JP3128375B2 - Cationic dye-dyed leather-like sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a leather-like sheet containing a dyeable polyurethane. More specifically, a polyester diol having a specific structure is blended as a part of the component constituting the polyurethane resin, and various physical properties such as durability, durability, etc., obtained by reacting, excellent in processability, and cationic The present invention relates to a cationic dye-dyed leather-like sheet characterized by using a polyurethane capable of being dyed.

[0002]

2. Description of the Related Art Polyurethane is excellent in mechanical performance. A polyurethane solution is impregnated and / or coated on a fibrous substrate, and wet-coagulated or dry-formed to form raised fibers on the surface of a fibrous structure. A leather-like sheet obtained by applying a surface finishing layer mainly composed of a leather is used in various fields. However, conventional polyurethanes did not have dyeing seats necessary for dyeing with dyes such as acid dyes and cationic dyes, so that they could not be dyed substantially. In the case of disperse dyes, dyeing is possible, but due to the looseness of the amorphous structure of the polyurethane, the dye is difficult to stay inside the resin, that is, the dyeing fastness is extremely poor, due to washing and friction, etc. Discoloration and fading were easily observed.

In an attempt to improve these drawbacks, dyeing seats have been introduced into polyurethane. For example, by using a compound having a sulfonic acid group, a polyurethane dyeable to a cationic dye can be obtained. It has been known. 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,
Depending on the method of the publication, aniline having a dyed seat is 1
It is functional and is introduced at the end of a polyurethane polymer molecule. Therefore, if a large amount of aniline is used to enhance the dyeing properties, the molecular weight of the polyurethane becomes too small, the viscosity of the polyurethane solution becomes too low, and not only the process passability deteriorates, but also the mechanical performance of the resin decreases. Is not preferred. Also, if the molecular weight of polyurethane is made large enough to satisfy the mechanical performance and processability (solution viscosity), it is not possible to introduce as much aniline as necessary to secure a sufficient dyeing seat. However, there were difficulties in implementing it industrially.

Japanese Patent Publication No. 46-2356 discloses 2,5-
Bifunctional such as sodium di (β-hydroxyethoxy) benzenesulfonate, sodium 3- (β-hydroxyethoxy) -5carboxybenzenesulfonate, sodium 2-amino-4- (β-hydroxyethoxycarbo) benzenesulfonate, and the like. It is disclosed that a reactive compound can be added and reacted at any point in the production stage of polyurethane or polyurea, and the copolymer obtained by the method can be emulsified in water. However, the polyurethane obtained by the method of this publication is suitable for emulsification in water, but upon application to artificial leather, it elutes or swells when poured into a coagulation bath composed of water and DMF or when dyed, There was a problem in the process passability, such as poor shape retention, and it was not applicable to industrial production of artificial leather.

JP-A-59-6210 discloses that at least one component (A) comprises a polyester polyol having terephthalic acid and / or isophthalic acid in an amount of 30 mol% or more of all carboxylic acids and containing a sulfonic acid group. A polyurethane resin composition comprising a high molecular weight polyol, (B) a diisocyanate, and (C) a chain linking agent is disclosed. However, the polyurethane obtained by the method disclosed in this publication contains terephthalic acid and / or isophthalic acid in an amount of 30 mol% or more of the total carboxylic acid, so that the resin is inferior in flexibility, cold resistance and the like. It is totally bad.

Further, Japanese Patent Publication No. 63-43507 discloses an ultrafine fiber containing copolymerized polyethylene terephthalate containing ethylene isophthalic acid sulfonate and -SO
_A leather-like sheet made of a silver layer made of polyurethane containing 3X is disclosed. In the method according to the publication, polyurethanes containing -SO ₃ X JP-B 55-
The use of the polyurethane disclosed in Japanese Patent No. 34815 is particularly excellent, and the superiority thereof is claimed. However, when the polyurethane disclosed in the same publication is used, the use of the polyurethane is industrially required as described above. There were difficulties to implement.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to introduce a dyeing seat of a cationic dye into a polyurethane, and to obtain a texture comprising an industrially applicable polyurethane having improved dyeing properties and a fibrous substrate, Excellent flexibility, durability, etc.
Another object of the present invention is to provide a leather-like sheet that can be dyed with a cationic dye.

