JP2002266253A - Artificial leather and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant artificial leather which does not generate an injurious gas, when burned, to which washing durability, dry cleaning durability and antifungal-water-repelling performances are imparted, and which has excellent flame retardancy, an excellent anti-fungal property and an excellent water-repelling property, and to provide a method for producing the same. SOLUTION: This artificial leather in which a polymeric elastomer is imparted to the interlaced products of ultrafine fibers and/or ultrafine fiber bundles is characterized by containing 1.5 to 10 wt.% of phosphazene compounds represented by formula (I) (X1 to X3 are each either of amino and phenoxy; Y1 to Y3 are each either of amino and phenoxy) and/or formula (II) (X1 to X4 are each either of amino and phenoxy; Y1 to Y4 are each either of amino and phenoxy), 0.1 to 5 wt.% of a benzimidazole-based compound, and 0.1 to 5 wt.% of a urethane-based compound containing a polyfluoroalkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial leather having a combined function of flame retardancy, mold resistance and water repellency, and a method for producing the same.

[0002]

2. Description of the Related Art In general, synthetic fibers, especially polyester fibers, are indispensable as materials for interior and clothing applications in view of dimensional stability, mechanical properties, durability and the like. However, synthetic fibers generally have poor self-extinguishing properties and have the property of burning, and it is extremely important to impart flame retardancy in the interior field, especially in artificial leather used for railway vehicles and automobile seats. For example, for a material used as a curtain or a blackout curtain as an interior material, a 45 ° micro burner method, a coil method, or a fire law such as JIS-L-1091, A-1 method or D method is prescribed. JIS-D-1201 or FMVSS No. 1 for materials used as automotive interior materials.
There are flammable laws and regulations such as 302.

[0003] Phosphorus, halogen,
Compounds containing elements such as antimony are preferably used. In order to make the polyester flame-retardant, for example, a method has been proposed in which a flame retardant is kneaded into the polymer at the stage of producing the raw yarn. However, from the viewpoint of the stability of the flame retardant and the polymer at the melting temperature, setting of the spinning temperature and flame retardant have been proposed. There are restrictions on the choice of
There is a problem with productivity.

On the other hand, the method of imparting flame retardancy by post-processing in the form of a sheet has the advantage that it can be processed freely as required. At present, flame retardancy is obtained by post-processing using a halogen compound. The method of providing is most commonly used. However, when a halogen-based compound is used as a flame retardant, harmful gases are likely to be generated at the time of combustion, and in recent years, the importance of global environmental issues has been emphasized, and momentum for technical improvement has been increasing.

[0005] Further, various phosphorus compounds having good flame retardancy and no generation of harmful gas have been studied.
At present, it is not used for post-processing. The reason is that phosphorus-based compounds as flame retardants are generally water-soluble in many cases and have poor affinity for polyester fibers. It has plasticizer properties and tends to induce dye bleed-out. In addition, conventional phosphorus-based flame retardant compounds, because the phosphorus content in the compound is small,
This is because there was a problem that it was necessary to provide a large amount.

On the other hand, various methods for imparting flame retardancy to the structure of a leather-like sheet have been conventionally proposed in Japanese Patent Publication Nos. 60-4306, 3-13356, and 3-20514. However, a resin containing a flame retardant is applied by a padding method or applied together with a binder, leaving a problem to be improved such as roughening of the texture of the obtained product.

[0007] In the case of textile products, sweat from the human body attached to the fiber surface and dirt in the air are used as nutrient sources.
Microorganisms such as germs and fungi that produce bad odors, cause skin disorders and diseases, and are adversely affected by hygiene. Under these circumstances, in order to create a safe and comfortable living environment, there is a demand for the development of a fiber product having both mold resistance, water repellency, stain resistance and flame retardancy.

[0008] However, a method of spraying a compound having fungicidal properties on fibers with a solution or an emulsion is disclosed in Japanese Patent Application Laid-Open No. 57-171771, but the effect alone has a long lasting effect. However, there was a problem that the fungicide would fall off due to washing or the like. Further, Japanese Patent Application Laid-Open No. 3-27183 proposes a method in which an acrylic resin is used in combination, but there is a problem that the texture of the fiber cloth is impaired. Further, when the fiber is treated with the flame-retardant polyester, the viscosity at the time of melting becomes high, and the drip property is deteriorated, so that there remains a problem that required flame retardancy cannot be obtained.

