JPH06192968A - Cation-dyeable leathery sheet - Google Patents

Abstract

PURPOSE:To obtain a leathery sheet, composed of a cation-dyeable polyurethane prepared by reacting a specific intermediate diol with a low-molecular diol and a diisocyanate and cation-dyeable fiber and excellent in improved color developing properties and durability. CONSTITUTION:This leathery sheet is composed of a cation-dyeable polyurethane prepared by substituting components (X) in a sulfonic acid group-containing compound of formula I (X is OH or oxyalkyl) with a dial of formula II or polymerizing a sulfonic acid group-containing radically polymerizable monomer in the presence of dimethylolpropionic acid and/or a compound containing two hydroxyl groups and one thiol group, then reacting the resultant sulfonic acid group-containing diol with a polymer diol, selected from the group of polyesters, polycarbonates, polylactones and polyethers and having 500-3000 molecular weight with an organic diisocyanate in the relationship of 0.5-0.99 NCO/OH equiv. ratio and subsequently reacting the obtained intermediate diol having terminal OH group with a low-molecular diol and diphenylmethane 4,4'- diisocyanate and especially cation-dyeable synthetic fiber. The leathery sheet is excellent in heat and cold resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a leather-like sheet having good dyeability. More specifically, it is excellent in various physical properties such as mechanical properties and durability obtained by mixing and reacting the specific components constituting the polyurethane resin in a specific combination composition in a specific order, and is excellent in processability. The present invention relates to a leather-like sheet having good dyeability, which is characterized by using a dyeable polyurethane resin.

[0002]

2. Description of the Related Art Polyurethane is excellent in mechanical performance, and a solution of polyurethane is impregnated and / or applied to a fibrous structure to form naps on the surface of the fibrous structure obtained by wet coagulation or dry coagulation. The leather-like sheet material obtained by providing a surface finishing layer as a main component is used in various fields. However, the conventional polyurethane resin cannot be dyed well because it does not have a dyeing seat required for dyeing with an acid dye or a cationic dye. Also,
Dyeing is possible with disperse dyes, but due to the looseness of the amorphous structure of polyurethane, the dye is difficult to stay inside the resin, that is, the dyeing fastness is extremely poor, and it can be easily washed or rubbed. Fading and fading were observed.

As an attempt to improve these drawbacks, a dyeing seat is introduced into a polyurethane resin. For example, by using a compound containing a sulfonic acid group,
It is known to obtain cationic dyeable polyurethanes. For example, JP-A-55-34815 discloses that a polyurethane having good dyeability can be obtained by reacting a bifunctional prepolymer with an aniline monomer or a metal salt of polysulfonic acid. However, according to the method of the publication, aniline having a dyeing seat is monofunctional and is introduced at the terminal of a polyurethane polymer molecule. Therefore, when a large amount of aniline is used to enhance the dyeability, the molecular weight of the polyurethane becomes too small, the viscosity of the polyurethane solution becomes too low, the process passability deteriorates, and the mechanical performance of the resin decreases. , Not preferable. Also, mechanical performance, process passability (solution viscosity)
If the size of the polyurethane molecule is increased to satisfy the above condition, it is not possible to introduce enough aniline to secure a sufficient dyeing seat, and there was a difficulty in implementing it industrially.

Japanese Patent Publication No. 46-2356 discloses 2,5.
-Sodium di (β-hydroxyethoxy) benzene sulfonate, sodium 3- (β-hydroxyethoxy) -5 carboxybenzene sulfonate, sodium 2-amino-4- (β-hydroxyethoxycarbo) benzene sulfonate,
It is disclosed that a bifunctional compound such as can be added and reacted at any time during the production step of polyurethane or polyurea, and the copolymer obtained by the method can be emulsified with water. However, the polyurethane obtained by the method of the publication is suitable for water emulsification, but when applied to artificial leather, it swells when added to a coagulation bath consisting of water and DMF, or when it elutes during dyeing. It was difficult to pass through the process such as poor holding property and could not be applied to the industrial production of artificial leather.

Japanese Patent Laid-Open No. 59-6210 discloses (A)
A high molecular weight polyol comprising at least one component of terephthalic acid and / or isophthalic acid in an amount of 30 mol% or more based on the total carboxylic acid, and a polyester polyol having a sulfonic acid group, (B) diisocyanate, and (C)
A polyurethane resin composition comprising a chain linking agent is disclosed. However, since the polyurethane obtained by the method of the publication contains 30 mol% or more of terephthalic acid and / or isophthalic acid in the total carboxylic acid, it is inferior in flexibility and cold resistance of the resin and is not suitable for application to artificial leather. It's totally bad.

Japanese Patent Publication No. 63-43507 discloses ultrafine fibers containing copolymerized polyethylene terephthalate containing ethylene isophthalate sulfonate and -SO ₃ X.
A leather-like sheet material comprising a silver surface layer made of polyurethane containing is disclosed. In the method according to the publication, polyurethanes containing -SO ₃ X JP-B 55-
It is shown that the use of the polyurethane disclosed in Japanese Patent No. 34815 is particularly excellent and asserts its superiority, but when the polyurethane disclosed in the same is used, it is carried out industrially as described above. Had some difficulties.

JP-A-4-248825 discloses vinyl sulfonated and non-sulfonated, hydroxy functional polyurethane copolymers prepared from macromonomers and their use in magnetic recording media. The publication shows that as an example of a method of making a sulfonated vinyl sulfonated hydroxy functional polyurethane copolymer, it can be prepared by reacting from about 2 to about 4 equivalents of an appropriate diol per equivalent of dimethylsodium sulfoisophthalate. ing. The most preferred diol has a hydroxy equivalent of about 200 (molecular weight 400) to about 2000.
A polycaprolactone diol having a molecular weight of 4000 is listed. Further, other diols include polyether diols, polycarbonate diols, polyester diols, etc., and their superiority is claimed. However, the polyurethane obtained by the method according to the publication does not form a sponge when applied to a coagulation bath consisting of water and DMF when applied to artificial leather.
It is difficult to industrially manufacture artificial leather having a good texture because it has a difficulty in process passage such as swelling during coagulation and dyeing or swelling and poor shape retention.