[0008]

According to the present invention, there is provided a leather-like sheet comprising a fiber base and a polyurethane resin, wherein the polyurethane resin comprises a sulfonic acid group-containing compound represented by the following general formula (I) as an acid component. And a polyurethane elastomer obtained by reacting an organic diisocyanate (B) with a polyester diol (A) having a number average molecular weight of 500 to 5,000 and containing an aliphatic low molecular diol having 4 or more carbon atoms as a diol component. It is a cationic dye-dyed leather-like sheet characterized by the following.

Embedded image (However, X is an OH group or an oxyalkyl group, and M is hydrogen or a monovalent metal.)

X in 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, particularly a methoxy group, is often used.

The polyester diol (A) can be obtained, for example, by reacting a sulfonic acid group-containing compound represented by the above general formula (I) as a dibasic acid with an aliphatic low molecular diol having 4 or more carbon atoms. . As the dibasic acid, one or more aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid besides the above-mentioned sulfonic acid group-containing compound. They can be used in combination. Among them, the leather-like sheet from which a dibasic acid having a methylene chain length of 4 to 8, such as adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc., has a good texture and durability. However, aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid reduce the solubility of the obtained polyester diol in the solvent used during urethanization, which not only hinders the polyurethane production process but also hardens the obtained polyurethane. However, it has disadvantages such as a decrease in cold resistance and a deterioration in the texture of the leather-like sheet, which is not preferable. The amount of the sulfonic acid group-containing compound represented by the general formula (I) varies depending on the dyeability, texture, durability and the like required for the leather-like sheet, but is at least 5 mol% of the total dibasic acid, It is often 10 mol%.

The aliphatic low molecular weight diol having 4 or more carbon atoms to be reacted with the dibasic acid includes butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol which may be substituted with a lower alcohol. One or a mixture of two or more aliphatic diols such as diol, nonanediol, decanediol and dodecanediol is used. Among them, the texture of a leather-like sheet obtained by obtaining one or a mixture of two or more aliphatic diols having a carbon chain length of 5 to 9 such as methylpentanediol, hexanediol, heptanediol, methyloctanediol, and nonanediol,
It has good durability and is suitably used. When the number of carbon atoms is 3 or less, the solubility of the sulfonic acid group-containing polyester diol is reduced, which is not only likely to cause troubles in the polyurethane production process, but also has a problem that the obtained leather-like sheet has a hard feel and is preferable. Absent.

The number average molecular weight of the polyester diol (A) used in the present invention is from 500 to 3000, and more preferably from 700 to 2500. 500
If the ratio is less than 1, the flexibility of the leather-like sheet tends to be lost or the feeling is lowered, which is not preferable. 300
If it exceeds 0, it may be difficult to obtain a leather-like sheet having a good balance of feeling, flexibility, cold resistance, heat resistance, and durability. There are difficulties in industrial production of diols, which is not preferred.

The polyester diol (A) may be a polyester diol, a polycarbonate diol, a polycaprolactone diol usually used in the production of polyurethane, as long as the object of the present invention is not impaired.
Polymer diols such as polyether diols can be mixed and used. Polyester diol (A) has a sulfonic acid group of 1 to 1000 μe with respect to polyurethane.
Among them, q / g is often used at 10 to 500 μeq / g.

The polyester diol used by mixing with the polyester diol (A) can be obtained, for example, by reacting a dibasic acid with a diol. Examples of the dibasic acid include aromatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, and brassic acid, aromatic dibasic acids such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. One of the basic acids or a combination thereof can be used. Among these, aliphatic dibasic acids, especially dibasic acids having a methylene chain length of 4 to 8, such as adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, etc., are more preferably used. As the diol, aliphatic alcohols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol and dodecanediol which may be substituted with a lower alcohol may be used. diol, cyclohexane diol, alicyclic diol of hydrogenated Kishirirengu recalls, etc., xylylene glycol, one or a mixture of two or more such aromatic diols such as are used, among them aliphatic diols, especially One or a mixture of two or more aliphatic diols having a carbon chain length of 4 to 9 such as butanediol, methylpentanediol, hexanediol, heptanediol, methyloctanediol, and nonanediol are preferred. Used to.

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, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, which may be substituted with a lower alcohol,
One or more kinds of 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 Among them, aliphatic diols are used. Among them, one or more aliphatic diols having a carbon chain length of 4 to 9, such as butanediol, methylpentanediol, hexanediol, heptanediol, methyloctanediol, and nonanediol, are used. A mixture of two or more is suitably used.

