JP2001279583A - Leather-like sheet with excellent water repellency, oil repellency and antistatic performance - Google Patents

Abstract

(57) [Abstract] [Problem] It has water repellency, oil repellency and antistatic performance,
Provide a suede-like leather-like sheet with excellent appearance. SOLUTION: It is composed of an ultrafine fiber and a polycarbonate-based polyurethane resin, and a fluorine atom-containing compound (A) is 0.05 to 0.05 to the total weight of the fiber and the polyurethane resin.
A leather-like sheet provided with 8% by weight and 0.01 to 5% by weight of an antistatic agent (B). Such a leather-like sheet comprises a fluorine atom-containing compound (A) and an antistatic agent (B). By treating the sheet in a bath in which is present.

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 both excellent water and oil repellency and good antistatic performance and having a high-class feel, and a method for producing the same.

[0002]

2. Description of the Related Art It is known to provide a textile product with a fluorine compound for the purpose of imparting water / oil repellency and antifouling performance to the textile. For example, Japanese Unexamined Patent Publication No. 7-34384 discloses that a textile product is treated with a salt of a divalent or higher-valent metal, and then treated with a fluoropolymer having a hydrophilic property capable of coordinating with the metal. A method for imparting water and oil repellency is described. Also, JP-A-2-259165 discloses that
A method is described in which a polyamide fiber is pretreated with a styrene sulfonic acid-based treating agent, and then treated with a fluorine-based water / oil repellent to apply a water / oil repellent treatment to the amide fiber.

[0003] Also, a technique for imparting an antistatic property in addition to water and oil repellency is also known.
No. 2,291,481 discloses 2,4-diphenyl-4-.
An acrylic monomer (a) having a perfluoroalkyl group, an acrylic monomer (b) having an oxyalkylene group, and an acrylic acid alkyl ester monomer each using methyl-1-pentene as an essential chain transfer agent Water-repellent, oil-repellent, dirt-removing, and antistatic properties obtained from a monomer (c) comprising at least one of a monomer and an alkyl methacrylate-based monomer. It has been proposed for use as an oil repellent.

[0004]

A leather-like sheet is generally provided with an elastic polymer typified by polyurethane on a non-woven fabric made of ultrafine fibers and fluffing the surface, or forming a resin coating layer on the surface. Although it is manufactured by providing, it is manufactured from a fiber material having a low hygroscopic property as an ultrafine fiber, and a polyurethane resin is also generally low in a hygroscopic property, so that the above JP-A-7-34384 and JP-A-2-259165 are used. According to the method described in Japanese Patent Application Laid-Open Publication No. H11-157, the antistatic performance is significantly deteriorated. This tendency is particularly true when the fineness of the constituent fibers is reduced for the purpose of high-quality suede tone, and when a highly hydrophobic polyurethane resin such as a polycarbonate-based polyurethane resin is used to obtain high durability. Will be noticeable.

[0005] In recent years, there has been a demand for artificial leather using a leather-like sheet using a polycarbonate-based polyurethane resin because of the demand for high durability. It has a higher chargeability than the case where it is used, and causes a deterioration in a feeling of wearing as clothing due to electrostatic discharge, a sticking to a body, a deterioration in a feeling of use in interior use, and the like, and there has been a demand for improvement. In order to impart antifouling properties to artificial leather, it is indispensable to provide water repellency and oil repellency as artificial leather. That is, imparting antistatic properties and water / oil repellency to artificial leather is extremely important, and particularly important for artificial leather using polycarbonate-based polyurethane.

In order to solve this problem, a method in which an antistatic agent is applied in advance before applying the fluorine-based water repellent or a method in which the antistatic agent is applied after the treatment with the fluorine-based water-repellent is first used. It is possible, but in the case of the former method,
Antistatic properties and water / oil repellency are not compatible due to elution of the antistatic agent or poor adhesion of the water repellent agent. Conversely, in the latter method, the antistatic ability is reduced due to poor permeability of the antistatic agent. It did not improve, and it was difficult to reach the practical level with either method.

[0007] A method of achieving both water repellency and oil repellency and antistatic performance by simply mixing a fluorinated water repellent and an antistatic agent has the best workability and the like. In this case, the water- and water- and oil-repellent emulsion is destroyed, the performance is reduced, and scum is generated. Note that the above-mentioned Japanese Patent Application Laid-Open No. 9-2914
No. 81 proposes the above-mentioned copolymer as a fiber processing agent having both excellent water repellency and oil repellency and good antistatic performance, but such a copolymer is light-fast. When it is applied to a suede-like artificial leather composed of microfibers and polyurethane resin, it causes deterioration of appearance and hardening of texture, and it is difficult to apply to this application. Met.

