JP2002266254A - Leather-like sheet and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a leather-like sheet which does not generate an injurious gas, when burned, to which a flame-retardant performance and a washing- durable anti-bacterial property are imparted, and which has a soft hand. SOLUTION: This leather-like sheet in which a polymeric elastomer is imparted to the interlaced products of ultrafine fibers and/or ultrafine fiber bundles is characterized by containing 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 phenoxyr Y1 to Y4 are each either of amino and phenoxy), a quaternary ammonium salt and/or a biguanido group-having compound, and an aminoplast resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet having a composite property excellent in flame retardancy and antibacterial properties and excellent in durability and performance.

[0002]

2. Description of the Related Art In general, synthetic fibers, particularly 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 a property that they burn poorly in self-extinguishing properties, and it is extremely important to provide flame retardancy in the interior field, especially in artificial leather used for railway vehicles and automobile seats, For example, materials used as curtains or blackout curtains as interior materials are specified by the 45 ° micro burner method, the coil method, or the fire service law such as JIS-L-1091, A-1 method or D method. It is required to pass the combustion test method,
For materials used as automotive interior materials, J
IS-D-1201 or FMVSS No. 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 freely processed as necessary, and currently the method of imparting flame retardancy by post-processing using a halogenated compound is the most principal. It is used regularly. 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 the importance of global environmental issues has recently been emphasized.

[0004] Further, various phosphorus compounds having good flame retardancy and no generation of harmful gas have been studied, but at present, they are not substantially used for post-processing. The reason for this is that most phosphorus-based compounds as flame retardants are generally water-soluble and have poor affinity with polyester fibers. It has plasticizer properties and tends to induce dye bleed-out. Further, the conventional phosphorus-based flame retardant compound has a problem that the phosphorus content in the compound is small, so that it needs to be provided in a large amount.

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

[0006] Fiber products also have a problem in that perspiration from the human body adhering to the fiber surface and bad odors are generated by bacteria and microorganisms that have been propagated by using dirt in the air as a nutrient source.

Hitherto, various antibacterial processed fiber products have been developed, and Japanese Patent Publication No. 2-30340 discloses a method of applying an organosilicone having a quaternary ammonium base. Ammonium salt antimicrobial agents provide laundry durability in cotton products, but do not have long-lasting efficacy on laundry in synthetic fiber products such as polyester fibers. In addition, Japanese Patent Laid-Open No. 1-1
In the processing method using a quaternary ammonium salt and a melamine resin in combination disclosed in Japanese Patent No. 1076, antimicrobial durability can be obtained, but in the case of flame-retardant polyester fibers, the melt viscosity during combustion increases, Necessary flame retardancy cannot be obtained due to low drip property.

Under these circumstances, in order to create a safe and comfortable living environment, it is desired to develop a leather-like sheet having both flame retardancy and antibacterial properties.

[0009]

DISCLOSURE OF THE INVENTION In view of the background of the prior art, the present invention has a combined function of imparting flame-retardant performance in which no harmful gas is generated during combustion and antibacterial property with washing durability, and It is intended to provide a soft leather-like sheet with a soft texture.

[0010]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the leather-like sheet of the present invention is a leather-like sheet obtained by adding a macromolecular elastic body to an entangled body of ultrafine fibers and / or ultrafine fiber bundles, wherein the following formulas (I) and / or (II) are used. And a compound having a quaternary ammonium salt and / or a biguanide group, and an aminoplast resin.