[0009]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention relates to a flame-retardant artificial leather which does not generate harmful gas during combustion, and has a washing durability and a dry-cleaning durability. Flame retardant with water-repellent and water-repellent properties
An object of the present invention is to provide an artificial leather excellent in both antifungal property and water repellency and a method for producing the same.

[0010]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the artificial leather of the present invention is an artificial leather obtained by adding a polymer elastic body to an entangled body of ultrafine fibers and / or ultrafine fiber bundles, by the following formulas (I) and / or (II). The phosphazene compound represented by 1.5
10 to 10% by weight, and 0.1 to 10% by weight of the benzimidazole compound
5% by weight and 0.1 to 5% by weight of a urethane compound containing a polyfluoroalkyl group.

[0011]

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(X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.)

[0013]

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(X _{1 to} X ₄ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) The artificial leather of the present invention The production method of (A) is a method in which an artificial leather obtained by adding a polymer elastic body to an entangled body of ultrafine fibers and / or ultrafine fiber bundles is represented by (A) the formula (I) and / or the formula (II). Phosphazene compound in a dye bath containing 5.0 to 20% by weight of solid content, the bath ratio is 1: 5 to
1: 100 and treating the artificial leather at 100 ° C. or higher, or immersing the artificial leather in a dispersion containing (B) the phosphazene compound in a solid content of 5.0 to 20% by weight to remove the artificial leather. After the liquid / drying, the phosphazene compound is subjected to either exhaustion treatment in an atmosphere of 150 ° C. or more, and then the benzimidazole-based compound is added in an amount of 0.1 to 10% by weight and a polyfluoroalkyl group. A mixed aqueous solution containing 0.1 to 10% by weight of a urethane compound containing
It is characterized by heat treatment.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is directed to an artificial leather excellent in both of the above-mentioned problems, that is, excellent in flame retardancy, mold resistance and water repellency, and studied a phosphazene compound, a benzimidazole compound and a polyfluoro compound. As a result of combining three specific types of urethane compounds containing an alkyl group into artificial leather, it has been found that such problems can be solved at once.

The ultrafine fibers in the present invention have an average fineness of 0.9 dtex or less, preferably 0.001 to 0.7 d.
tex, particularly preferably 0.01 to 0.2 dtex. Those having the average fineness range are good in terms of texture as artificial leather.

Examples of the polymer forming such ultrafine fibers include polyamides such as nylon 6, nylon 66, nylon 12, and copolymers thereof, polyethylene terephthalate and copolymers thereof, polybutylene terephthalate and copolymers thereof. And polyesters such as polypropylene terephthalate are preferably used. Among them, polyesters are preferably used in view of the effects of the present invention.

As a method for producing these ultrafine fibers, a method in which a single component is directly spun can be used, but it is formed by composite spinning or mixed spinning using polymers of at least two components having different properties from each other. More preferably, a method is used in which at least one component is dissolved and removed, or the composite fiber is separated or separated by physical or chemical action to make it ultrafine. The form of the conjugate fiber and the ultrafine fiber is not particularly limited.

As the polymer to be separated and dissociated by dissolution and removal of the composite fibers or by physical and chemical actions, the above-mentioned polyamides, polyesters, polyolefins such as polyethylene, polystyrene and polypropylene are preferably used.

The entangled body in the present invention means to shorten the conjugate fiber, form a web by means of card cross wrapper or random webber, papermaking method, etc., and then perform an entanglement treatment such as needle punch or water jet punch. Is formed. Also, it means a sheet formed by directly forming a web from spinning such as melt blowing and performing an entanglement treatment.

The elastic polymer used in the present invention includes, for example, polyurethane elastomer, acrylonitrile
Butadiene rubber, butadiene rubber, natural rubber, polyvinyl chloride, polyamide and the like are preferably used.
Among them, polyurethane elastomers are preferably used from the viewpoints of workability, product quality, texture and the like. Such a polyurethane elastomer has an average molecular weight of 50
Polyurethane elastomers using 0 to 3000 polyester diols, polyether diols and polycarbonate diols alone or in combination are preferably used. Further, as the polymer elastic body used in the present invention, a water-soluble emulsion-type resin may be used other than the solvent solution, and the polymer elastic body is not limited thereto.