JP-A-4-178416 and JP-A-4-178417 have a radically polymerizable unsaturated bond in the presence of a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group. A method for producing a polyurethane resin by reacting a macromonomer (A) obtained by radical polymerization of a monomer, a polyol (B) and a polyisocyanate (C), and a polyurethane resin composition comprising the resin are disclosed. Those publications disclose 3-mercapto- as a mercaptan chain transfer agent having two or more hydroxyl groups and one mercapto group.
Styrene sulfonic acid is exemplified as 1,2-propanediol as a monomer having a radically polymerizable unsaturated bond. However, the polyurethane resin obtained by the method of those publications, because the reaction sequence is not particularly limited, or because each component in the resin does not have a controlled array structure, during polymerization, The viscosity does not rise sufficiently, and it is difficult to obtain a polyurethane resin with a sufficient balance of physical properties such as heat resistance, cold resistance, and strength, and it can be used as an adhesive, paint, or coating resin. Was not applicable to the production of artificial leather-like sheets.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to introduce a dyeing seat of a cationic dye into polyurethane, and to use an industrially applicable polyurethane resin having improved dyeing properties, Texture, flexibility, cold resistance, heat resistance,
A leather-like sheet that can be dyed with a cationic dye having excellent durability.

[0010]

The present invention provides a sulfonic acid group-containing compound represented by the following general formula (I), wherein the component X is:
Sulfonic acid group-containing compound obtained by substantially substituting with a diol represented by the general formula (II), or in the presence of a compound containing dimethylolpropionic acid and / or two hydroxyl groups and one thiol group. Polymer diol (B) having a number average molecular weight of 500 to 3000 selected from the group consisting of sulfonic acid group-containing diol (A) obtained by polymerizing a radically polymerizable monomer, polyester, polycarbonate, polylactone and polyether, and organic The terminal OH intermediate diol (D) obtained by reacting the diisocyanate (C1) in a quantitative relationship such that the equivalent ratio of NCO / OH is 0.5 to 0.99 and the low molecular weight diol (E ), A solution of polyurethane obtained by reacting diphenylmethane-4,4'-diisocyanate (C2) with a fibrous structure And a cationic dye dyeable leather-like sheet.

[Chemical 2] (However, X is an OH group or an oxyalkyl group) HO-R-OH (II) (however, R is an alkylene group or polyoxyalkylene group having a molecular weight of 400 or less)

In the present invention, in order to improve the dyeability of polyurethane, the sulfonic acid group-containing diol (A) is not a hard segment (chain extender) or a molecular terminal of the polyurethane, but an intermediate soft segment. It is introduced into the body diol (D) to serve as a dyeing seat for the cationic dye. That is, the polyurethane used in the present invention can introduce a required amount of dyeing seat without adversely affecting the molecular weight and the crystallinity of the hard segment. Therefore, the compounding amount of the sulfonic acid group-containing diol (A) is not particularly limited and varies depending on its molecular structure, required dyeability, dye used, etc., but is 1 to 1000 μeq / g as a sulfonic acid group with respect to polyurethane. Especially, 2-500μe
It is preferably q / g.

X of the sulfonic acid group-containing compound represented by the general formula (I) is an OH group or an oxyalkyl group.
The structure of the oxyalkyl group is not particularly limited, but an oxy lower aliphatic group, especially a methoxy group is preferably used. The structure of R of the diol represented by the general formula (II) is not particularly limited as long as it is an alkylene group or a polyoxyalkylene group, but the molecular weight is 400 or less, and especially 3
0 to 300 is preferable. When the molecular weight exceeds 400, the sulfonic acid group-containing ratio of the obtained sulfonic acid group-containing diol becomes small, and it depends on the required dyeability, dye used, etc., but a large amount of sulfonic acid group-containing diol is used. In some cases, it is not desirable in terms of mechanical properties, flexibility, cold resistance, etc. of the polyurethane resin. The X component of the sulfonic acid group-containing compound represented by the general formula (I) is
The method of substituting with the diol represented by the general formula (II) is not particularly limited, and a known method can be used. That is,
It can be obtained in the presence or absence of a sulfonic acid group-containing compound and a diol catalyst, if necessary, by heating at 120 to 250 ° C. under reduced pressure and stirring. Known catalysts can be used,
For example, titanium tetraisopropoxide, zinc acetate, manganese acetate, etc. can be used at 10 to 500 ppm.

Further, a sulfone obtained by polymerizing a sulfonic acid group-containing radical-polymerizable monomer in the presence of the dimethylolpropionic acid and / or the compound having two hydroxyl groups and one thiol group used in the present invention. The acid group-containing diol (A) can be obtained by a known method.
For example, in the presence of 3-mercapto-1,2-propanediol, monomers of 2-acrylamido-2-methylpropanesulfonic acid or styrenesulfonic acid are added to azobisisobutyronitrile, azobisisovaleronitrile, vanzoylperoxide. Polymerization can be performed using an initiator such as oxide. Further, it is acceptable to use butyl acrylate, methyl methacrylate, butyl methacrylate, ethyl acrylate and other perfluoroalkyl-free methacrylates, acrylates, and other copolymerizable vinyl monomers in combination within a range that does not impair the object of the present invention. Absent. The molecular weight of the sulfonic acid group-containing diol (A) thus obtained is not particularly limited, and is 400 to 20,000, but 500 to
It is preferably 4000. If it exceeds 20,000 and is too large, a polymer having no hydroxyl group is likely to be formed during production, and it may be difficult to be effectively used for polyurethane, which may be a difficulty in industrial production.

The polymer diol (B) used in the present invention is selected from the group consisting of polyesters, polycarbonates, polylactones and polyethers. The number average molecular weight is 500 to 3000, more preferably 70.
The range of 0 to 2500 is selected. If it is less than 500, the flexibility of the leather-like sheet material tends to be lost, or the texture tends to deteriorate, which is not preferable. If it exceeds 3,000, the concentration of urethane groups will inevitably decrease, and not only is it difficult to obtain a leather-like sheet material with well-balanced feeling, flexibility, cold resistance, heat resistance, and durability, The polymer
This is not preferable because of the difficulty in industrial production of diol.