Polylactone diols include, for example, poly-ε-caprolactone diol, poly-trimethyl-ε
-Caprolactonediol, poly-β-methyl-δ-valerolactonediol and the like. Polyether diols include, for example, polytetramethylene glycol,
Polypropylene glycol, polyethylene grayed recall like.

The organic diisocyanate (B) is, for example, diphenylmethane-4,4'-diisocyanate,
Aromatic diisocyanates such as 2,4- or 2,6-tolylene diisocyanate, meta- or para-phenylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hydrogenated MDI, etc. And the like are used. Of these, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, and cyclohexane diisocyanate are often preferred because of the good surface properties and feeling of the sheet obtained by coagulation with a non-solvent.

In order to produce the polyurethane resin used in the present invention, the polyester diol (A) and the organic diisocyanate (B) are used as essential raw materials, but a chain extender may be used if desired. . Such a chain extender may be any one as long as it is used for the production of ordinary polyurethane, and a low molecular weight compound having a molecular weight of 400 or less and having two or more active hydrogen atoms in a molecule is usually used. You. Representative examples of such low molecular weight compounds include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, which may be substituted with a lower alcohol. aliphatic diols such as dodecanediol, cyclohexanediol, alicyclic diols such as hydrogenated Kishirirenguri co Lumpur,
One or two kinds of aromatic diols such as xylylene glycol, further diols such as diethylene glycol, diamines such as ethylenediamine, propylenediamine, xylylenediamine, isophoronediamine, piperazine, and also dihydrazide such as adipic dihydrazide and isophthalic dihydrazide. The above mixture is used. Among them, aliphatic diols, especially ethylene glycol and butanediol, are used for leather-like sheets,
It is suitably used in terms of balance of flexibility, cold resistance and heat resistance.

Although the amount of the chain extender is not particularly limited,
Its molecular structure, the blending amount of polyester diol (A),
Although it depends on the molecular weight of the polymer diol and the type of the organic diisocyanate, usually, the equivalent ratio of the chain extender / polymer diol to the total amount of the polymer diol including the polyester diol (A) is 0.5 to 7 and preferably 1 to 5.
The leather-like sheet obtained with 5.5 is often suitable in terms of feel, flexibility, cold resistance and heat resistance.

The amount of the organic diisocyanate (B) used is not particularly limited, and the viscosity of the polyurethane solution, the sulfonic acid group-containing polyester diol (A), the polymer diol,
It depends on the molecular weight of the chain extender, the water content in the system, etc., but usually the equivalent ratio of (A) to the polymer diol, NCO and active hydrogen group from the chain extender (NCO / active hydrogen)
Of 0.95 to 1.2, especially 0.97 to 1.1.

A catalyst is not always required when the polymerization method used in the present invention is carried out, but catalysts used in the production of ordinary polyurethane, for example, metal compounds such as titanium tetraisopropoxide, dibutyltin dilaurate, tin octate, etc. Tetramethylbutanediamine,
Tertiary amines such as 1,4-diaza (2,2,2) bicyclooctane can be used.

As the solvent for the polyurethane obtained by the method used in the present invention, commonly used solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, ethyl acetate, methyl ethyl ketone and tetrahydrofuran are used.

When the polyurethane obtained by the method used in the present invention is used, various additives used in conventional polyurethanes such as a flame retardant such as a phosphorus compound and a halogen-containing compound, an antioxidant, an ultraviolet absorber, 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-finished leather-like sheet having a polyurethane coating layer on the surface.
The fibers are not particularly limited to fibers dyed with a cationic dye, but fibers made of fibers dyed with a cationic dye are preferable in order to prevent the cut surface of the leather-like sheet from having a different color. On the other hand, in the case of a fiber-naped suede-like leather-like sheet, there is no particular limitation as long as the sheet is made of a fiber that can be dyed with a cationic dye, and synthetic fibers such as polyacrylonitrile and sulfonic acid group-modified polyester,
Alternatively, natural fibers such as wool can be used.

As the fibrous structure, a woven fabric, a knitted fabric or a non-woven fabric is used, but a non-woven fabric is preferable in terms of easy formation of uniform nap, surface smoothness when forming a coating layer, and the like. The nonwoven fabric may be one in which a knitted fabric for reinforcement or the like is laminated inside as required. Above all, the average fineness of three-dimensional entanglement is 0.1 denier or less, and furthermore 0.005 to
A nonwoven fabric made of a 0.1 denier ultrafine fiber bundle is preferable.