As a method for producing the artificial leather of the present invention, for example, a conjugate fiber having an island component having an average fineness of 0.9 dtex or less after ultra-fine-graining is made into a short fiber, and is made by means such as a card cloth wrapper or a random webber. A web is made, and then an entangled sheet is made by performing a needle punch or a water jet punch. The entangled sheet is subjected to a densification treatment or a sizing agent such as polyvinyl alcohol, if necessary, to remove sea components, and then to apply a polymer elastic body.

An artificial leather can be obtained by subjecting such a sheet containing a polymer elastic body to half cutting (half cutting: cutting into several pieces in the thickness direction) as necessary, and brushing at least one surface. However, the artificial leather used in the present invention is not limited to such a production method.

The artificial leather of the present invention may have a surface finished with a silver surface after being provided with a polymer elastic body and then not raised. In addition, such artificial leather may have a structure in which an entangled body of ultrafine fibers and / or ultrafine fiber bundles is entangled or integrated with a woven fabric, knitted fabric, spunbond, spunlace, or the like.

The phosphazene compound of the present invention is different from an aminophosphazene compound conventionally used as a water-soluble flame-retardant compound, in which such a water-soluble aminophosphazene compound is modified by controlling the solubility in water by a substituent. The use of a crystalline compound is important and a major feature.

That is, by changing the aminophosphazene compound of the present invention to such a modified compound, the affinity for ultrafine fibers is enhanced, and the aminophosphazene compound is exhausted despite being solid at room temperature. It was something that could be done.

Even if a conventional water-soluble phosphazene compound is used for the ultrafine fibers of the present invention, such a compound is not exhausted at all and cannot impart flame retardancy.

That is, the present invention provides, as such a modified phosphazene compound, the following formula (I) and the following (I)
I) At least one compound represented by the formula is used.

[0029]

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(X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.)

[0031]

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(X _{1 to} X ₄ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) The following (I) As apparent from the formula and the following formula (II), by introducing a phenoxy group to a part of the amino group,
The present inventors have sought to obtain a water-insoluble phosphazene compound, and have determined that the phosphazene compound can be exhausted simultaneously with dyeing in the same manner as a disperse dye. That is, by using such a specific compound,
It was possible for the first time to perform flame retardant treatment.

As the phosphazene compound, those having a total number of phenoxy groups of 2 or more in the phosphazene compound are particularly preferably used from the viewpoint of the exhaustion efficiency of the polyester fiber. Further, the phosphazene compound used in the present invention contains nitrogen having a flame-retardant assisting action, and thus exhibits a more effective flame-retardant effect.

In actual use of the phosphazene compound of the present invention, it is preferable to use it by finely dispersing it in water.
The method for finely dispersing in water is not particularly limited, but the following method is preferably used from the viewpoint of dispersion efficiency.

That is, the phosphazene compound, the dispersant, and water are mixed, stirred, and dispersed. A method of pulverizing and dispersing this dispersion with a glass bead pulverizer is preferably used. As another method for finely dispersing the compound in water, a method in which a solvent capable of dissolving the phosphazene compound is used, followed by mixing with water while stirring to emulsify the compound can be employed.

It is preferable that the phosphazene compound has a fine particle size from the viewpoint of uniform exhaustion to artificial leather and stability of the dispersion, and the phosphazene compound preferably has a particle size of 10 μm or less. It is preferably 5 microns or less, particularly preferably 1 micron or less. That is, if it exceeds 10 microns, it is difficult to obtain dispersion stability when used as a flame-retardant processing agent, the exhaustion property is reduced, and as a result the utilization efficiency is undesirably reduced. As the lower limit, the finer the finer, the better. However, considering workability and economical efficiency in the process of producing fine particles, a particle size of about 0.5 μm is a standard.

The amount of the phosphazene compound of the present invention is, for example, FMVSS No. In order to satisfy the flame retardancy that passes 302 (automotive interior material combustion test standard), it depends on the phosphorus element content in the phosphazene compound.
It is preferable to add 1.0% by weight of phosphorus element. If it is less than 0.3% by weight, sufficient flame retardancy cannot be obtained. Further, if the weight exceeds 1.0% by weight, there is no problem, but the flame retardant performance is saturated, which is economically disadvantageous.

As a method of exhausting such a phosphazene compound into artificial leather, the easiest method is to introduce a finely dispersed phosphazene compound into a dyeing bath and to simultaneously perform dyeing and flame-retardant processing. It is. In that case,
In consideration of the exhaustion efficiency, the phosphorus element in the phosphazene compound is preferably 0.3% based on the total weight of the artificial leather.
The dosage is adjusted so as to be exhausted in the range of １．０1.0% by weight.