The polyester diol used in the present invention can be obtained, for example, by reacting a dibasic acid with a diol. Examples of dibasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. It is possible to use one type of basic acid or a combination thereof. Among them, aliphatic dibasic acids, particularly adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and other dibasic acids having a methylene chain length of 4 to 8 are more preferably used. Aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol and dodecanediol, which may be substituted with lower alcohols. Aliphatic diols such as diols, cyclohexane diols, hydrogenated xylylene glycols, etc., and aromatic diols such as xylylene glycol, etc. are used alone or as a mixture of two or more thereof. Among them, aliphatic diols, especially butane are used. Diol, methylpentanediol, hexanediol, heptanediol, methyloctanediol,
One kind or a mixture of two or more kinds of aliphatic diols having a carbon chain length of 4 to 9 such as nonanediol is preferably used.

The polycarbonate diol 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. As the diol, ethylene glycol optionally substituted with a lower alcohol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol,
Aliphatic diols such as heptanediol, octanediol, nonanediol, decanediol and dodecanediol, alicyclic diols such as cyclohexanediol and hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol. Mixtures of two or more species are used, among which aliphatic diols, especially butanediol, methylpentanediol, hexanediol, heptanediol, methyloctanediol, nonanediol, and other aliphatic diols having a carbon chain length of 4 to 9 Alternatively, a mixture of two or more kinds is preferably used.

Polylactone diols are, for example, poly-
ε-caprolactone diol, poly-trimethyl-ε-
Examples thereof include caprolactone diol and poly-β-methyl-δ-valerolactone diol. Examples of the polyether diol include polytetramethylene glycol, polypropylene glycol, polyethylene glycol and the like.

The organic diisocyanate (C1) is, for example, diphenylmethane-4,4'-diisocyanate,
Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, meta or paraphenylene diisocyanate, 1,5 naphthylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI, etc. A non-aromatic diisocyanate or the like is used. Among them, in the case of diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, the surface properties and feel of the sheet-like product obtained by coagulating with a non-solvent Is preferable and is preferable.

The intermediate diol (D) having a substantially OH terminal constitutes a substantially soft segment of the obtained polyurethane, and comprises the component (A), the polymer diol (B), and the organic diisocyanate (C1). And NC
It is obtained by reacting in a quantitative relationship such that the equivalent ratio of O / OH is 0.5 to 0.99. NCO / OH equivalent ratio is 0.5
If the amount is less than the above, the amount of the urethane bond incorporated into the intermediate diol having an OH terminal is substantially small, although it varies depending on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1). It is difficult to balance the surface slimyness, texture, flexibility, cold resistance, and heat resistance of the leather-like sheet, probably because it is too small or the molecular weight becomes too small, and the effect of the present invention cannot be sufficiently obtained. . When the NCO / OH equivalent ratio exceeds 0.99,
Although it depends on the blending amount of the component (A), the molecular weight of the polymer diol (B), and the type of the organic diisocyanate (C1), the amount of the urethane bond incorporated into the intermediate diol having an OH terminal is too large, or Furthermore, it is difficult to balance the surface properties, feeling, flexibility, cold resistance, and heat resistance of the leather-like sheet material, possibly because the molecular weight becomes too large, which is not preferable.

As the low molecular weight diol (E), ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, which may be substituted with a lower alcohol,
Aliphatic diols such as heptanediol, octanediol, nonanediol, decanediol, dodecanediol, cyclohexanediol, hydrogenated xylylene glycol, alicyclic diols, xylylene glycol,
Aromatic diols such as, and further, one kind or a mixture of two or more kinds such as diethylene glycol is used,
Among them, aliphatic diols, especially ethylene glycol and butanediol are preferably used in terms of the balance of the texture, flexibility, cold resistance, heat resistance and the like of the leather-like sheet material. The amount of the low molecular diol (E) used is not particularly limited, but its molecular structure, the amount of the component (A) blended, the molecular weight of the polymer diol (B), the type of organic diisocyanate,
Although it varies depending on the NCO / OH equivalent ratio, a leather-like sheet is usually obtained in which the equivalent ratio of (E) / (B) to the polymer diol (B) is 0.5 to 7 among 1 to 5.5. In many cases, it is suitable in terms of texture, flexibility, cold resistance, and heat resistance.

The amount of diphenylmethane-4,4'-diisocyanate (C2) used is not particularly limited, but the viscosity of the polyurethane solution, the sulfonic acid group-containing diol (A),
Molecular weight of polymer diol (B), sulfonic acid group-containing diol (A), NCO / OH equivalent ratio of polymer diol (B) and organic diisocyanate (C1), reaction solvent, sulfonic acid group-containing diol (A), polymer diol ( B), N depends on (C1) and (C2), though it depends on the water content in the low molecular diol (D).
The equivalent ratio (NCO / OH) of CO and hydroxyl groups from the sulfonic acid group-containing diol (A), the polymer diol (B) and the low molecular diol (D) is 0.95 to 1.2, and above all 0.97 to 1 It is preferable to use the above.

Further, a catalyst is not always necessary when carrying out the polymerization method used in the present invention, but catalysts used in usual polyurethane production, for example, metals such as titanium tetraisopropoxide, dibutyltin dilaurate, tin octate, etc. Compound, tetramethylbutanediamine,
A tertiary amine such as 1,4-diaza (2,2,2) bicyclooctane can be used. Examples of the solvent for the polyurethane obtained by the method used in the present invention include dimethylformamide, dimethylacetamide, N-
A commonly used solvent such as methylpyrrolidone, toluene, ethyl acetate, methyl ethyl ketone, or tetrahydrofuran is used. Polyurethane obtained by the method used in the present invention, various additives used in conventional polyurethane in use, for example, phosphorus compounds, flame retardants such as halogen-containing compounds, antioxidants, ultraviolet absorbers,
Pigments, dyes, plasticizers, surfactants and the like can be added.

