JP2001019735A - Polyurethane resin and leathery sheetlike material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin excellent in dyeability for a cationic dye and further excellent in dynamic characteristics, durability, processing characteristics, etc., by using a compound having a specific structure as a part of a component constituting a polyurethane resin. SOLUTION: This resin is obtained by copolymerizing a compound having a sulfonic acid quaternary phosphonium salt group which is preferably a 5-quaternary phosphonium sulfoisophthalic acid bisdiol ester represented by the formula (X is a 2-10C alkylene; R1 to R4 are each a 1-10C alkyl or the like) [e.g. 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonic acid tetrabutylphosphonium salt] in an amount of 2.0-250 mol/106 g in a polyurethane resin. The resin is preferably obtained by reacting a polymer diol having 50-4,000 average molecular weight with the above compound, a low-molecular chain extender (e.g. ethylene glycol) and an organic diisocyanate (e.g. diphenylmethane diisocyanate).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin having excellent dyeing properties, and a leather-like sheet using the resin. More specifically, a polyurethane resin obtained by using a compound having a specific structure as a part of a component constituting the polyurethane resin, which has excellent dyeing properties for a cationic dye, and has excellent mechanical properties, durability, and processing properties. And a leather-like sheet made of the polyurethane resin and having excellent dyeability of a cationic dye.

[0002]

2. Description of the Related Art Polyurethane resins have excellent mechanical properties and durability, and are frequently used in leather-like sheet materials such as artificial leather. However, conventional polyurethane resins, which are usually dyed with an acid dye, have a problem that they are inferior in washing fastness and wet rub fastness. On the other hand, dyeing is possible with a disperse dye, but there is a problem that the dye easily migrates due to the looseness of the amorphous structure of the polyurethane resin.

For this reason, dyeing with a metal complex salt dye or incorporating a pigment into a polyurethane resin has been carried out. However, the former method has a problem that a clear dyed product cannot be obtained depending on the color. On the other hand, in the latter method, when a fibrous base material is impregnated into a leather-like sheet, it is difficult to match the color development of the fiber with the color of the resin, and the "irritation phenomenon" tends to occur. is there.

In order to solve these problems, attempts have been made to introduce a dyeing seat having an affinity for a cationic dye in a polyurethane resin. For example, Japanese Unexamined Patent Publication
JP-A-240585 and JP-A-6-192968 propose polyurethane resins obtained by copolymerizing a compound having a sulfonic acid metal base in a soft segment of the polyurethane resin. Certainly, according to these methods, the dyeability of the cationic dye becomes good, and a dyed article having excellent clarity can be obtained. However, due to the introduction of the metal sulfonate group, the resistance of the polyurethane resin itself is reduced. There is a problem in durability such as a decrease in hydrolyzability and light resistance, and further improvement is desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made on the basis of the above-mentioned prior art, and it is an object of the present invention to provide a polyurethane which is excellent in mechanical properties, durability, processing properties, etc. and has good dyeability of a cationic dye. An object of the present invention is to provide a resin and a leather-like sheet having excellent dyeability of a cationic dye using the polyurethane resin.

[0006]

According to the study of the present inventors, a first object of the present invention is to provide a compound having a quaternary phosphonium sulfonic acid base in a polyurethane resin.
It has been found that this can be achieved by a polyurethane resin characterized by being copolymerized in an amount of 0 to 250 mol / 10 ⁶ g.

Another object of the present invention is to provide a leather-like sheet comprising a fibrous base material and a polyurethane resin, wherein at least a part of the polyurethane resin is the above-mentioned polyurethane resin. It has been found that a cationic dyeable leather-like sheet can be achieved.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polyurethane resin referred to in the present invention comprises a soft segment mainly composed of a polymer diol such as polyester diol, polycarbonate diol, polylactone diol and polyether diol, and a hard segment composed of polyurethane or polyurea. And a block copolymer consisting of

[0009] Such a polyurethane resin may have a stoichiometric excess (OH / NCO =
0.5-0.9) or too small (NCO / OH = 0.5-
0.9) to produce an intermediate diol or an intermediate diisocyanate in which both terminal groups are hydroxyl groups or isocyanate groups, and then reacting the organic diisocyanate with a low molecular weight chain extender. The amounts of the organic diisocyanate and the low molecular weight chain extender vary depending on the type and amount of the polymer diol, and also on the type of the organic diisocyanate or low molecular weight chain extender. The molecular weight chain extender is 1 to 5 equivalents, and the organic diisocyanate is 0.95 to 1.2 with respect to the total equivalent number of the polymer diol and the low molecular weight chain extender.
It is preferable to use 0 equivalent.

[0010] These reactions may be performed in a solventless system or in an organic solvent. As a solvent that can be used, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and the like are preferable. Toluene, methylethylketone, tetrahydrofuran, and the like may be added in an appropriate amount to the extent that solubility is not impaired.