The effects of the present invention will not be impaired by appropriately adding other dyes, pH adjusters, leveling agents and the like used in ordinary dyeing to such a dyeing bath. As such a dye bath, it is preferable to adopt a dye bath ratio of 1: 5 to 1: 100, and more preferably 1: 5 to 1:50, from the viewpoint of the exhaustion efficiency of the phosphazene compound.

The treatment temperature in the bath exhaustion treatment is as follows:
Preferably 100 ° C. or higher, more preferably 120 ° C. to 1
The temperature should be 30 ° C. If the treatment temperature is lower than 100 ° C., it is not possible to impart sufficient flame retardancy particularly to polyester fibers. Therefore, from the viewpoint of exhaustion efficiency, 1
The treatment is preferably performed in a bath at a temperature of 20 ° C to 130 ° C for 30 to 60 minutes. After the exhaustion treatment in the bath, it is preferable to perform ordinary washing, reduction washing, and drying.

As another exhaustion method, artificial leather is immersed in a fine dispersion of the phosphazene compound of the present invention.
Next, the solution is drained with a mangle, dried at a temperature of 100 to 120 ° C., and then subjected to heat treatment for exhaustion treatment. The temperature condition of the exhaustion treatment is preferably 150 ° C.
Above, more preferably at 170 ° C to 200 ° C for 10 seconds to
It is preferable to perform processing in a processing time in the range of 180 seconds. 150
When the temperature is lower than 0 ° C, sufficient exhaustion of the phosphazene compound cannot be obtained, and the flame retardancy is insufficiently imparted. When the temperature exceeds 200 ° C., the exhaustion property of the phosphazene compound is sufficient,
It is not preferable because yellowing of the ultrafine fibers may occur. After the exhaustion treatment, a step of washing with 40 to 60 ° C. hot water and simply removing the phosphazene compound attached on the surface may be used.

Further, in the step of producing the artificial leather of the present invention, an artificial leather is produced by using a polymer elastic material in which the phosphazene compound has been kneaded in advance, and then treated simultaneously with dyeing to obtain a polyester fiber. It is also a preferred method to apply the phosphazene compound to obtain flame-retardant artificial leather.

Next, examples of the benzimidazole compound used in the present invention include, for example, 2
-(4-Thiazolyl) benzimidazole, 2-methoxycarbonylamino-benzimidazole and the like are preferably used, but are not limited thereto. The amount of the benzimidazole compound attached to the fiber is
Preferably 0.1 to 5% by weight, more preferably 0.1 to 5% by weight.
3% by weight is deposited. If the content is less than 0.1% by weight, there is a problem that sufficient antibacterial and antifungal properties cannot be obtained. On the other hand, if the content is more than 5% by weight, water repellency decreases, which is not preferable.

As the urethane compound containing a polyfluoroalkyl group used in the present invention, a compound represented by the following formula (III) is preferably used.

[0045]

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In the above formula (III), Rf is a group having 4 carbon atoms.
-16 linear or branched polyfluoroalkyl groups, preferably those having a perfluoroalkyl group at the end, but those containing a hydrogen atom or a chlorine atom at the end, Those containing a perfluoroalkylene-containing group or the like can also be used.
A preferred embodiment of the Rf group is a perfluoroalkyl group, particularly preferably a group having 4 to 12 carbon atoms. X
Is, -R -, - CON (Rf ) -Q-, or -SO ₂
N (R ₁ ) -Q- (where R is an alkylene group, R ₁ is a hydrogen atom or a lower alkyl group, and Q is a divalent organic group)
And an alkylene group having 1 to 20 carbon atoms is preferable. A and A1 are preferably each —O—, —N (R ₂ ) — (where R ₂ represents a hydrogen atom or a lower alkyl group). Z is a non-hydrophilic monovalent organic group, including an alkyl group, an aryl group, and a hetero atom;
It represents X-Rf or the like, but is preferably a lower alkyl group from the viewpoint of water repellency and oil repellency. Y is a divalent organic group, preferably has 24 or less carbon atoms, and particularly preferably has 6 to 6 carbon atoms.
Fifteen are preferred, and one containing at least one aromatic or aliphatic ring is preferably employed in view of rigidity of the urethane molecule and improvement of durability. Further, n is one or more positive numbers, and particularly preferably 1 to 3 is selected.