[0008]

DISCLOSURE OF THE INVENTION The present invention provides excellent water repellency and excellent water repellency.
It is an object of the present invention to provide a leather-like sheet having both oil repellency and good antistatic performance, and having a high-class feel. As a result of intensive studies to solve this problem, the inventor has found that
In the treatment of a leather-like sheet comprising a strong hydrophobic fiber and a polycarbonate-based polyurethane resin, a specific ratio of an antistatic agent, a water / oil repellent treatment agent, preferably a nonionic surfactant is treated in the same bath. It has been found that a leather-like sheet having both water-repellent oil-repellent performance and antistatic performance, in which a water-repellent and an antistatic agent substantially coexist on the surface, can be obtained.

That is, the present invention comprises a fiber and a polycarbonate-based polyurethane resin, and the weight ratio (fiber / polycarbonate-based polyurethane resin) is 95/5.
In a leather-like sheet having a weight ratio of 40 to 60, the fluorine-containing compound (A) is 0.05 to 8% by weight based on the total weight of the fiber and the polyurethane resin, a cationic antistatic agent, and an anionic antistatic agent. At least one antistatic agent (B) selected from the group consisting of an amphoteric antistatic agent and a nonionic antistatic agent is provided in an amount of 0.01 to 5% by weight, a water repellency of 70 points or more, and a friction voltage of 800 V. A leather-like sheet characterized by the following:
The nonionic surfactant (H) having an LB value of 8 or more is used in an amount of 0.01 to 0.01% based on the total weight of the fiber and the polyurethane resin.
1.0% by weight of a fluorine atom-containing compound
(A), antistatic agent (B), nonionic surfactant (H)
The present invention relates to a leather-like sheet having excellent water / oil repellency and good antistatic performance, and having a luxurious feel, characterized in that the weight composition ratio satisfies the following relationship. 0 ≦ (H) / (A) ≦ 0.25 0 ≦ (H) / (B) ≦ 1.5

In the present invention, as the polycarbonate-based polyurethane resin constituting the leather-like sheet, one using polycarbonate diol (C) as at least a part of the raw material polymer diol, preferably polycarbonate diol (C) is a polyurethane diol A polyurethane resin containing 5% by weight or more based on the total weight of the polymer diol used in the production, more preferably a number average molecular weight of 50%
A diol mixture comprising a polycarbonate polymer diol (C) of 0 to 3000 and a polymer diol (D) having a number average molecular weight of 500 to 3,000 selected from the group consisting of polyester diol, polylactone diol and polyether diol (D) ( E) and the organic diisocyanate (F) at an equivalent ratio of NCO / OH of 0.5
The intermediate diol (G) having a substantially terminal OH obtained by reacting in a quantitative relationship such that it becomes 0.99 was used as a soft segment, and this was reacted with a diisocyanate compound and a chain extender. A so-called segmented polyurethane resin is suitably used in terms of light resistance, flexibility and the like.

The weight ratio of the polycarbonate polymer diol (C) to the diol mixture (E) is desirably from 5% by weight to 80% by weight. If the content is less than 5% by weight, the hydrophobicity and light resistance, which are the characteristics of the leather-like sheet using the polycarbonate-based polymer diol (C), are reduced, and the chargeability is sufficiently low even without the treatment of the present invention, and the antistatic property is obtained. No need to perform processing. Also,
Since the content of the polycarbonate-based polymer diol (C) is low, the physical properties such as light resistance are reduced, and the resin is unsuitable as a leather-like sheet. If it exceeds 80% by weight,
The obtained polyurethane becomes rigid, and the flexibility required as a leather-like sheet is impaired, which is not preferable.

The number average molecular weight of the polymer diol (C) or (D) is preferably from 500 to 3,000, more preferably from 700 to 2,500. If it is less than 500, the flexibility of the polyurethane tends to be lost and the heat resistance tends to decrease, which is not preferable. Conversely, if it exceeds 3,000, the urethane group concentration is inevitably reduced,
Not only is it difficult to obtain urethane having a good balance of mechanical properties, flexibility, cold resistance, heat resistance, and durability, but also there are difficulties in the industrial production of the polymer diol, which is not preferable.

The polycarbonate diol (C) used in the present invention can be obtained, for example, by reacting a carbonate compound with a diol. As the carbonate compound, dimethyl carbonate, diphenyl carbonate, ethylene carbonate and the like can be used.
Diols are lower alcohols and may be substituted fats such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol and dodecanediol. Aliphatic diols, cyclohexanediols, alicyclic diols such as hydrogenated xylylene glycol, and one or a mixture of two or more aromatic diols such as xylylene glycol are used. Among them, aliphatic diols, especially butanediol, One or a mixture of two or more aliphatic diols having a carbon chain length of 4 to 9 such as methylpentanediol, hexanediol, heptanediol, octanediol, and nonanediol are cold-resistant and flexible. It is preferably used in terms of.