The fibers constituting the fibrous structure do not necessarily have to be dyed in the case of a silver-leathered leather-like sheet having the above-mentioned polyurethane coating layer on the surface thereof, and in particular, fibers dyed with a cationic dye. Although not limited thereto, in order to prevent a discoloration of the cut surface of the leather-like sheet, it is preferable to use a fiber that is dyed with a cationic dye. On the other hand, in the case of a fiber napped suede-like leather-like sheet, there is no particular limitation as long as it is composed of fibers dyeable with a cationic dye, and synthetic fibers such as polyacrylonitrile, sulfonic acid group-modified polyester, or natural fibers. For example, wool can be used.
A woven fabric, a knitted fabric, or a non-woven fabric is used as the fibrous structure, and the non-woven fabric is preferable from the viewpoints of easy formation of uniform naps and surface smoothness when forming the coating layer. The non-woven fabric may have a knitted fabric for reinforcement or the like laminated inside if necessary. Above all, the average fineness of three-dimensional entanglement is 0.
A non-woven fabric composed of an ultrafine fiber bundle having a denier of 1 denier or less, and further 0.005 to 0.1 denier is preferable.

The entangled non-woven fabric composed of such an ultrafine fiber bundle is a spinnable thermoplastic resin dyeable with a cationic dye,
For example, it can be derived from a sulfonic acid group-modified polyester ultrafine fiber generating fiber composed of two or more kinds of polymer components containing a known sulfonic acid group-modified polyester resin.
There are no particular restrictions on the other polymers that make up the ultrafine fiber-generating fiber, and the sulfonic acid group-modified polyester resin has a different solubility or decomposability in a solvent or a decomposing agent, and a resin having a low affinity with the sulfonic acid group-modified polyester resin. And a resin having a melt viscosity lower than that of the sulfonic acid group-modified polyester resin under spinning conditions. For example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, ethylene-
It is selected from an α-olefin copolymer, polystyrene, a styrene-isoprene copolymer, a hydrogenated product of a styrene-isoprene copolymer, a stellene-butadiene copolymer, a hydrogenated product of a stellene-butadiene copolymer, and the like. Fibers composed of a sulfonic acid group-modified polyester resin and another polymer are mixed at a predetermined mixing ratio and dissolved in the same dissolution system,
A method of forming a mixed system and spinning, a method of dissolving in a separate dissolving system, a method of forming a mixed system by repeating joining-splitting a plurality of times in a spinning machine head to form a mixed system, dissolving in a separate dissolving system,
By the method of defining the fiber shape in the spinneret of the spinning machine and performing spinning, the sulfonic acid group-modified polyester resin component in the fiber is 40 to 80% by weight, and the sulfonic acid group-modified polyester resin ultrafine fiber component in the fiber is Five or more, preferably 50 to 800, sulfonic acid group-modified polyester ultrafine fiber generating fibers are obtained. If necessary, the ultrafine fiber-generating fiber may have a fineness of 2 to 15 denier, an average fineness (calculated value) of the sulfonic acid group-modified polyester ultrafine fiber component of 0.2 denier or less, through ordinary fiber treatment steps such as stretching and heat setting. Is a fiber of 0.005 to 0.1 denier. The ultrafine fiber-generating fibers are defibrated with a card to form a random web or a crosslap web through a web bar, and the obtained fiber web is laminated to have a desired weight and thickness. Then, the fiber web is subjected to a fiber entanglement treatment using a needle punch, a water jet, an air jet or the like by a conventionally known method to obtain a fiber entangled nonwoven fabric.

Next, a composition obtained by adding a coagulation regulator, a mold release agent, a plasticizer, a stabilizer, an antioxidant, a lightproofing agent, a colorant and the like to the nonwoven fabric solution of the polyurethane obtained above if necessary. The liquid is impregnated and / or applied, and wet coagulation or dry coagulation is performed. In the case of ultrafine fiber generation type fibers, prior to impregnation and application of the polyurethane composition liquid to the fiber entangled nonwoven fabric,
Alternatively, after impregnation and coating, it is treated with a solvent of other resin constituting the fiber and a non-solvent of the fiber to transform it into an ultrafine fiber. The amount of the polyurethane resin in the sheet-like material composed of the fiber structure and the polyurethane resin is not particularly limited, but it is often used in a weight fraction of 10 to 60%, especially 15 to 45%. If the amount of polyurethane used is too low, the texture is rather flat, and if it is less than 10%, it becomes remarkable. If the amount of polyurethane is large, it becomes hard,
It tends to have a texture without bulging. The tendency becomes remarkable when it is used in excess of 60%.

Further, this sheet-like material is provided with a porous or non-porous coating layer obtained from the above polyurethane on the surface, if necessary, to obtain a silver-tone leather-like sheet, or at least one surface thereof is provided. It can be made into a fiber-like napped suede-like leather-like sheet by applying a brushing treatment. Further, if necessary, it is possible to perform slice division into an arbitrary thickness in the thickness direction at an arbitrary stage. The obtained leather-like sheet is dyed with a cationic dye to form a leather-like sheet excellent in color developability, fastness, surface slimyness, texture, flexibility, cold resistance, heat resistance, durability, etc. You can

[0027]

The thus-obtained leather sheet material of the present invention is useful for various purposes such as clothing, shoes, bags, furniture, vehicle interior materials and sundries. Polyurethane resin can be dyed with a cationic dye without losing its desirable mechanical properties and processability, and a leather-like sheet material having a good texture without impairing its desirable properties in the manufacturing process of the leather-like sheet material. Although the mechanism of action obtained is not clear, sulfonic acid group-containing diol (A), 500-300
0 of the polymer diol (B) and the organic diisocyanate (C1) have an NCO / OH equivalent ratio of 0.5 to 0.99.
And a low molecular weight diol (E), which is a OH intermediate diol (D) obtained by reacting in a quantitative relationship such that While maintaining the desired microphase-separated state of the segment and the hard segment, the sulfonic acid serving as the dyeing seat of the cationic dye is introduced, and thus the polyurethane resin is impregnated, and the above-mentioned preferable characteristics of the leather sheet material serving as the coat layer are obtained. It is thought that this was given.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. <Production of Sulfonic Acid Group-Containing Diol (A)> Reference Example 1 296 parts by weight of dimethylsodium sulfoisophthalate,
A three-necked flask was charged with 656 parts by weight of a mixture of 1,9-nonanediol and methyloctanediol (weight ratio 60:35), 1.1 parts by weight of sodium acetate, and 0.2 parts by weight of titanium tetraisopropoxide. While being accompanied, it is heated to 180 ° C. under a nitrogen stream. The temperature is further raised to 220 ° C. according to the distillation rate of methyl alcohol. When the amount of distillate of methyl alcohol reached 63 parts by weight, the mixture was cooled, and the viscous reaction product obtained was analyzed by NMR. As a result, no methyl group was detected, and a sulfonic acid group-containing diol was substantially obtained. .