The amount of the polyfluoroalkyl group-containing compound to be attached is preferably 0.1 to 5% by weight with respect to the fiber. If less than 0.1% by weight,
Sufficient water repellency cannot be obtained, and mold resistance becomes insufficient. On the other hand, when it exceeds 5% by weight, it is not practically preferable in terms of cost.

As a method for providing the benzimidazole compound and the polyfluoroalkyl group-containing compound, 0.1 to 10% by weight of the benzimidazole compound and 0% of the polyfluoroalkyl group-containing compound after the phosphazene compound exhaustion treatment are applied. An aqueous solution of 1 to 10% by weight is applied to the fiber surface by any method such as immersion treatment, spray treatment, foam treatment, gravure treatment, etc.
Drying and heat treatment at 00 to 200 ° C. are performed. In the case of an aqueous solution in which the concentration of the benzimidazole compound is less than 0.1% by weight, sufficient fungicidal performance cannot be obtained. On the other hand, when the amount of the aqueous solution exceeds 10% by weight, the water-repellent performance is reduced, which is not practically preferable in terms of cost.

Further, even if the mixed solution contains an appropriate amount of a blocked isocyanate compound, the mixed solution may be used.

As such a heat treatment, a tenter one-step finish in which drying and setting are performed simultaneously can be employed. Heat treatment at a temperature lower than 100 ° C. is not sufficient in terms of durability. On the other hand, when the temperature exceeds 200 ° C., there is a risk of yellowing and embrittlement of the fiber, which is not practically preferable.

[0051]

The present invention will be described in more detail with reference to the following examples. The performance evaluation in the examples was performed by the following method. <Washing method> Home washing machine VH-3410 (Toshiba Corporation)
), 0.2% by weight of weak alkaline detergent "Zab" (registered trademark, manufactured by Kao Corporation) at a temperature of 40 ° C ± 2 ° C, a bath ratio of 1:30, and a treatment for 5 minutes. The solution is drained, dehydrated and rinsed twice for 2 minutes while overflowing. Such a series of operations is defined as one washing. <Evaluation of flame retardancy> JIS L-1091D method (number of times of flame contact)
It measured based on.

The measurement was carried out based on FMVSS No. 302 (combustion standard for automotive interior materials). <Evaluation of fungicide resistance> JIS Z-2911 6.2.2
(Fiber product test; wet method). <Evaluation of water repellency> Measured based on JIS L-1092 spray method.

(Examples 1 to 3, Comparative Examples 1 and 2) The island component was polyethylene terephthalate, the sea component was polystyrene,
An island / sea ratio = 80/20% by weight, a number of islands of 16 islands, and a staple of a polymer mutual array fiber having a composite fineness of about 4 dtex was used. The staple was formed into a web with a card / cloth wrapper. / M < ² > felt was made, this felt was shrunk and dried.
Next, the felt was impregnated with a polyvinyl alcohol aqueous solution and dried.

The sheet was immersed in trichlene, pressed, deseached, and dried. Next, a solution obtained by dissolving a polyester-polyether-based polyurethane in dimethylformaldehyde was impregnated to a solid content of about 35 parts per island fiber, wet-coagulated, dried after removing dimethylformamide and polyvinyl alcohol. .

Next, this sheet was sliced so as to be に in the thickness direction, and the non-sliced surface was subjected to a brushing treatment with sandpaper to obtain an artificial leather in which polyurethane was added to an entangled body of ultrafine fiber bundles. .

Next, using a treating solution containing a dye and a phosphazene compound having the following composition, the mixture was treated at 130 ° C. for 60 minutes at a bath ratio of 1:20 by a liquid jet dyeing machine. <Blending of dyeing and phosphazene compound exhaustion treatment liquid> Disperse dye Dianix Yellow F3G-E (manufactured by Daystar Shahvan Co., Ltd.) 0.10% by weight Dianix Red ACE (〃) 0.06% by weight Dianix Blue FBL-E ( 〃) 0.03% by weight Auxiliary agent Ionnet TD-208 (manufactured by Sanyo Chemical Co., Ltd.) 1.0 g / l Fixer PH-500 (manufactured by Sanyo Chemical Co., Ltd.) 1.0 g / l phosphazene compound [tetraphenoxydiaminocyclo] Triphosphasedin (50% dispersion)] 10.0% by weight Ionet TD-208, which is an auxiliary agent, has an effect of promoting dye dispersibility in a dye bath.
H-500 is an auxiliary usually used as a pH adjuster for a dye bath.