The polymer diol (D) used in the present invention is a polymer diol having a number average molecular weight of 500 to 3,000 selected from the group consisting of polyester diol, polylactone diol and polyether diol. In the present invention, the polyetherester diol is included in the polyetherdiol.

[0015] Among them, the polyester diol can be obtained, for example, by reacting a dibasic acid with a diol.
Dibasic acids include succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
An aliphatic dibasic acid such as brassic acid, or one or a combination of aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid can be used. Among them, aliphatic dibasic acids, particularly dibasic acids having a methylene chain length of 4 to 8, such as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, are more preferably used in terms of flexibility and economy. Can be As a diol,
Lower diols, which may be substituted, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, aliphatic diols such as dodecanediol, One kind of alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol and aromatic diols such as xylylene glycol or a mixture of two or more kinds thereof is used in terms of cold resistance, flexibility and durability. Among them, aliphatic diols are one or more aliphatic diols having a carbon chain length of 4 to 9, such as butanediol, methylpentanediol, hexanediol, heptanediol, octanediol, and nonanediol. Rakara mixture of two or more is cold resistance selected, flexibility, are preferably used in terms of durability.

Examples of the polylactone diol include poly-ε-caprolactone diol, poly-trimethyl-
ε-caprolactone diol, poly-β-methyl-δ-
Valerolactone diol and the like.

The polyether diol includes, for example, polytetramethylene glycol, polypropylene glycol, polyethylene glycol and the like, and also includes polyether ester diol generally used for polyurethane.

Intermediate diol (G) used in the present invention
Is a method in which a mixture of polymer diol (E) containing polymer diols (C) and (D) as essential components has an equivalent ratio of organic diisocyanate (F) to NCO / OH of 0.5 to 0.99.
It is obtained by reacting in a quantitative relationship such that NCO /
If the equivalent ratio of OH is less than 0.5, it is difficult to balance the flexibility, cold resistance and heat resistance of the obtained polyurethane resin composite, and the effect of the present invention cannot be sufficiently obtained. Also N
If the equivalent ratio of CO / OH exceeds 0.99, it is difficult to balance the surface properties, feeling, flexibility, cold resistance and heat resistance of the leather-like sheet, which is not preferable.

The organic diisocyanate (F) used in the present invention is, for example, an aromatic diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, or an aromatic diisocyanate. Non-aromatic diisocyanates and the like are used. Above all, a non-aromatic (that is, aliphatic or alicyclic) diisocyanate such as hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and a polyurethane solution obtained. Is impregnated into a non-woven fabric and then wet-coagulated with a non-solvent so that the surface properties and the feeling of the sheet obtained are improved.

No solvent is required for preparing the intermediate diol (G). However, when the viscosity of the intermediate diol (G) is high and it is difficult to handle it, for example, when NCO / OH is close to 1, the reaction is carried out in a solvent. May be. Such solvents include, for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate,
A commonly used solvent such as methyl ethyl ketone and tetrahydrofuran is used.

In the present invention, a low-molecular-weight diol having a molecular weight of less than 500 is mixed with each of the polymer diol (E) and the intermediate diol (G) as long as the object of the present invention is not impaired. Although there is no particular limitation, components normally used as chain extenders such as low molecular weight linear diols such as ethylene glycol, butanediol and hexanediol, and aromatic diols such as xylylene glycol are substantially Is not preferred in terms of the mechanical properties, flexibility, and cold resistance of the polyurethane resin.

As the type of diisocyanate used for the hard segment of the polyurethane resin of the present invention, that is, used for the chain extension reaction, 4,4-diphenylmethane diisocyanate is desirable from the viewpoint of economy and process passability. There is no particular limitation on the amount of 4,4-diphenylmethane diisocyanate used, and the viscosity of the polyurethane solution, the molecular weight of the polymer diol, the reaction solvent, the polymer diol,
Although it depends on the water content in the low molecular weight diol, the NCO / OCO is usually used in terms of the mechanical strength of the obtained polyurethane resin and the storage stability of the polyurethane resin solution.
H equivalent ratio of 0.90 to 1.2, more preferably 0.95
１．１1.10. It is also possible to use 4,4′-diphenylmethane diisocyanate in combination with another isocyanate as long as the effects of the present invention are not impaired. Such isocyanates include 2,4- or 2,6-
Non-aromatics such as aromatic diisocyanates such as tolylene diisocyanate, meta- or para-phenylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate Diisocyanate and the like are used.