Reference Example 2 296 parts by weight of dimethylsodium sulfoisophthalate,
371 parts by weight of diethylene glycol, 0.85 part by weight of sodium acetate, and 0.17 part by weight of titanium tetraisopropoxide were charged in a three-necked flask to obtain a sulfonic acid group-containing diol having no methyl group in the same manner as in Reference Example 1. It was

Reference Example 3 296 parts by weight of dimethylsodium sulfoisophthalate,
254 parts by weight of ethylene glycol, sodium acetate 0.
5 parts by weight and titanium tetraisopropoxide 0.1
Part by weight was placed in a three-necked flask, and a sulfonic acid group-containing diol having no methyl group was obtained in the same manner as in Reference Example 1.

Comparative Reference Example 1 296 parts by weight of dimethylsodium sulfoisophthalate,
4100 parts by weight of polytetramethylene glycol having a number average molecular weight of 1000, 4.4 parts by weight of sodium acetate, and 0.9 parts by weight of titanium tetraisopropoxide were charged in a three-necked flask, and a methyl group was prepared in the same manner as in Reference Example 1. A sulfonic acid group-containing diol was obtained.

Example 1 57.4 parts by weight of the reaction product of Reference Example 1 as the sulfonic acid group-containing diol (A), and polyhexylene carbonate 3 having a number average molecular weight of 1000 as the polymer diol (B).
11 parts by weight and 489 parts by weight of polybutylene adipate having a number average molecular weight of 1000, and a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate as an organic diisocyanate (C1) (weight ratio 80:20) 1
65 parts by weight (NCO / OH = 0.95), and DMF4
760 parts by weight was charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate diol (D).
After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured by GPC and found to be 67,000. In a DMF solution of the intermediate diol (D) obtained above, 106 parts by weight of ethylene glycol as a low molecular diol (E), diphenylmethane-4,4'-diisocyanate (C2) 4
58 parts by weight were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000. To 100 parts by weight of the obtained polyurethane solution, 92 parts by weight of DMF, 1.5 parts by weight of Crisbon Assister SD7 (trademark: Dainippon Ink Co., Ltd.), 1.5 parts by weight of Crisbon Assister SD14 (trademark: Dainippon Ink Co., Ltd.) Was added to obtain an impregnating liquid.

On the other hand, polyethylene terephthalate 50 copolymerized with 5 mol% of sodium sulfoisophthalate component
By using staple fibers of ultrafine fiber-generating fibers obtained by melt spinning 50 parts by weight of polyethylene and 50 parts by weight of high-fluidity polyethylene (polyethylene terephthalate obtained by copolymerizing 5 mol% of sodium sulfoisophthalate component is an ultrafine fiber component) To produce a web, which was used as a needle punch entangled nonwoven fabric. This entangled nonwoven fabric was impregnated with the above impregnating liquid and then put into a 25% aqueous solution of DMF to coagulate. Then, it is treated in hot toluene to dissolve and remove the polyethylene component,
A sheet-like material having a thickness of 1.4 mm was obtained. The sheet-like material was divided into two, and the divided surfaces were buffed with sandpaper to have a thickness of 0.56 mm. Further, the surface at the time of coagulation was treated with an emery buffing machine to form a fiber raised surface. When the sheet-shaped material having the fiber raised surface was dyed under the following conditions,
A leather-like sheet was obtained which was dyed in bright colors and had a good texture. The dyeing fastness of this leather-like sheet was excellent in both the fastness to washing and the fastness to rubbing, which was grade 5 or higher. Dye Catillon Brill Red 4GH Dye concentration 5.0 g / liter Acetic acid 0.2 g / liter Sodium acetate 0.1 g / liter Bath ratio 50: 1 Temperature 130 ° C Time 60 minutes

Comparative Example 1 The same raw material composition as in Example 1 was put into a reactor all at once and reacted at a predetermined temperature for a predetermined time under a nitrogen stream to obtain a concentration of 25%.
A polyurethane solution having a weight average molecular weight of 380,000 was obtained. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1. The entangled nonwoven fabric used in Example 1 was impregnated with the above impregnating liquid, and then put into a 25% aqueous solution of DMF to coagulate. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. Thus, when the polyurethane obtained without passing through the intermediate (D) obtained by reacting the sulfonic acid group-containing diol (A), the polymer diol (B) and the organic diisocyanate (C1) is used, A good sheet was not obtained, and the superiority of the technique of going through the intermediate (D) of the present invention is clear in comparison with Example 1.

Comparative Example 2 In Example 1, 3 parts of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (weight ratio 80:20) was used as the organic diisocyanate (C1).
5 parts by weight (NCO / 0H = 0.20) and 5 parts DMF
An intermediate diol (D) was obtained in the same manner except that the amount was changed to 135 parts by weight. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured by GPC and found to be 11,000. Ethylene glycol 1 was added as a low molecular diol (E) to the DMF solution of the intermediate diol (D) obtained above.
06 parts by weight and 646 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 370,000. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1.

The entangled nonwoven fabric used in Example 1 was impregnated with the above-mentioned impregnating liquid, and then added to a 25% aqueous solution of DMF.
Coagulated. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. Thus, sulfonic acid group-containing diol (A), polymer diol (B), organic diisocyanate (C1)
When a polyurethane obtained via the intermediate (D) obtained by reacting N with NCO / OH of 0.2 was used, a sheet having a good texture was not obtained, and the sulfonic acid group-containing diol (A) of the present invention was not obtained. The superiority of the technique through the intermediate (D) obtained by reacting the polymer diol (B) and the organic diisocyanate (C1) with NCO / OH of 0.5 or more is clear in comparison with Example 1.