[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 Is a method of producing a leather-like sheet in which a polymer elastic body is provided to an entangled body of ultrafine fibers and / or ultrafine fiber bundles, wherein (A) the formula (I) and / or (II) Is immersed in a dispersion containing a phosphazene compound, and subjected to exhaustion treatment of the phosphazene compound at a temperature of 100 ° C. or more in the dispersion, and then has a quaternary ammonium salt and / or a biguanide group. Providing a mixed treatment liquid containing a compound and an aminoplast resin, or (B) a dispersion containing a phosphazene compound represented by the formula (I) and / or (II); Quaternary ammonium salts and Alternatively, after a treatment of immersion in a mixed treatment solution comprising a compound having a biguanide group and an aminoplast resin, followed by dehydration and drying, heat treatment at a temperature of 150 ° C. or more. It is.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention has the above object, that is, it has a combined function of imparting anti-bacterial properties and a flame-retardant property that does not generate harmful gas during combustion, and has a soft texture. The leather-like sheet was studied diligently, and a combination of a phosphazene compound, a compound having a quaternary ammonium salt and / or a biguanide group, and three or four specific compounds of an aminoplast resin was included in the leather-like sheet. However, they have sought to solve these problems 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 a leather-like sheet.

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 leather-like sheet 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 reduction is made into a short fiber, and a card cloth wrapper or a random webber is used. To form an entangled sheet by applying 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.

The leather-like sheet can be obtained by half-cutting (cutting: cutting into several pieces in the thickness direction) the above-mentioned sheet containing a polymer elastic material, if necessary, and brushing at least one surface. Although it is possible, the artificial leather used in the present invention is not limited to such a production method.

The leather-like sheet of the present invention may have a surface finished with a silver surface without being raised after a polymer elastic body is provided on the surface. 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 the leather-like sheet and stability of the dispersion, and the phosphazene compound preferably has a particle size of 10 μm or less. It is more 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, but it is preferably 0.1 to the total weight of the leather-like sheet.
It is preferable to add the phosphorus element so as to contain 3 to 1.0% by weight. 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.

Next, specific examples of the compound having a quaternary ammonium salt or a biguanide group used in the present invention include:
3- (trimethoxylyl) propyldimethyloctadecyl ammonium chloride, benzalkonium chloride, benzethonium chloride, polyoxyethylenetrimethylammonium chloride, alkyltrimethylammonium salt,
Phenododecium bromide, isooctylphenoxyethoxyethyldimethylbenzylammonium chloride,
(3,4-dichlorobenzyl) dodecyldimethylammonium chloride, alkyldimethylethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, diisobutylcresoxyethoxyethylbenzylammonium salt, 1,1'-hexamethylenebis [5
-(P-chlorophenylbiguanide)] hydrochloride, dodecylguanidine hydrochloride, poly-oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride (hereinafter referred to as PMIEC), bis- (p-chloro-
Examples thereof include, but are not limited to, phenylbiguanide) hexane and polyhexamethylenebiguanidine hydrochloride. In addition, the quaternary ammonium salt has a quaternary ammonium salt in the main chain.
It is preferable that the compound has an ammonium salt and that the compound having a biguanide group has a biguanide group in the main chain from the viewpoint of washing durability of antibacterial performance.

The amount of the compound having a quaternary ammonium salt or a biguanide group or the amount of the compound having a quaternary ammonium salt and a biguanide group is 0.05 to 3% by weight based on the total weight of the leather-like sheet. And more preferably 0.1 to 2% by weight. If the amount is less than 0.05% by weight, there is a problem that sufficient antimicrobial washing durability cannot be obtained. On the other hand, if the amount exceeds 3% by weight, the flame retardancy tends to decrease.

Next, the aminoplast resin in the present invention includes melamine resins such as trimethylol melamine and hexamethylol melamine, urea resins such as dimethylol propylene urea, dimethylol ethylene urea and dimethylol hydroxy urea, and dimethylol uron. However, the present invention is not limited thereto. The amount of adhesion of these resins is set to 0.1.
Within a range of from 0.01 to 0.5% by weight, preferably from 0.05 to 0.5% by weight.
0.3% by weight.

In addition, as long as the flame retardancy is not impaired, a synthetic resin such as urethane, epoxy or acrylic may be used.