Examples of the chain extender include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol which may be substituted with a lower alcohol. , Aliphatic diols such as dodecane diol, cyclohexane diol, alicyclic diols such as hydrogenated xylylene glycol, aromatic diols such as xylylene glycol, and also one or a mixture of two or more kinds such as diethylene glycol and lower diamines. Among them, aliphatic diols, especially ethylene glycol and butanediol, are preferably used in terms of balance of texture, flexibility and heat resistance of the obtained polyurethane resin and leather-like sheet. That. The amount used is not particularly limited, but its molecular structure, the blending amount of the polymer polyol component,
Although it depends on the molecular weight, the amount of 4,4'-diphenylmethane diisocyanate used, and the NCO / OH equivalent ratio, it is usually 0.4 to 2 in the equivalent ratio to the polymer polyol.
A value of about 0 is often suitable in terms of texture, flexibility, cold resistance, and heat resistance of the obtained polyurethane resin and leather-like sheet.

A catalyst is not always required when polymerizing the polyurethane resin, but catalysts used in the production of ordinary polyurethanes, for example, metal compounds such as titanium tetraisopropoxide and dibutyltin dilaurate, tetramethylbutanediamine, , 4-diazabicyclo (2,
2,2) Tertiary amines such as octane can be used.

As the solvent for the polyurethane resin, for example, commonly used solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methyl ethyl ketone and tetrahydrofuran are used.

When the polyurethane resin thus obtained is used, various additives used in conventional polyurethanes, such as flame retardants such as phosphorus compounds and halogen-containing compounds, as long as the effects of the present invention are not impaired, Antioxidant,
UV absorbers, pigments, dyes, plasticizers, surfactants and the like can be added.

When such a polyurethane resin is used for a leather-like sheet, the fibrous substrate constituting the leather-like sheet may be a knitted fabric obtained from fibers of polyamide, polyester, polyacryl or the like, or natural fibers such as wool. Any of woven cloth, non-woven cloth and the like can be used. Among them, a nonwoven fabric made of three-dimensionally entangled ultrafine fibers having an average fineness of 0.1 decitex or less is most preferable because it is suitable in terms of texture, touch, and high-grade appearance. Such an ultrafine fiber can be derived from an ultrafine fiber-generating fiber composed of two or more polymer components including a known fiber-forming polyamide resin or polyester resin. For example, a fiber having a sea-island structure in which a polyamide resin or a polyester resin is used as an island component and a polymer which can be easily removed by a solvent or the like is used as a sea component is a typical example of the ultrafine fiber generating fiber.

Examples of the polyamide resin that can be used for the microfiber-generating fiber include 6-nylon and
At least one kind of polyamide selected from 6,6-nylon, 6,10-nylon and other spinnable polyamides having an aromatic group may be mentioned, and the polyester resin may be modified with sulfoisophthalic acid or the like. And at least one polyester selected from polyethylene terephthalate, polybutylene terephthalate, and other spinnable polyesters.

On the other hand, other polymers constituting the ultrafine fiber-generating fiber, for example, the sea component polymer, differ from polyamide resin or polyester resin in solubility or decomposability in a solvent or a decomposer, and differ from polyamide resin or polyester resin. A resin having a low affinity and a resin having a melt viscosity smaller than that of a polyamide resin or a polyester resin fat under spinning conditions are preferable, for example, polyethylene, polypropylene, ethylene-propylene copolymer,
Ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-α-olefin copolymer, polystyrene, styrene-isoprene copolymer, hydrogenated styrene-isoprene copolymer, styrene-
Examples include butadiene copolymers and hydrogenated styrene-butadiene copolymers.

Then, the fiber comprising the polyamide or polyester resin and another polymer is mixed at a predetermined mixing ratio,
Dissolving in the same dissolving system, forming a mixed system and spinning,
In addition, a method in which each polymer is dissolved in a separate dissolving system and the joining-division is repeated a plurality of times at a spinning machine head to form a mixed system and spinning, and further dissolving in separate dissolving systems,
It is manufactured by a method such as spinning while defining the fiber shape in the spinneret. The polyamide resin or polyester resin component in the fiber cross section is 40 to 80% by weight of the polyamide resin or polyester resin component occupying in the fiber. 5
Polyamide- or polyester-based ultrafine fiber-generating fibers in a number of at least 50, preferably 50 to 800 fibers are obtained. If necessary, the ultrafine fiber-generating fiber is subjected to a normal fiber processing step such as drawing or heat setting to produce a fiber having a fineness of 2 to 15 dtex. The average fineness (calculated value) of the polyamide or polyester ultrafine fiber component constituting the ultrafine fiber generating fiber is preferably 0.2 dtex or less, more preferably 0.005 to 0.1 dtex.