Comparative Example 3 280 parts by weight of the reaction product of Comparative Reference Example as the sulfonic acid group-containing diol (A) and polyhexylene carbonate 3 having a number average molecular weight of 1000 as the polymer diol (B).
11 parts by weight and 489 parts by weight of polybutylene adipate having a number average molecular weight of 1000, and 165 parts by weight of a mixture (80:20) of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate as an organic diisocyanate (C1) (NCO / OH = 0.95), and DMF5430
Part by weight was placed in a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate diol. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 71,000. Intermediate diol (D) obtained above
106 parts by weight of ethylene glycol as a low-molecular diol (E) in a DMF solution of diphenylmethane-4,4'-
458 parts by weight of diisocyanate (C2) was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000.
A sheet-like product was obtained in the same manner as in Example 1 except that the polyurethane solution obtained above was used, and the dyeing was successful, but the obtained product was hard and stiff and stiff. It had a bad feeling. in this way,
When the diol is 1000, a sheet having a good texture cannot be obtained, and the effect of using the diol having a molecular weight of 400 or less is clear in comparison with Example 1.

Example 2 48.3 parts by weight of the reaction product of Reference Example 2 as the sulfonic acid group-containing diol (A), and polyhexylene carbonate 5 having a number average molecular weight of 2000 as the polymer diol (B).
51 parts by weight and 516 parts by weight of polybutylene adipate having a number average molecular weight of 2000, 533 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000, and 188 parts by weight of diphenylmethane-4,4'-diisocyanate as an organic diisocyanate (C1) (NCO / OH = 0.7
5), and 9553 parts by weight of DMF are charged into the reactor,
An intermediate diol was obtained by reacting under a nitrogen stream at a predetermined temperature for a predetermined time. After confirming that the isocyanate group was depleted, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured by GPC and found to be 40,000.

DMF of the intermediate diol (D) obtained above
248 parts by weight of ethylene glycol as a low molecular diol (E) and 1100 parts by weight of diphenylmethane-4,4'-diisocyanate (C-2) were added to the solution and reacted.
A polyurethane solution having a weight average molecular weight of 380,000 was obtained. To 100 parts by weight of the obtained polyurethane solution, 19 parts by weight of DMF, 1.5 parts by weight of Crisbon Assister SD7 (trademark: Dainippon Ink Co., Ltd.), and 1.5 parts by weight of Crisbon Assister SD14 (trademark: Dainippon Ink Co., Ltd.) Parts were added to obtain a coating liquid. The entangled nonwoven fabric used in Example 1 was impregnated with the impregnating solution used in Example 1 above, and then the above coating solution was coated to a thickness of 0.5 mm, followed by a 25% aqueous solution of DMF. It was put in and solidified. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 2.2 mm and having a good silver surface. When the obtained sheet-shaped material was dyed in the same manner as in Example 1, it was dyed vividly, and the superiority of the present invention is clear.

Comparative Example 4 48.3 parts by weight of the reaction product of Reference Example 2 as the sulfonic acid group-containing diol (A) and polyhexylene carbonate 5 having a number average molecular weight of 2000 as the polymer diol (B).
11 parts by weight and 516 parts by weight of polybutylene adipate having a number average molecular weight of 2000, 533 parts by weight of polytetramethylene glycol having a number average molecular weight of 2000, and 256 parts by weight of diphenylmethane-4,4'-diisocyanate as an organic diisocyanate (C1) (NCO / OH = 1.0
2) and 8818 parts by weight of DMF were charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate.
After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 220,000. In the DMF solution of the intermediate obtained above, as a low molecular diol (E), 248 parts by weight of ethylene glycol, diphenylmethane-4,4
1043 parts by weight of'-diisocyanate (C2) was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000. A sheet-like product with a silver surface was obtained in the same manner as in Example 2 except that the polyurethane solution obtained above was used. However, the foaming state on the silver surface was poor and hard, and the texture was poor. Thus, the sulfonic acid group-containing diol (A), the polymer diol (B), and the organic diisocyanate (C1) were added to the NCO.
When a polyurethane obtained through the intermediate (D) obtained by reacting / OH at 1.02 is used, a sheet having a good texture cannot be obtained, and the sulfonic acid group-containing diol (A) of the present invention, the polymer The superiority of the technique through the intermediate (D) obtained by reacting the diol (B) and the organic diisocyanate (C1) with NCO / OH of 0.99 or less is clear in comparison with Example 2.

Example 3 44.3 parts by weight of the reaction product of Reference Example 3 as the sulfonic acid group-containing diol (A), and polyhexylene carbonate 6 having a number average molecular weight of 2000 as the polymer diol (B).
00 parts by weight and 1000 parts by weight of polybutylene adipate having a number average molecular weight of 2000, organic diisocyanate (C1)
As diphenylmethane-4,4'-diisocyanate 200 parts by weight (NCO / OH = 0.80), and DMF
8641 parts by weight of was added to a reactor and reacted at a predetermined temperature for a predetermined time under a nitrogen stream to obtain an intermediate diol. After confirming that the isocyanate group was depleted, the weight average molecular weight (in terms of polystyrene) of the intermediate diol was measured by GPC and found to be 48,000.

DMF of the intermediate diol (D) obtained above
186 parts by weight of ethylene glycol and 841 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added to the solution as a low molecular diol (E) and reacted to obtain a polyurethane solution having a weight average molecular weight of 370,000. 92 parts by weight of DMF to 100 parts by weight of the obtained polyurethane solution,
Crisbon Assister SD7 (trademark: Dainippon Ink and Chemicals, Inc.) 1.5 parts by weight, and Crisbon Assister SD
1.5 parts by weight of 14 (trademark: Dainippon Ink and Chemicals, Inc.) was added to obtain a coating liquid. The entangled non-woven fabric used in Example 1 was impregnated with the above impregnating liquid, and then put into a 25% aqueous solution of DMF for coagulation. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet.
When the obtained sheet-like material was dyed in the same manner as in Example 1, it was slightly stiff, but in practice, a vividly dyed sheet-like material having a sufficient texture was obtained, which is an advantage of the present invention. Is clear.