An entangled nonwoven fabric comprising such an ultrafine fiber bundle
Is a spinnable thermoplastic resin that can be dyed with a cationic dye,
For example, a known sulfonic acid group-modified polyester resin
Sulfonic acid group modification consisting of two or more polymer components
It can be derived from polyester ultrafine fiber generating fiber.
Other polymers constituting microfiber-generating fibers are particularly restricted
No, with sulfonic acid group modified polyester resin and solvent
The dissolution or decomposability of the
Resin with low affinity for sulfonic acid group-modified polyester resin
And a sulfonic acid group-modified polyester under spinning conditions.
Resin with a lower melt viscosity than
good. For example, polyethylene, polypropylene, ethylene
-Propylene copolymer, ethylene-vinyl acetate copolymer
Body, ethylene-acrylate copolymer, ethylene
-Α-olefin copolymer, polystyrene, styrene-
Isoprene copolymer, styrene-isoprene copolymer
Hydrogenated product, styrene-butadiene copolymer, styrene-butadiene
It is selected from hydrogenated products of a tadiene copolymer. And su
It consists of a sulfonic acid group-modified polyester resin and another polymer.
Fibers are mixed at a predetermined mixing ratio andFusionDissolved in the systemFusion
To form a mixed system and spin.FusionDissolved in the system
FusionAnd the joining-division is repeated a plurality of times at the spinning machine head.
Method of forming a mixed system and spinning, separate meltingFusionDissolved in the systemFusion
And spinning with the fiber shape defined by the spinneret
Sulfonic acid group-modified polyester
The fat component is 40 to 80% by weight, and the sulfone in the fiber
5 or more acid-modified polyester resin microfiber components are preferred.
Sulfonic acid group modification preferably in the range of 50 to 800
Polyester ultrafine fiber generating fiber is obtained. Extra fine fiber generation
Mold fibers may be processed as usual, such as by drawing or heat setting.
Fineness of 2 to 15 denier after processing
Average fineness of polyester extra fine fiber component (calculated value) 0.2
Denier or less, preferably 0.005 to 0.1 denier
Fiber.

The microfiber-generating fiber is defibrated with a card, and a random web or a cross-wrap web is formed through a webber. The obtained fiber web is laminated to a desired weight and thickness. Next, the fiber web is subjected to a fiber entanglement treatment by 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, the fiber-entangled nonwoven fabric is obtained by adding a coagulation controlling agent, a release agent, a plasticizer, a stabilizer, an antioxidant, a light stabilizer , a colorant, and the like, if necessary, to the above-mentioned polyurethane solution. And then impregnated and / or applied to a fibrous substrate and wet or dry coagulated. In the case of ultrafine fiber-generating fibers, impregnation of the polyurethane composition liquid into the fiber entangled non-woven fabric prior to or after application, after impregnation, application, is treated with a solvent for the other resin constituting the fiber and a non-solvent for the fiber to produce ultrafine fibers. Metamorphose. The amount of the polyurethane resin occupying the sheet-like material composed of the fibrous structure and the polyurethane resin is not particularly limited, but is 10 to 60% by weight, especially 15 to
It is often used at 45%. If the amount of urethane used is small, it has a rather loose texture and 10%
If it is less than that, it becomes remarkable. If the amount of urethane is large, it tends to be hard or have a texture without swelling. 60%
When it is used beyond the range, the tendency becomes remarkable.

Further, the sheet-like material may be further provided with a porous or non-porous coating layer obtained from the above-mentioned polyurethane, if necessary, to give a leather-like sheet with silver, or at least one surface thereof. By raising the skin, it is possible to obtain a fiber-napped suede-like leather-like sheet. Further, if necessary, it can be slice-divided into an arbitrary thickness in the thickness direction at an arbitrary stage. The resulting leather-like sheet is dyed with a cationic dye to produce a leather-like sheet with excellent color development, fastness, surface sliminess, texture, flexibility, cold resistance, heat resistance, durability, etc. Can be.

[0030]

The leather sheet of the present invention thus obtained is useful for various uses such as clothing, shoes, bags, furniture, vehicle interior materials, and miscellaneous goods. Polyurethane resin can be dyed with cationic dyes without losing its desirable mechanical properties and processing suitability, and without deteriorating its desirable properties in the production process of leather-like sheet, a leather-like sheet with good texture was obtained. Although the mechanism of action is not clear, since it is obtained from the sulfonic acid group-containing polyester diol (A) and the organic diisocyanate (B), the soft segment and the hard segment constituting the polyurethane resin maintain a desirable microphase separation state. On the other hand, it is considered that since the sulfonic acid serving as a dyeing seat of the cationic dye was introduced, the leather sheet-like material impregnated with the polyurethane resin and provided as the coating layer was given the above-described preferable characteristics.