Next, the ultrafine fiber-generating fiber is opened with a card, passed through a web to form a random web or a cross-wrap web, and the obtained fiber web is laminated to a desired weight and thickness. Next, the fiber web is subjected to a fiber entanglement treatment by needle punching, water jet, air jet, or the like to obtain a fiber entangled nonwoven fabric.

Then, the nonwoven fabric is coated with a coagulation controlling agent, a release agent, a plasticizer, a stabilizer, an antioxidant, an anti-lightproofing agent, a pigment, a dye and the like, if necessary, in the solution of the polyurethane resin obtained above. Impregnating or applying the composition liquid obtained by adding the composition liquid within a range that does not impair the effects of the invention, and performing wet coagulation or dry coagulation. In the case of ultrafine fiber-generating fibers, the solvent of one resin constituting the ultrafine fiber-generating fibers and the other resin (such as polyamide or the like) before or after impregnation or application of the composition liquid to the fiber-entangled nonwoven fabric Polyester) to obtain ultrafine fibers.

The amount of the polyurethane resin occupying the sheet thus obtained is not particularly limited.
It is often used at 0 to 60%, especially 15 to 45%. If the amount of the polyurethane resin used is small, the feeling is rather stiff, and if it is less than 10%, it becomes remarkable. On the other hand, if the amount of the polyurethane resin used is large, the polyurethane resin tends to be hard or have a texture without swelling.
When the content is more than 0%, the tendency becomes remarkable.

The sheet thus produced can be subjected to a raising treatment with sandpaper or the like on at least one surface, if necessary, to give a fiber-naped suede-like leather-like sheet. Further, a porous or non-porous coating layer obtained from polyurethane can be further provided on at least one surface to obtain a leather-like sheet with silver. Also, the slice can be divided into arbitrary thicknesses in an arbitrary thickness at an arbitrary stage. Furthermore, when performing subtle color adjustment according to consumer's taste, fluorescent dye, trace acid dye, metal-containing complex salt dye,
It may be dyed with a sulfur dye, a sullen dye, a direct dye or a disperse dye, or may be subjected to a softening treatment by a liquid dyeing machine or the like for the purpose of softening the texture.

In the present invention, it is added to a leather-like sheet.
As the fluorine atom-containing compound (A), commercially available water repellents
Anything that has been used can be used. A series of examples
A fluoroalkyl group-containing water repellent is exemplified. Fluoro
Although the alkyl group is not particularly limited, for example, CF
_Three(CF_Two)₇(CH_Two)₁₁OCOCH = CH_Two , CF_Three(CF _Two)
_FourCH_TwoOCOC (CH_Two) = CH_Two3 to 2 carbon atoms such as
Containing 0, preferably 4 to 15 fluoroalkyl groups.
Unsaturation represented by acrylate or methacrylate
Polymerizable without esters and fluoroalkyl groups
Copolymers with one or more compounds may be mentioned.
In this case, a polymerizable polymer containing no fluoroalkyl group is used.
Compounds include, for example, ethylene, vinyl acetate,
Nil, vinyl chloride, vinylidene halide, acrylonitrile
Ryl, styrene, α-methylstyrene, acrylic acid and
Alkyl esters of methacrylic acid and its alkyl esters
And acrylamide and the like.

The amount of the fluorine atom-containing compound (A) used is
It is 0.05 to 8% by weight based on the total weight of the fibers and polyurethane constituting the artificial leather. If the amount is less than 0.05% by weight, the water repellent effect cannot be obtained. If the amount is more than 8% by weight, the antistatic property and the water / oil repellency are not compatible due to elution of the antistatic agent or poor adhesion of the water repellent agent.

In the present invention, the antistatic agent (B) to be added to the leather-like sheet is at least selected from the group consisting of cationic antistatic agents, anionic antistatic agents, nonionic antistatic agents and amphoteric antistatic agents. It is a kind of antistatic agent, preferably an anionic antistatic agent. As the antistatic agent (B), those used as commercially available antistatic agents can be used. The following compounds may be mentioned as examples. As anionic antistatic agents, compounds such as higher alcohol potassium phosphates and sodium alkyl sulfonates are used. As cationic antistatic agents, fatty acid quaternary ammonium ion salts and polyamine quaternary salts are used. And the like, and nonionic antistatic agents include polyhydric alcohol fatty acid ester compounds, polyglycol phosphate ester compounds, polyoxyethylene alkyl allyl ether compounds, and the like. And compounds such as betaine-type amphoteric surfactants and imidazoline-type amphoteric surfactants.