Comparative Example 5 750 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000 and number average molecular weight of 2 were used as the polymer diol (B) without using the sulfonic acid group-containing diol (A).
1250 parts by weight of polybutylene adipate, diphenylmethane as an organic diisocyanate (C1)
200 parts by weight of 4,4'-diisocyanate (NCO / O
H = 0.8) and DMF9684 parts by weight were charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate diol. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 52,000. 186 parts by weight of ethylene glycol as a low molecular diol (E) in a DMF solution of the intermediate diol obtained above,
Diphenylmethane-4,4'-diisocyanate (C-
2) Add 842 parts by weight and react to give a weight average molecular weight of 3
80,000 polyurethane solutions were obtained. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 3. Furthermore, when a sheet-like material having a napped surface impregnated with the above impregnating liquid in the entangled nonwoven fabric was dyed under the following conditions, the fiber part was dyed, but the polyurethane part was not dyed sufficiently and looked good. It is bad, and the effect of using the sulfonic acid group-containing diol (A) of the present invention is clear in comparison with Example 3.

Example 4 Obtained from 3-mercapto-1,2-propanediol as a sulfonic acid group-containing diol (A), a 1: 1 mixture of sodium 2-acrylamido-2-methylpropanesulfonate and vinyl acetate. 200 parts by weight of diol having an average molecular weight of 2000, and polyhexylene carbonate 300 having a number average molecular weight of 1000 as the polymer diol (B)
Parts by weight and 600 parts by weight of polybutylene adipate having a number average molecular weight of 1000, and 165 parts by weight of a mixture (80:20) of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (NCO / OH) as the organic diisocyanate (C1). = 0.95), and 5490 parts by weight of DMF were charged into a reactor and reacted at a predetermined temperature for a predetermined time under a nitrogen stream to obtain an intermediate. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 65,000. Ethylene glycol 1 was added as a low molecular diol (E) to the DMF solution of the intermediate diol (D) obtained above.
06 parts by weight and 461 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 400,000. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1. After the entangled nonwoven fabric of Example 1 was impregnated with the above-mentioned impregnating liquid, it was processed into a sheet-like material having a raised surface in the same manner and dyed, and it was dyed in a vivid color and had a good texture. A sheet is obtained, and the superiority of the present invention is clear.

Comparative Example 6 333 parts by weight of polyhexylene carbonate having a number average molecular weight of 1000 and a number average molecular weight of 1 were used as the polymer diol (B) without using the sulfonic acid group-containing diol (A).
667 parts by weight of polybutylene adipate, 165 parts by weight of a mixture (80:20) of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate as an organic diisocyanate (C1) (NCO / OH = 0.9).
5) and 5190 parts by weight of DMF were charged into a reactor and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain an intermediate.
After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 62,000. To the DMF solution of the intermediate diol obtained above, 106 parts by weight of ethylene glycol and 458 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) as a low molecular diol (E) were added and reacted to obtain a concentration of 25% and a weight average. A polyurethane solution having a molecular weight of 390,000 was obtained. Using the obtained polyurethane solution, an impregnating liquid was prepared in the same manner as in Example 1. Furthermore, when a sheet-like material having a napped surface impregnated with the above impregnating liquid in the entangled nonwoven fabric was dyed under the following conditions, the fiber part was dyed, but the polyurethane part was not dyed sufficiently and looked good. It is bad, and the effect of using the sulfonic acid group-containing diol (A) of the present invention is clear in comparison with Example 4.

Comparative Example 7 The same raw material composition as in Example 4 was put into a reactor all at once and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to give a concentration of 25%.
A polyurethane solution having a weight average molecular weight of 400,000 was obtained. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1. The entangled nonwoven fabric used in Example 4 was impregnated with the above impregnating liquid, and then put into a 25% aqueous solution of DMF for coagulation. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. Thus, when the polyurethane obtained without passing through the intermediate (D) obtained by reacting the sulfonic acid group-containing diol (A), the polymer diol (B) and the organic diisocyanate (C1) is used, A good sheet was not obtained, and the superiority of the technique of going through the intermediate (D) of the present invention is clear in comparison with Example 4.

Comparative Example 8 In Example 4, 35 parts by weight (NCO / OH = 0.20) of a mixture (80:20) of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate was used as the organic diisocyanate (C1). 20) and DMF 5540 parts by weight except that the weight average molecular weight (polystyrene conversion) of 12,000 was similarly obtained. In a DMF solution of the intermediate diol (D) obtained above, 106 parts by weight of ethylene glycol as a low molecular diol (E), diphenylmethane-4,4'-diisocyanate (C2) 64
7 parts by weight was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 400,000. Using the obtained polyurethane solution, an impregnating solution was prepared in the same manner as in Example 1. Example 4
After impregnating the above-mentioned impregnating liquid into the entangled nonwoven fabric used in
It was put into a 25% aqueous solution of MF to coagulate. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 1.4 mm. The obtained sheet-like material was hard and had an extremely poor feel to the touch, and was hardly called a leather-like sheet. Thus, the sulfonic acid group-containing diol (A), the polymer diol (B), and the organic diisocyanate (C1) were added to NCO / OH.
When a polyurethane obtained through the intermediate (D) obtained by reacting with 0.2 is used, a sheet having a good texture cannot be obtained, and the sulfonic acid group-containing diol (A) and polymer diol ( B), organic diisocyanate (C1) N
The superiority of the technique via the intermediate (D) obtained by reacting with CO / OH of 0.5 or more is clear in comparison with Example 4.