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

<Production of Sulfonic Acid Group-Containing Polyester Diol (A)> Reference Example 1 296 parts by weight of dimethyl sodium sulfoisophthalate
A mixture of 146 parts by weight of adipic acid, 1,9-nonanediol and methyloctanediol in a weight ratio of 60:35 12
80 parts by weight, 1.1 parts by weight of sodium acetate and 0.2 parts by weight of titanium tetraisopropoxide are charged into a three-necked flask, and heated to 180 ° C. under a nitrogen stream while stirring. The temperature is further raised to 220 ° C. according to the distillation rate of methyl alcohol and water. Further, the degree of vacuum was gradually increased by a vacuum pump to complete the polymerization, and a sulfonic acid group-containing polyester diol having a number average molecular weight of 2,000 was obtained. From the elemental analysis value, the sulfonic acid group concentration was 1.4 meq / g.

Reference Example 2 592 parts by weight of dimethyl sodium sulfoisophthalate
202 parts by weight of sebacic acid, 640 parts by weight of 3-methyl-1,5-pentanediol, 0.85 parts by weight of sodium acetate, and 0.2 parts by weight of titanium tetraisopropoxide are charged into a three-necked flask, and stirred while stirring. Heat to 180 ° C. under air flow. The temperature is further increased to 220 ° C. according to the distillation rate of methyl alcohol. The temperature is further raised to 220 ° C. according to the distillation rate of methyl alcohol and water. Further, the degree of vacuum was gradually increased by a vacuum pump to complete the polymerization, and a sulfonic acid group-containing polyester diol having a number average molecular weight of 2,000 was obtained. From the elemental analysis value, the sulfonic acid group concentration was 1.8 meq / g.

Reference Example 3 A three-necked flask was charged with 59 parts by weight of dimethyl sodium sulfoisophthalate, 200 parts by weight of dimethyl terephthalate, 300 parts by weight of ethylene glycol, 0.1 part by weight of sodium acetate, and 0.1 part by weight of zinc acetate. Heat to 180 ° C. in a nitrogen stream while stirring. After reacting for 3 hours while distilling off methyl alcohol, the polymerization was completed by gradually raising the temperature and reducing the pressure, and a sulfonic acid group-containing polyester diol having a number average molecular weight of 2,000 was obtained. The sulfonic acid group concentration was 0.94 meq / g based on the elemental analysis value.

[0035] Example 1 DMF10130 reaction product 200 parts by weight of the Reference Example 1 part by weight of the sulfonic acid group-containing Poriesu Te <br/> Rujioru (A), polyhexylene carbonate 900 with a number average molecular weight of 2,000 as a polymer diol Parts by weight and 900 parts by weight of polybutylene adipate having a number average molecular weight of 2,000, 217 parts by weight of ethylene glycol as a chain extender, and diphenylmethane-4,4 'as an organic diisocyanate (B)
1160 parts by weight of diisocyanate were added and reacted to obtain a polyurethane solution having a viscosity of 400 poise (temperature of 30 ° C.). To 100 parts by weight of the solution, 92 parts by weight of DMF and Chris Bon Assister SD7 (trade name: Dainippon Ink Co., Ltd.)
1.5 parts by weight, Chris Bon Assister SD14 (trademark:
(Dai Nippon Ink Co., Ltd.) (1.5 parts by weight) to obtain an impregnating liquid.

An ultrafine fiber-generating fiber (sodium sulfoisophthalate component) obtained by melt-spinning 50 parts by weight of polyethylene terephthalate obtained by copolymerizing 5 mol% of a sodium sulfoisophthalate component and 50 parts by weight of polyethylene having high fluidity. Was made using staple fibers of polyethylene terephthalate, which is an ultrafine fiber component obtained by copolymerizing 5 mol% of the above, to give a needle punch entangled nonwoven fabric. After impregnating this impregnating liquid into this entangled nonwoven fabric, 25% of DMF
It was put into an aqueous solution and coagulated. Then, the mixture was treated in hot toluene to dissolve and remove the polyethylene component, thereby obtaining a sheet having a thickness of 1.4 mm. This sheet was sliced and divided into two parts, and the divided surfaces were buffed with sandpaper to a thickness of 0.56 mm. Further, the surface at the time of solidification was treated with an emery buffing machine to form a napped surface.