The amount of the antistatic agent (B) to be applied is 0.01 to the total weight of the fibers constituting the artificial leather and the polyurethane.
~ 5% by weight. If the amount is less than 0.01% by weight, the antistatic effect cannot be obtained, and if the amount is more than 5% by weight, the antistatic property due to elution of the water repellent or poor adhesion of the antistatic agent,
Water and oil repellency are no longer compatible, and the effects of the present invention cannot be obtained. When a nonionic antistatic agent having an HLB value of 8 or more is used as the antistatic agent (B), the role of the antistatic agent (B) and the role of the nonionic surfactant (H) having an HLB value of 8 or more are considered. It also works at the same time. In such a case, a nonionic surfactant (H) having another HLB value of 8 or more may be further added in order to enhance the stability of the water / oil repellent / antistatic bath.

The weight ratio of the fluorine atom-containing compound (A) to the antistatic agent (B) is not particularly limited as long as the weight ratio to each leather-like sheet is within a suitable range. Is within the range. 2 ≦ (A) / (B) ≦ 10

In the present invention, as the nonionic surfactant (H) to be added to the leather-like sheet, those used as commercially available surfactants can be used. By using one or a plurality of surfactants having the following structures, optimum performance according to the system is developed. The following compounds may be mentioned as examples. That is, examples thereof include alkyl and alkyl allyl polyoxyethylene ethers, polyoxyethylene ethers of glycerin esters, polyethylene glycol fatty acid esters, and fatty acid alkanolamides.

In the present invention, the nonionic surfactant (H) added to the leather-like sheet preferably has an HLB value of 8 or more. When the HLB value is less than 8, the hydrophilicity is insufficient, and the HLB value is precipitated in a treatment aqueous solution, so that the effect as a surfactant cannot be obtained. The use amount of the nonionic surfactant (H) is preferably 0.01 to 1.0% by weight.
In both cases of less than 0.01% by weight and more than 1.0% by weight, the effect of stabilizing the processing bath cannot be obtained, causing separation and solidification of the chemical, and any of water repellency, oil repellency and antistatic property. One will be slightly inferior.

In the present invention, the method of applying the fluorine atom-containing compound (A), the antistatic agent (B), and the nonionic surfactant (H) to the leather-like sheet is as follows. The coating is not limited as long as it is applied, but is usually performed by dip-nip coating or gravure coating.

The present invention is characterized in that a fluorine atom-containing compound (A) and an antistatic agent (B), preferably a nonionic surfactant (H), are treated in the same bath. When the treatment is performed in separate treatment baths, the performance of the water repellency and / or the antistatic property is reduced, and the effect of the present invention cannot be obtained.

According to the present invention, a conventional polycarbonate-based polyurethane having a water repellency of 70 points or more and a friction band voltage of 800 V or less is used, and cannot be achieved by artificial leather made of polyamide or polyester ultrafine fibers. A leather-like sheet having both water / oil repellency and antistatic properties can be obtained. In the present invention, the water repellency means a value measured by the method A of JIS-L1018, and the frictional charged voltage means a charged voltage one minute after stopping measured by the method B of JIS-L1094. ing.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. The thickness (fineness) of the ultrafine fiber referred to in the present invention is determined by taking a photograph of a cross section of the ultrafine fiber bundle obtained by removing the sea component polymer from the ultrafine fiber forming fiber with an electron microscope, The number of ultrafine fibers present in the cross section was counted, and the fineness (decitex) of the ultrafine fiber bundle was divided by the number.

Example 1 500 parts by weight of polyhexylene carbonate diol having a number average molecular weight of 2000, 200 parts by weight of polymethylpentane adipate diol having a number average molecular weight of 2000, and 47 parts by weight of 1,6-hexamethylene diisocyanate as an organic diisocyanate (F) Parts (NCO / OH = 0.8
0), N, N-dimethylformamide (DMF) 300
Parts by weight into a reactor and heated at 110 ° C. for 2 hours under a nitrogen stream.
The reaction was carried out for an hour to obtain a DMF solution of the intermediate diol (G). After confirming that the isocyanate group had disappeared, the viscosity of the DMF solution of the intermediate diol (G) was measured and found to be 68 Pa · s at 70 ° C. To a DMF solution of the intermediate diol (G) obtained above, 41.3 parts by weight of ethylene glycol as a chain extender, 180 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI), and 2505 parts by weight of DMF were added. Reaction, concentration 25% by weight, weight average molecular weight (polystyrene conversion; DM
F solution) 400,000 polyurethane solutions were obtained. 92 parts by weight of DMF was added to 100 parts by weight of the obtained polyurethane solution to prepare an impregnating liquid.