Here, the reason why the antibacterial performance is durable is that the compound having a quaternary ammonium salt or a biguanide group of the present invention or the compound having a quaternary ammonium salt and a biguanide group is applied to the fiber surface. It is presumed that the fiber surface layer was exhausted by the heat treatment. In addition, whether the compound having a quaternary ammonium salt and a biguanide group is present in the surface layer of the fiber is determined as follows.
It can be confirmed by dyeing the treated sample with a gold-containing dye or the like and observing the fiber cross section with an optical microscope.

As a method of exhausting the phosphazene compound of the present invention into the leather-like sheet used in the present invention, it is easiest to put a finely dispersed phosphazene compound in a dyeing bath and to simultaneously carry out dyeing and flame-retardant processing. It is a way. In that case, in consideration of the exhaustion efficiency, the phosphorus element in the phosphazene compound of the present invention is exhausted in the range of 0.3 to 1.0% by weight based on the total weight of the leather-like sheet used in the present invention. Adjust the input amount.

Other dyes used for ordinary dyeing, p
The effect of the present invention is not impaired even if an H adjuster, a leveling agent and the like are appropriately added. In light of the exhaustion efficiency of the phosphazene compound, the dye bath ratio is preferably 1: 5 to 1: 100, and more preferably 1: 5 to 1:50.

The treatment temperature in the bath exhaustion treatment is 1
The temperature is set to 00 ° C. or higher. If the treatment temperature is lower than 100 ° C., there arises a problem that the flame retardancy cannot be sufficiently imparted particularly to the polyester fiber. Therefore,
From the viewpoint of exhaustion efficiency, it is 30 to
It is preferable to perform the treatment in a bath for 60 minutes, and then perform ordinary washing, reduction washing, and drying.

Thereafter, immersion treatment, spray treatment and foam treatment are carried out using a liquid mixture containing a quaternary ammonium salt or a compound having a biguanide group or a compound having a quaternary ammonium salt and a biguanide group and an aminoplast resin. And applied to the leather-like sheet by any method such as gravure treatment, preferably at 150 ° C. or higher,
More preferably, the heat treatment is performed under a temperature condition of 170 ° C to 200 ° C. The heat treatment time is preferably from 10 seconds to
The treatment is performed for 180 seconds, more preferably for 30 seconds to 120 seconds. If the temperature is lower than 100 ° C., the durability is insufficient.
When the temperature exceeds 00 ° C., embrittlement and yellowing of the fiber occur, which is not preferable.

Further, as another production method, a phosphazene compound represented by the above formula (I) or (II) of the present invention, a compound having a quaternary ammonium salt or a biguanide group, or a quaternary ammonium salt and a biguanide A compound having a group and an aminoplast resin are immersed in a mixed solution, drained with a mangle, dried at a temperature of 100 to 120 ° C, and then at a temperature of 150 ° C or higher, preferably 170 ° C to 200 ° C, It is preferable to perform the exhaust treatment under a heat treatment condition of a treatment time of 10 seconds to 180 seconds, preferably 30 seconds to 120 seconds. When the temperature is lower than 150 ° C., sufficient exhaustion of the flame retardant of the present invention cannot be obtained, and the flame retardancy is insufficiently imparted. When the temperature exceeds 200 ° C., the exhaustion of the flame retardant of the present invention is sufficient, but yellowing of ultrafine fibers occurs, which is not preferable. After exhaustion treatment of the flame retardant of the present invention, a step of washing with warm water at 40 to 60 ° C may be used.

[0048]

The present invention will be described below in more detail with reference to examples. The performance evaluation in the examples was performed by the following method. <Washing method> Home washing machine VH-3410 (Toshiba Corporation)
), 0.2% weak alkaline detergent "Zab" (registered trademark, manufactured by Kao Corporation), temperature 40 ° C ± 2 ° C, bath ratio, 1: 3
After treatment at 0 for 5 minutes, drainage and dehydration are performed, and rinsing is repeated twice for 2 minutes while overflowing. This is one wash. <Flame retardancy evaluation> FMVSS No.302 (combustion standard for automotive interior materials) Passed within 100mm / min. JIS-L1091D method (coil method) Passed 3 or more times of flame contact. <Evaluation of antibacterial property> The law was adopted. The test strain was Stapylococcus-aureus I
ID1677 (MRSA) was used. The test method was as follows. The test solution was poured into a sterilized sample cloth, the number of viable cells was measured after culturing at 35 ° C. for 18 hours, and the number of cells relative to the number of cells was measured.