When the sheet having the napped surface is dyed under the following conditions, the sheet is dyed in a vivid color, and a leather-like sheet having a good texture is obtained. The superiority of the present invention is evident. GRL dye concentration 5.0 g / l acetic acid 0.2 g / l sodium acetate 0.1 g / l bath ratio 50: 1

Comparative Example 1 1000 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000 and a number average molecular weight of 200 were used as the polymer diol without using the sulfonic acid group-containing diol (A).
0, 1000 parts by weight of polybutylene adipate, 217 parts by weight of ethylene glycol as a chain extender, 1165 parts by weight of diphenylmethane-4,4'-diisocyanate as an organic diisocyanate (B), and DMF10150
A part by weight was put into a reactor, and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to obtain a polyurethane solution having a viscosity of 410 poise (30 ° C.). The obtained polyurethane solution was used in Example 1.
Was prepared in the same manner as described above. A dyed leather-like sheet was obtained in the same manner as in Example 1 except that this impregnating liquid was used. In the obtained leather-like sheet, the fibers were dyed, but the polyurethane portion was not dyed at all, and had a spotted pattern, which was not practical.

Example 2 400 parts by weight of the reaction product of Reference Example 2 as a sulfonic acid group-containing diol (A), 600 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000 as a polymer diol and polybutylene adipate having a number average molecular weight of 2,000 1
000 parts by weight, 1010 parts by weight of diphenylmethane-4,4'-diisocyanate as an organic diisocyanate (B), 186 parts by weight of ethylene glycol as a chain extender, and 7460 parts by weight of DMF are charged into a reactor at a predetermined temperature under a nitrogen stream. Reaction viscosity 400 poise (3
(0 ° C.). 20 parts by weight of toluene was added to 100 parts by weight of the obtained polyurethane solution to prepare a coating solution. The above coating solution was applied on release paper so as to have a dry thickness of 50 μm, and was immediately superimposed on the 1.4 mm thick sheet obtained in Example 1, transferred and dried, and the silver surface layer was dried. To obtain a sheet-like material. When the obtained sheet was dyed in the same manner as in Example 1, the sheet was vividly dyed, and the superiority of the present invention is clear.

Comparative Example 2 750 parts by weight of polyhexylene carbonate having a number average molecular weight of 2,000 and 1250 parts by weight of polybutylene adipate having a number average molecular weight of 2,000 as a polymer diol without using the sulfonic acid group-containing diol (A), and an organic diisocyanate (B) ), 1015 parts by weight of diphenylmethane-4,4'-diisocyanate, 186 parts by weight of ethylene glycol as a chain extender, and 7460 parts by weight of DMF are charged into a reactor, and reacted under a nitrogen stream at a predetermined temperature for a predetermined time to have a viscosity of 420 poise ( 30 ° C.). A sheet-like material having a silver surface layer was obtained and dyed in the same manner as in Example 2 except that the polyurethane solution obtained above was used, and staining was performed. And was not substantially stained.

Comparative Example 3 The reaction was carried out in the same manner as in Example 2 except that the polyester diol of Reference Example 3 was used as the sulfonic acid group-containing diol (A). No solution could be obtained.

[0042]

The leather-like sheet of the present invention uses a polyurethane resin which is excellent in various physical properties such as mechanical properties and durability, workability, and can be dyed with a cationic dye. A leather-like sheet that can be dyed with a cationic dye excellent in flexibility, cold resistance, heat resistance, and durability, and has excellent coloring and durability when dyed with a cationic dye. It is useful for various applications such as furniture, vehicle interior materials, and miscellaneous goods.

Claims (1)

(57) [Claims] 1. A leather-like sheet comprising a fiber substrate and a polyurethane resin, wherein the polyurethane resin comprises:
A sulfonic acid group-containing compound represented by the following general formula (I) is contained as an acid component, and an aliphatic low molecular diol having 4 or more carbon atoms is contained as a diol component.
A cationic dye-dying leather-like sheet comprising a polyurethane elastomer obtained by reacting a polyester diol (A) with an organic diisocyanate (B). Embedded image (However, X is an OH group or an oxyalkyl group, and M is hydrogen or a monovalent metal ion.)