Example 5 A diol 55 having an average molecular weight of 1100 obtained from sodium styrenesulfonate and 3-mercapto-1,2-propanediol as a sulfonic acid group-containing diol (A).
Parts by weight, number average molecular weight 2 as polymer diol (B)
600 parts by weight of polyhexylene carbonate and 1300 of polybutylene adipate having a number average molecular weight of 2000
Parts by weight, 188 parts by weight of diphenylmethane-4,4'-diisocyanate (NCO / OH = 0.75) as an organic diisocyanate (C1), and 10490 parts by weight of DMF are charged into a reactor, and a predetermined temperature is maintained for a predetermined time under a nitrogen stream. The reaction was performed to obtain an intermediate. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 43,000. Ethylene glycol 2 as a low-molecular diol (E) was added to the DMF solution of the intermediate diol (D) obtained above.
48 parts by weight and 1105 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 430,000. A coating solution was prepared using the obtained polyurethane solution in the same manner as in Example 2. The entangled nonwoven fabric used in Example 4 was impregnated with the impregnating solution used in Example 4 above, and then the above coating solution was coated to a thickness of 0.5 mm, followed by DMF.
Was poured into a 25% aqueous solution to solidify. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet-like material having a thickness of 2.2 mm and having a good silver surface. When the obtained sheet material was dyed in the same manner as in Example 4, it was dyed vividly, and the superiority of the present invention is clear.

Comparative Example 9 In Example 5, 256 parts by weight of diphenylmethane-4,4'-diisocyanate (C1) (NCO / OH =) was used.
1.02) and DMF to 10510 parts by weight in the same manner except that the weight average molecular weight (in terms of polystyrene) 2
40,000 intermediates were obtained. Intermediate diol (D) obtained above
Of DMF solution as a low molecular diol (E), 248 parts by weight of ethylene glycol, diphenylmethane-4,4'-
1042 parts by weight of diisocyanate (C2) was added and reacted to obtain a polyurethane solution having a weight average molecular weight of 410,000. A sheet-like product with a silver surface was obtained in the same manner as in Example 5 except that the polyurethane solution obtained above was used. However, the foaming state of the silver surface was poor and the product had a poor texture. Thus, the fluorine-containing diol (A), the polymer diol (B) and the organic diisocyanate (C1) were added to NCO / OH.
When a polyurethane obtained through the intermediate (D) obtained by reacting with 1.02 is used, a sheet with good texture cannot be obtained, and the sulfonic acid group-containing diol (A) and polymer diol ( The superiority of the technique of B) and the intermediate (D) obtained by reacting the organic diisocyanate (C1) with NCO / OH of 0.99 or less is clear in comparison with Example 5.

Example 6 Obtained from 3-mercapto-1,2-propanediol as a sulfonic acid group-containing diol (A), a 1: 1 mixture of sodium 2-acrylamido-2-methylpropanesulfonate and vinyl acetate. 200 parts by weight of diol having an average molecular weight of 2000, 800 parts by weight of polyhexylene carbonate having a number average molecular weight of 2000 as diol (B) and 100 parts of polybutylene adipate having a number average molecular weight of 2000.
0 parts by weight, 200 parts by weight of diphenylmethane-4,4'-diisocyanate (NCO / OH = 0.80) as an organic diisocyanate (C1), and 9680 parts by weight of DMF were charged into a reactor and a predetermined temperature was maintained under a nitrogen stream. The reaction was carried out for a time to obtain an intermediate. After confirming that the isocyanate group was gone, the weight average molecular weight (in terms of polystyrene) of the intermediate was measured by GPC and found to be 48,000. Ethylene glycol 18 was added as a low-molecular diol (E) to the DMF solution of the intermediate diol (D) obtained above.
6 parts by weight and 840 parts by weight of diphenylmethane-4,4'-diisocyanate (C2) were added and reacted to obtain a polyurethane solution having a weight average molecular weight of 390,000. An impregnating liquid was prepared in the same manner as in Example 1 using the obtained polyurethane solution. The entangled non-woven fabric used in Example 4 was impregnated with the above impregnating solution, and then put into a 25% aqueous solution of DMF for coagulation. Then, it was treated in hot toluene to dissolve and remove the polyethylene component to obtain a sheet. The obtained sheet-like material was a little hard, but it is practically sufficient,
When a dyeing test was conducted in the same manner as in Example 4, a sheet dyed in a vivid color was obtained, and the superiority of the present invention is clear.

[0051]

The leather-like sheet of the present invention has excellent physical properties such as mechanical properties and durability, is suitable for processing, and uses a polyurethane resin which can be dyed with a cationic dye. A leather-like sheet that can be dyed with a cationic dye that has excellent flexibility, cold resistance, heat resistance, and durability. By dyeing with a cationic dye, it has excellent color development and durability, and can be used for clothing, shoes, and bags. It is useful for various purposes such as, furniture, vehicle interior materials, and sundries.

Claims (2)

[Claims] 1. A sulfonic acid group-containing diol (A) obtained by substantially replacing the X component of a sulfonic acid group-containing compound represented by the following general formula (I) with a diol represented by the general formula (II). Of a polymer diol (B) having a number average molecular weight of 500 to 3000 selected from the group consisting of polyesters, polycarbonates, polylactones and polyethers and an organic diisocyanate (C1) at an NCO / OH equivalent ratio of 0.5 to 0. By reacting the terminal OH intermediate diol (D) obtained by reacting in a quantitative relationship such as 99, the low molecular diol (E) and diphenylmethane-4,4'-diisocyanate (C2) A leather-like sheet dyeable with a cationic dye, which comprises the obtained polyurethane and a fiber structure. [Chemical 1] (However, X is an OH group or an oxyalkyl group) HO-R-OH (II) (however, R is an alkylene group or polyoxyalkylene group having a molecular weight of 400 or less) 2. A sulfonic acid group-containing diol obtained by polymerizing a sulfonic acid group-containing radically polymerizable monomer in the presence of dimethylolpropionic acid and / or a compound having two hydroxyl groups and one thiol group. The number average molecular weight selected from the group consisting of (A), polyester, polycarbonate, polylactone and polyether is 50.
The polymer diol (B) of 0 to 3000 and the organic diisocyanate (C1) have an NCO / OH equivalent ratio of 0.5 to
A terminal O obtained by reacting in a quantitative relationship such that 0.99
H intermediate diol (D) and low molecular diol (E),
Diphenylmethane-4,4'-diisocyanate (C
2) A cationic dye-dying leather-like sheet comprising a polyurethane and a fibrous structure obtained by reacting with 2).