Under the condition of log (B / A)> 2, log
(B / C) was defined as the difference in the number of bacteria, and 1.6 times or more was regarded as the acceptable level. Here, A represents the number of bacteria collected and dispersed immediately after inoculation of the unprocessed product, B represents the number of bacteria collected and dispersed after 18 hours of culturing of the unprocessed product, and C represents the number of bacteria collected and dispersed after culturing the processed product for 18 hours.

(Examples 1-2, Comparative Examples 1-3) Polyethylene terephthalate as the island component, polystyrene as the sea component,
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. Immerse this sheet in Tricline,
After being squeezed and dewatered, it was dried. Then, polyester-
A solution obtained by dissolving a polyether-based polyurethane in dimethylformaldehyde is converted into a solid content of about 3 per island fiber.
It was impregnated so as to be 5 parts, wet coagulated, dried after removing dimethylformamide and polyvinyl alcohol.

Next, this sheet is sliced so as to be halved in the thickness direction, and the non-sliced surface is subjected to a raising treatment with sandpaper to obtain a leather-like sheet in which polyurethane is added to an entangled body of ultrafine fiber bundles. Was.

Next, a treating solution containing a dye and a flame retardant having the following composition was used, and the bath ratio was set to 1:20 by a liquid jet dyeing machine.
The treatment was performed at 30 ° C. for 60 minutes. <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 Industries, Ltd.) and 2 g of sodium hydroxide (30%)
Washing in a treatment solution consisting of 1 g / l of hydrosulfite at 80 ° C. for 20 minutes.
After washing with hot water for a minute, further washing with water was performed.

Next, 0.04 solution% (comparative example 1), 1.0 solution% (example 1), and 2.0 solution% of poly-oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride were used. (Example 2) Trimethylolmelamine was added to each aqueous solution containing 3.5 solution% (Comparative Example 2) in an amount of 0.1%.
After preparing a treatment liquid to which 2% by solution was added, the leather-like sheet previously treated with flame retardant was immersed, squeezed with a pickup 100%, dried with a pin tenter at 120 ° C. × 2 minutes, and dried at 180 ° C.
Heat treatment was performed for 30 seconds to obtain a leather-like sheet.

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

The flame retardancy and antibacterial properties of the obtained leather-like sheet were evaluated, and the results are shown in Tables 1 and 2. For comparison, the amount of trimethylolmelamine was set to 0.6 solution% (Comparative Example 3).
And treated under the same processing conditions as in Example 1.

As shown in Tables 1 and 2, the content of the antibacterial agent was 0.1%.
At less than 05% by weight (Comparative Example 1), the antibacterial properties after washing were insufficient. When it exceeds 3.0% by weight (Comparative Example 2)
Then, the flame retardancy decreased. When the content of the aminoplast resin was 0.5% by weight or more (Comparative Example 3), the flame retardancy also decreased.

(Examples 3 and 4, Comparative Examples 4 and 6) Except that a phosphazene compound represented by the above formula (II) (total ratio of phenoxy groups to amino groups was 50:50) was used as a flame retardant. The same treatment and evaluation as in Examples 1 and 2 were performed, and the results are shown in Tables 1 and 2. Both flame retardancy and antibacterial properties showed the same good results as in Examples 1 and 2.

