency evaluation were performed on the test cloth obtained after 0 times of washing and after 20 times of commercial washing.
Table 2 shows the results.

Excellent oil repellency and stain removability were exhibited after 0 washes and after 20 commercial washes.

(Example 9) As a first step, a processing solution having the following composition, namely, "Sumitec Resin M-3"
(Melamine resin manufactured by Sumitomo Chemical Co., Ltd., solid content 80
%) 7.0% by weight, 0.3% by weight of ammonium persulfate,
A test sample was immersed in a treatment solution of 0.2% by weight of a penetrant "CB-01" (manufactured by Cosmo Chemical Co., Ltd.) and 92.5% by weight of water, squeezed at a pickup rate of 80%, and immediately squeezed with a hanging-type steamer. It was steamed at a humidity of 100% RH and a temperature of 105 ° C. for 3 minutes. Thereafter, soaping, washing and drying were performed.

Next, the same treatment as in Example 1 was performed on the above treated cloth as a second step.

The test cloth thus obtained was evaluated for antifouling property and oil repellency after 0 times of washing and after 20 times of commercial washing.
Table 2 shows the results.

Both after 0 washes and after 20 washes, excellent oil repellency and dirt removal properties were exhibited.

(Comparative Example 1) A dispersion composed of A shown in Table 1 was prepared, squeezed with a pickup of 80%, and a solid content of A: 0.96 wt% with respect to the fiber weight was adhered. Drying and drying heat treatment at 180 ° C. for 40 seconds were performed.

The antifouling property evaluation and the oil repellency evaluation were performed on the finished test cloth and after 20 times of commercial washing.
Table 2 shows the results.

In the case of this comparative example, although the oil repellency was high and the stain was not easily obtained after finishing, the removability of the adhered stain was poor and the washing durability was poor.

(Comparative Example 2) A dispersion composed of B shown in Table 1 was prepared, squeezed with a pickup of 80%, and a solid content of B: 0.64 wt% with respect to the fiber weight was adhered. Drying and drying heat treatment at 180 ° C. for 40 seconds were performed.

The antifouling property evaluation and the oil repellency evaluation were performed on the finished test cloth and after 20 times of commercial washing.
Table 2 shows the results.

In the case of this comparative example, the oil repellency was low and the stain was easy to be stained.

[0138]

[Table 1]

[0139]

[Table 2]

[0140]

According to the present invention, it is possible to provide a fiber structure having an antifouling property, which has never existed before, and in particular, it is possible to provide a material suitable for a wide range of uses such as a uniform, a kitchen garment, and an apron. is there.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A41D 31/00 503 D06M 10/02 D06M 10/02 13/298 13/298 14/32 14/32 15 / 277 15/277 15/423 15/423 101: 32 // D06M 101: 32 11/08 (72) Inventor Hirotoshi Goto 1-1-1, Sonoyama, Otsu-shi, Shiga Pref. Toray Company, Shiga Plant (72) Inventor Koichi Saito 1-1-1, Sonoyama, Otsu City, Shiga Prefecture F-term (reference) in Shiga Plant of Toray Industries, Inc. 3B011 BA01 BA02 3B031 AA20 AB00 4L031 AA18 AB01 AB31 BA18 BA33 BA34 CB01 CB05 DA19 4L033 AA07 AB04 AC03 AC15 BA41 CA22 CA36 CA45 CA48 CA50 CA58 DA04

Claims (18)

[Claims] 1. A fibrous structure characterized in that a resin composition comprising a compound containing phosphorus and a fluoro group and a fluorine-containing resin adheres to the fiber surface. 2. The compound having phosphorus and a fluoro group represented by the following general formula [I].
The fiber structure according to any one of the preceding claims. Embedded image 3. The fiber structure according to claim 1, wherein the compound containing phosphorus and a fluoro group is a phosphoric acid compound having a fluoroalkyl group having 5 to 10 carbon atoms. 4. The method according to claim 1, wherein the fluorine-containing resin is composed of a polymerizable monomer and / or polymer of a (meth) acrylate having a terminal perfluoroalkyl group having 6 to 14 carbon atoms. The fiber structure according to any one of claims 1 to 3. 5. The fiber structure according to claim 1, wherein the compound containing phosphorus and fluoro groups accounts for 20% by weight or more of the resin composition. 6. The resin composition according to claim 1, wherein the content of the fluorine-containing resin is in the range of 0.5 to 2.5 times the content of the phosphorus and fluoro group-containing compound. The fiber structure according to any one of the above. 7. The fibrous structure according to claim 1, wherein said resin composition contains a hydrophilic compound. 8. The fiber structure according to claim 7, wherein said hydrophilic compound is a polyalkylene glycol or a block copolymer of a polyalkylene glycol and a synthetic resin. 9. The fibrous structure according to claim 8, wherein said synthetic resin is a polyester, urethane resin or silicone resin. 10. The fibrous structure according to claim 1, wherein the resin composition is a fiber coated with a resin film adhered on the resin film. 11. The fiber structure according to claim 10, wherein said resin film is a melamine resin. 12. The fiber structure according to claim 1, wherein said fiber is a fiber having a hydrophilic group. 13. The fiber having a hydrophilic group has at least one hydrophilic group selected from a hydroxyl group, a carboxyl group, a sulfone group, a sulfonyl group, an amino group, an amide group, an ether group and an ester group. 13. The fibrous structure according to claim 12, wherein: 14. The fibrous structure according to claim 12, wherein said fiber having a hydrophilic group is a fiber obtained by plasma treatment. 15. The fiber structure according to claim 12, wherein the fiber having a hydrophilic group is obtained by graft-polymerizing a hydrophilic vinyl monomer. 16. The fiber structure according to claim 12, wherein the fiber having a hydrophilic group has a hydrophilic group imparted thereto by the attachment of a hydrophilic organic compound. 17. The fiber structure according to claim 1, wherein the fibers constituting the fiber structure are polyester fibers. 18. The fibrous structure according to claim 1, wherein the fibrous structure is for a uniform, a kitchen garment, or an apron.