Next, 1 g / l of Sandet G-29 (manufactured by Sanyo Chemical Co., Ltd.) and 2 g of sodium hydroxide (30%)
/ L, 1 g / l of hydrosulfite in a treatment liquid at 80 ° C for 20 minutes, and then reduced at 60 ° C for 1 minute.
After washing with hot water for 0 minutes, further washing with water was performed.

Thereafter, in the above formula (III), Rf is C ₉ F ₁₉ CH ₂ CH ₂ O, X is CONH (CH ₂ ) ₆ , A is NH, A1 is O, Y is (CH ₂ ) ₆ , Z To C ₉ F ₁₉ CH ₂ C
H ₂ , 0.1% by weight of a polyfluoroalkyl group-containing urethane compound having n = 2, 0.05% by weight of 2-methoxycarbonylaminobenzimidazole (Comparative Example 1), 0.1% by weight (implementation) Example 1), a treatment solution containing 1.0 solution% (Example 2), 5.0 solution% (Example 3), and 7.0 solution% (Comparative Example 2) was prepared, and the dyed fabric was immersed. Then, it was squeezed at a pickup rate of 100%, dried with a pin tenter at 120 ° C. for 2 minutes, and heat-treated at 170 ° C. for 30 seconds to obtain a polyester-based fiber structure.

Here, the solution% means the number of g of the solid content in 100 cc of the solution.

The obtained fiber structure has flame retardancy, mold resistance,
The water repellency was evaluated and the results are shown in Table 1.

As shown in Table 1, the flame retardancy was acceptable when the number of times of flame contact was 3 or more. When the content of the fungicide was less than 0.1% by weight (Comparative Example 1), the fungicide was insufficient. When the content was 5% by weight or more (Comparative Example 2), the water repellency was reduced.

(Examples 4 to 6, Comparative Examples 3 and 4)
I) The same treatment and evaluation as in Examples 1 to 3 were carried out except that the phosphazene compound represented by the formula (the total ratio of phenoxy groups: amino groups was 50:50) was used, and the results are shown in Table 1. .

Regarding the flame retardancy, all passed 3 or more times of flame contact. 0.1% by weight of fungicide
If less than (Comparative Example 3), the antifungal property was insufficient. 5
When the content was more than the weight% (Comparative Example 4), the water repellency was reduced.

(Examples 7 to 9, Comparative Examples 5 to 6) Example 1
The dyed and exhausted fabric was treated under the same conditions as described above, with 2-methoxycarbonylaminobenzimidazole being 2.0% by weight, and in the above formula (III), Rf was C ₉ F ₁₉ CH _2.
CH ₂ O, CONH and X (CH _{2) 6,} the NH, A1 and A O, the Y (CH _{2) 6,} a _{Z C 9 F 19 CH 2 CH} 2, n = 2
0.05% (Comparative Example 5), 0.1% (Example 7), 1.0% (Example 8), 5.0% (%) After immersion in the treatment liquid prepared in Example 9), squeezing was performed at a pickup rate of 100%, followed by drying with a pin tenter at 120 ° C. for 2 minutes and heat treatment at 170 ° C. for 30 seconds to obtain a polyester-based fiber structure.

The fungicidal and water repellent properties of the obtained fiber structure
The flame retardancy was evaluated, and the results are shown in Table 2.

For comparison, the dyed and exhausted cloth of Example 7 was replaced with a polyfluoroalkyl group-containing acrylic compound.
It was immersed in a treatment solution containing 0.0 solution% and 2.0 solution% of 2-methoxycarbonylaminobenzimidazole, and treated under the same conditions as in Example 7 (Comparative Example 6).

The results are shown in Table 2. Although mold resistance and water repellency were sufficient, flame retardancy was reduced.

(Examples 10 to 12, Comparative Example 7) Example 1
Using the same fabric used in step 2, tetraphenoxydiaminocyclotriphosphazene (50% by weight dispersion) was added in 2.5%.
Solution% (Example 10), 5 Solution% (Example 11), 10
The cloth was immersed in a treatment bath prepared to have a solution% (Example 12) and a 1.0 solution% (Comparative Example 7), squeezed at a pickup rate of 100%, dried with a pin tenter at 120 ° C. for 1 minute, and dried at 180 ° C. C. x 1 minute.