On the other hand, a staple fiber of an ultrafine fiber generating type fiber (6-nylon is an ultrafine fiber component) obtained by mixing and spinning 60 parts by weight of 6-nylon and 40 parts by weight of highly fluid polyethylene is used for web. And weigh 650 g /
A needle-punch entangled nonwoven fabric having an m ² and a thickness of 2.2 mm was obtained.
After impregnating the entangled nonwoven fabric with the above impregnating liquid, DMF
And coagulated. Then, it is treated in hot toluene to dissolve and remove the polyethylene component,
A 1.35 mm thick sheet was obtained. The sheet was divided into two slices, and the divided surfaces were buffed with sandpaper to adjust the thickness to 0.54 mm. Further, the surface at the time of coagulation was treated with an emery buffing machine to form a fiber napped surface. The thickness of the fibers at this time was 0.01 dtex on average. When the sheet having the fiber raised surface was dyed under the following conditions, the sheet was dyed in a vivid color and a leather-like sheet having a good texture was obtained. Dye concentration 5.0 g / L Ammonium acetate 0.6 g / L Formic acid 1.0 g / L Bath ratio 50: 1

The leather-like sheet is dipped under the following conditions.
When the treatment liquid was applied through the nip, the texture was the same as that before the treatment, and the sheet was a good leather-like sheet. The fluorine atom-containing compound (A) used in the treatment solution was Dickguard F-90.
C (manufactured by Dainippon Ink) and the antistatic agent (B) is ZER
In OSTAT FC (manufactured by Ciba-Geigy), the nonionic surfactant (H) is Sepalon AK (manufactured by Daikyo Chemical). From the pickup ratio calculated from the weight ratio of the leather-like sheet before and after the water-repellent and oil-repellent and antistatic treatment, the fluorine atom-containing compound (A), the antistatic agent (B) and the nonionic surfactant (H) were compared with the fibers. 0.6% by weight, 0.09% by weight and 0.06% by weight were added to the total weight of the polyurethane resin. Table 2 shows the performance of the obtained leather-like sheet. Composition of treatment liquid of Example 1 Fluorine atom-containing compound (A): 10 g / liter Antistatic agent (B): 1.5 g / liter Nonionic surfactant (H): 1.0 g / liter

Example 2 Under the same conditions as in Example 1, up to dyeing, the concentrations of the fluorine atom-containing compound (A) and the antistatic agent (B) in the treatment bath in the water / oil repellency and antistatic treatment were as follows: The procedure was carried out under the same conditions as in Example 1 except that the treatment was carried out without adding a nonionic surfactant. From the pickup rate, the fluorine atom-containing compound (A) and the antistatic agent (B) are based on the total weight of the fiber and the polyurethane resin.
The leather-like sheet was provided with 0.3% by weight and 0.06% by weight, respectively. Fluorine atom-containing compound used (A)
The brand of the antistatic agent (B) is the same as that used in Example 1. Table 2 shows the performance of the obtained leather-like sheet. Composition of treatment liquid of Example 2 Fluorine atom-containing compound (A): 5 g / liter Antistatic agent (B): 1 g / liter

Comparative Example 1 The same procedure as in Example 1 was carried out under the same conditions as in the dyeing, and in the water / oil repellency and antistatic treatment, the composition of the fluorine atom-containing compound (A ), A leather-like sheet provided with an antistatic agent (B) and a nonionic surfactant (H) in an amount of 10% by weight, 1.5% by weight and 1% by weight, respectively, based on the total weight of the fiber and the polyurethane resin. Manufactured. The brands of the fluorine atom-containing compound (A), antistatic agent (B) and nonionic surfactant (H) used are the same as those used in Example 1. Table 2 shows the performance of the obtained leather-like sheet. Composition of treatment liquid of Comparative Example 1 Fluorine atom-containing compound (A): 100 g / liter Antistatic agent (B): 15 g / liter Nonionic surfactant (H): 10 g / liter

Comparative Examples 2 to 5 Leather-like sheets were produced under the same conditions as in Example 1 until dyeing, and in the subsequent water / oil repellency and / or antistatic treatment, water repellency was obtained as shown in Table 1 below. Dip once or twice without treating the agent and antistatic agent in the same bath
Nip processing was performed. The pickup rate and the amount of the treatment agent applied were the same as in Example 1. The brands of the fluorine atom-containing compound (A), antistatic agent (B) and nonionic surfactant (H) used are the same as those used in Example 1.
Table 2 shows the performance of the obtained leather-like sheet.