(Examples 5 and 6, Comparative Examples 7 and 8) Example 1
Using the same leather-like sheet obtained in the above, using a dyeing treatment solution having the following composition, by a liquid jet dyeing machine, a bath ratio of 1:20 and 1
The treatment was performed at 30 ° C. for 60 minutes. Thereafter, drying was performed at 120 ° C. × 1 minute. <Blending of dyeing treatment liquid> Disperse dye Dianix Yellow F3G-E (manufactured by Taisha Shahvan Co., Ltd.) 0.02% by weight Dianix Red ACE (〃) 0.03% by weight Dianix Blue FBL-E (〃) 0.30 % By weight Ionette 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 Next, tetraphenoxydiaminocyclotrioxide, which is a phosphazene compound, is used. 1.0% phosphazene (50% dispersion)
4. Solution% (Comparative Example 7), 2.5 Solution% (Example 5),
A treatment solution containing 0% by solution (Example 6) and 15% by solution (Comparative Example 8) was prepared.
Oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride) was added to a treatment liquid containing 1.0% ows and trimethylolmelamine at a 0.2% solution.
After soaking the previously obtained dyed cloth, the pickup rate is 100%
After drying at 120 ° C for 1 minute with a pin tenter,
Heat treatment was performed at 0 ° C. × 1 minute. The flame retardancy and antibacterial properties of the obtained leather-like sheet were evaluated, and the results are shown in Tables 3 and 4.

As shown in Tables 3 and 4, at a level of less than 0.2% by weight as the phosphorus element of the flame retardant (Comparative Example 7), the antibacterial properties were sufficient, but the flame retardancy was insufficient. . In addition, at the level of 10% by weight or more as a phosphazene compound (Comparative Example 8), flame retardancy and antibacterial performance were obtained, but the rub fastness of the treated cloth was reduced.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

According to the present invention, antibacterial properties which are friendly to the global environment, maintain flame-retardant properties that meet flameproof standards, and have excellent washing durability without generating harmful gases during combustion. Can be stably provided. Such a leather-like sheet is suitably used not only for materials such as interior materials for automobiles and furniture, but also for materials such as bags, shoes and gloves, and also for clothing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) D06M 15/423 D06M 15/423 15/673 15/673 F term (reference) 4F055 AA02 BA11 CA11 CA13 EA04 EA05 EA12 EA14 EA24 EA29 FA18 FA19 FA23 FA39 GA02 HA04 4J002 AC001 AC011 AC031 AC071 BD041 CK021 CL001 CQ012 EN136 ER026 FD136 4L033 AA07 AA08 AB07 AC05 AC10 AC11 BA83 CA36 CA51 CA52 4L047 AA27 AB08 BA03 BA07 CA19

Claims (6)

[Claims] A phosphazene compound represented by the following formula (I) and / or (II) in a leather-like sheet in which a polymer elastic body is provided to an entangled body of ultrafine fibers and / or ultrafine fiber bundles. And a compound having a quaternary ammonium salt and / or a biguanide group, and an aminoplast resin. 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 leather-like sheet according to claim 1, wherein the ultrafine fibers are 0.9 dtex or less. 3. The leather-like sheet according to claim 1, wherein the total number of phenoxy groups in the phosphazene compound is 2 or more. 4. The leather-like sheet according to claim 1, wherein the quaternary ammonium salt has a quaternary ammonium salt in a main chain. 5. The leather-like sheet according to claim 1, wherein the compound having a biguanide group has a biguanide group in a main chain. 6. A leather-like sheet in which a polymer elastic body is provided to an entangled body of ultrafine fibers and / or ultrafine fiber bundles,
(A) A dispersion containing a phosphazene compound represented by the following formula (I) and / or the following formula (II):
After immersion and exhaustion treatment of the phosphazene compound in the dispersion at a temperature of 100 ° C. or higher, a mixed treatment liquid containing a compound having a quaternary ammonium salt and / or a biguanide group and an aminoplast resin is used. Or (B) a dispersion containing a phosphazene compound represented by the following formula (I) and / or (II); and a compound having a quaternary ammonium salt and / or a biguanide group. A method for producing a leather-like sheet, comprising: performing a treatment of immersion in a mixed treatment solution comprising an aminoplast resin and a dewatering / drying treatment, followed by heat treatment at a temperature of 150 ° C. or more. 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.)