Thereafter, in the above formula (III), Rf is C ₉ F ₁₉ CH ₂ CH ₂ O, X is CONH (CH ₂ ) ₆ , A is NH, A1 is O, Y is (CH ₂ ) ₆ , Z To C ₉ F ₁₉ CH ₂ C
A treatment liquid containing 0.1% by weight of a polyfluoroalkyl group-containing urethane compound having H ₂ and n = 2 and 1.0% by weight of 2-methoxycarbonylaminobenzimidazole is prepared, and exhaustion treatment is performed first. After immersing the applied dyed fabric,
Aperture at 100% pickup rate, 120 with pin tenter
After drying at a temperature of 170C for 2 minutes, a heat treatment was performed at 170C for 30 seconds to obtain a polyester fiber structure. The fungicidal properties, water repellency, and flame retardancy of the obtained fiber structure were evaluated, and the results are shown in Table 3.
As shown in Table 3, sufficient flame retardancy, mold resistance and water repellency were obtained. However, at a level of 1.0% by weight as a flame retardant (Comparative Example 7), although mold resistance and water repellency could be obtained, sufficient flame retardancy was not obtained.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

According to the present invention, a fungicide which does not generate harmful gas during combustion, is environmentally friendly, maintains flame-retardant performance that meets flameproof standards, and has excellent washing durability. It is possible to stably provide artificial leather having water repellency and water repellency. Such artificial leather is used for automobile interior materials and
It is suitably used not only for materials such as interiors such as furniture and bags, shoes and gloves but also for clothing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D04H 1/42 D04H 1/42 X D06M 13/352 D06M 13/352 15/576 15/576 15/673 15 / 673 F-term (reference) 4F055 AA02 BA11 CA11 CA13 CA16 EA04 EA05 EA12 EA14 EA24 EA29 FA18 FA19 FA39 GA02 HA04 4J002 AC014 AC034 AC074 BB032 BB122 BC032 BD044 CF051 CF061 CF071 CK024 AC002 GT01 AC03 GT04 AC11 AC15 BA83 BA89 CA51 CA52 CA53 4L047 AA27 AB07 AB08 BA03 CB10 CC01 CC16 DA00

Claims (5)

[Claims] A phosphazene compound represented by the following formula (I) and / or (II) in artificial leather in which a polymer elastic body is added to an entangled body of ultrafine fibers and / or ultrafine fiber bundles. 1.5 to 10% by weight, 0.1 to 5% by weight of a benzimidazole-based compound, and 0.1 to 5% by weight of a urethane-based compound containing a polyfluoroalkyl group.
Artificial leather characterized by containing 5% by weight. Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.) (X _{1 to} X ₄ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) 2. The artificial leather according to claim 1, wherein the ultrafine fibers are 0.9 dtex or less. 3. The artificial leather according to claim 1, wherein the total number of phenoxy groups in the phosphazene compound is 2 or more. 4. An artificial leather in which a polymer elastic body is provided to an entangled body of ultrafine fibers and / or ultrafine fiber bundles,
(A) In a dyeing bath containing the phosphazene compound represented by the following formula (I) and / or the following formula (II) in a solid content of 5.0 to 20% by weight, the bath ratio is 1: 5 to 1: 100. And 1
Treating the artificial leather at 00 ° C. or higher, or (B)
5.0 to 20% by weight of the phosphazene compound in solid content
The artificial leather is immersed in a dispersion containing
After subjecting the phosphazene compound to an exhaustion treatment in an atmosphere of 50 ° C. or more, the benzimidazole compound is 0.1 to 10% by weight, and the urethane compound containing a polyfluoroalkyl group is A method for producing artificial leather, comprising applying a mixed aqueous solution containing 0.1 to 10% by weight and heat-treating the mixed aqueous solution. Embedded image (X _{1 to} X ₃ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₃ are either an amino group or a phenoxy group.) (X _{1 to} X ₄ in the formula (I) are either an amino group or a phenoxy group. Y _{1 to} Y ₄ are either an amino group or a phenoxy group.) 5. The phosphazene compound according to claim 3, wherein the total number of phenoxy groups in the phosphazene compound is 2 or more.
The method for producing the artificial leather according to the above.