[0052]

[Table 1]

Treatment liquid composition in water repellent treatment: Fluorine atom-containing compound (A): 10 g / l Treatment liquid composition in antistatic treatment: 1.5 g / l

Example 3 Of the polyurethane raw materials, the composition of the diol to be subjected to the prepolymer reaction was 400 parts by weight of polyhexylene carbonate diol having a number average molecular weight of 2,000 and a number average molecular weight of 20.
The ultrafine fiber-generating fiber (polyethylene terephthalate is obtained by mixing and spinning 65 parts by weight of polyethylene terephthalate and 35 parts by weight of highly flowable polyethylene by melt-spinning to 300 parts by weight of polymethylpentane adipate diol of No. 00 A leather-like sheet was produced under the same conditions as in Example 1 except that the composition was an ultrafine fiber component). The thickness of the ultrafine fibers is the same as in Example 1. The brands of the fluorine atom-containing compound (A), antistatic agent (B) and nonionic surfactant (H) used are the same as those used in Example 1. Table 2 shows the performance of the obtained leather-like sheet.

[Processing Stability] Emulsion stability of the treatment liquids subjected to the water / oil repellency and antistatic treatment used in the above Examples and Comparative Examples was evaluated in the following manner in the state of dispersion after standing for 3 days. ：: stably dispersed ×: components aggregated and suspended matter was observed −: not evaluated because emulsion alone was present in the bath In addition, the leather-like sheet produced by the above method was not evaluated. It was evaluated by the following evaluation method. [Water repellency] Measured by A method of JIS-L1018. [Charging voltage] Measured by the B method of JIS-L1094. Charged voltage one minute after stopping. [Dry friction fastness] Measured according to JIS-L0823. [Light resistance] Measured according to JIS-L0824. [HLB value] Measured by the method described in Handbook of Surfactants.

[0056]

[Table 2]

From the results of the above Examples and Comparative Examples, the water and oil repellency and the charge repellency were improved by treating the water and oil repellent of the present invention, the antistatic agent, and preferably the nonionic surfactant in the same bath. Balanced performance that satisfies practical performance, ie, water repellency of 70 points or more and frictional voltage of 800 V
It is clear that the following performance is exhibited.

[0058]

The leather-like sheet obtained according to the present invention comprises:
It retains water and oil repellency and antistatic properties at a high level, and has good mechanical properties such as tensile strength, dry friction fastness, and light resistance, so it can be used for bags for sports equipment, shoes, bags, bags, etc. It can be effectively used for a wide range of applications such as shapes, boxes, buildings such as houses, interior materials for transportation such as boats, cosmetic materials for furniture, and clothing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F055 AA02 BA11 CA12 CA18 DA07 EA03 EA05 FA18 FA19 FA20 HA04 HA19 4L033 AA08 AB07 AC03 AC06 BA20 CA50

Claims (5)

[Claims] 1. A leather-like sheet comprising a fiber and a polycarbonate-based polyurethane resin and having a weight ratio (fiber / polycarbonate-based polyurethane resin) of 95/5 to 40/60, based on the total weight of the fiber and the polyurethane resin. On the other hand, the content of the fluorine atom-containing compound (A) is 0.05 to
8% by weight of at least one antistatic agent (B) selected from the group consisting of cationic antistatic agents, anionic antistatic agents, amphoteric antistatic agents, and nonionic antistatic agents.
A leather-like sheet having a water repellency of 70 points or more and a friction band voltage of 800 V or less, provided in an amount of from 0.01 to 5% by weight. 2. A polycarbonate polyurethane resin,
A mixed diol comprising a polycarbonate polymer diol (C) having a number average molecular weight of 500 to 3000 and a polymer diol (D) having a number average molecular weight of 500 to 3000 selected from the group consisting of polyester, polylactone and polyether ( E) and an organic diisocyanate (F) in a quantitative relationship such that the equivalent ratio of NCO / OH is 0.5 to 0.99. The leather-like sheet according to claim 1, which is a polyurethane resin obtained by chain-extending a resin. 3. A nonionic surfactant (H) having an HLB value of 8 or more, based on the total weight of the fiber and the polyurethane resin.
The leather-like sheet according to claim 1, which is provided in an amount of 0.01 to 1.0% by weight. 4. The composition according to claim 1, wherein the weight composition ratio of the fluorine atom-containing compound (A), the antistatic agent (B) and the nonionic surfactant (H) having an HLB value of 8 or more satisfies the following relationship. Leather-like sheet. 0 ≦ (H) / (A) ≦ 0.25 0 ≦ (H) / (B) ≦ 1.5 5. A leather-like sheet comprising a fiber and a polycarbonate-based polyurethane resin and having a weight ratio (fiber / polycarbonate-based polyurethane resin) of 95/5 to 40/60, is prepared by treating a fluorine-containing compound (A), A method for treating a leather-like sheet, comprising performing the same bath treatment with an aqueous solution to which an inhibitor (B) and a nonionic surfactant (H) having an HLB value of 8 or more are added.