The polymer diol used in the present invention includes polyester diol, polycarbonate diol, polylactone diol, polyether diol and the like as described above, and the number average molecular weight is 50.
A range of 0 to 4000, particularly a range of 800 to 3000 is suitable.

The polyester diol is, for example, one or more aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid. Dicarboxylic acid component and aliphatic diols such as ethylene glycol, diethylene glycol, propylene glycol, butanediol (tetramethylene glycol), methylpentanediol, hexanediol and octanediol; alicyclics such as cyclohexanediol and hydrogenated xylylene diol It can be obtained by reacting one or more aromatic diols such as diol and xylylene diol with a diol component.

The carbonate diols include, for example, carbonate compounds such as dimethyl carbonate, diphenyl carbonate and ethylene carbonate and fats having 2 to 9 carbon atoms such as ethylene glycol, propylene glycol, butanediol, methylpentanediol, hexanediol and octanediol. It is obtained by reacting with a group diol compound.

As the polylactone diol, poly-ε-caprolactone diol, poly-β-methyl-δ
Valerolactone diol; and polyether diols include polytetramethylene glycol, polypropylene glycol, polyethylene glycol, and copolymers thereof.

Next, organic diisocyanates include aromatic diisocyanates such as diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and xylylene diisocyanate; aliphatic diisocyanates such as butylene diisocyanate, hexamethylene diisocyanate and cyclohexyl methane diisocyanate; and isophorone diisocyanate. , 4 '
Alicyclic diisocyanates such as -dicyclohexylmethane diisocyanate;
More than one species may be used in combination. Among them, diphenylmethane diisocyanate, tolylene diisocyanate or isophorone diisocyanate is preferred.

Next, the low molecular weight chain extender has a molecular weight of 400
The following diols, diamines, hydrazine or hydrazine derivatives, specifically, diols such as ethylene glycol and butylene glycol, butylenediamine, hexamethylenediamine, xylylenediamine,
Examples thereof include diamines such as isophoronediamine and 4,4'-diaminodicyclohexylmethane, and hydrazine derivatives such as hydrazine, dicarboxylic acid hydrazide, and amino acid hydrazide.

In the polyurethane resin production reaction of the present invention, a catalyst is not necessarily required, but titanium tetraisopropoxide, dibutyltin dilaurate, 1,4-
Diaza (2,2,2) bicyclooctane (DABCO)
Or the like may be used as a catalyst.

In the present invention, a quaternary phosphonium sulfonic acid salt represented by the following formula must be copolymerized in the polymer chain of the polyurethane resin.

[0019]

Embedded image

In the above formula, A is an aromatic group or an aliphatic group, and among them, an aromatic group, particularly a 3,5-dicarboxybenzenesulfonic acid residue (1,3,5-substituted benzene) is preferred. X ₁ and X ₂ are ester-forming functional groups or functional groups having reactivity with isocyanate groups, and include functional groups having a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an acyloxy group, and the like. Preferred specific examples include: _{-COOH, -COO (CH 2) m} OH, -OH, -OC
H ₂ CH ₂ OH (provided that, m is an integer of 2 to 10) can be mentioned such as, inter alia, -COO (CH _{2) m} OH are preferred. Note that X ₁ and X ₂ may be the same or different. R ₁ , R ₂ , R ₃ and R ₄ are an alkyl group,
It is an aryl group or an aralkyl group, preferably an alkyl group having 2 to 6 carbon atoms, particularly preferably a butyl group. R ₁ ,
R ₂ , R ₃ and R ₄ may be the same or different. n is a positive integer, usually 1 or 2.

Specific examples of the quaternary phosphonium salt of sulfonic acid include tetrabutyl phosphonium salt of 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonic acid and 3,5-bis (4-hydroxybutoxycarbonyl) benzene. Tetrabutylphosphonium sulfonic acid salt, benzyltributylphosphonium salt of 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonic acid, tetrabutylphosphonium salt of 2,6-bis (2-hydroxyethoxycarbonyl) naphthalene-4-sulfonic acid and the like And tetrabutylphosphonium 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonate is particularly preferred.

In order to copolymerize the quaternary phosphonium salt of sulfonic acid in the main chain of the polyurethane resin, the quaternary phosphonium salt of sulfonic acid is added and copolymerized at any stage of the above-mentioned polyurethane resin production reaction. I just need. That is, the quaternary phosphonium salt of sulfonic acid may be added and copolymerized during the production of the polymer diol, or when the polymer diol is reacted with an organic diisocyanate to form an intermediate diol (or an intermediate diisocyanate), A quaternary phosphonium salt of sulfonic acid having a reaction activity with a group may be added and copolymerized. Further, when the intermediate diol (or intermediate diisocyanate) is reacted with a low-molecular-weight chain extender and an organic diisocyanate, Sulfonic acid having an activity to react with isocyanate groups
Grade phosphonium salts may be added and copolymerized. When a polymer diol is reacted with a low molecular weight chain extender and an organic diisocyanate without producing an intermediate diol (or an intermediate diisocyanate), a quaternary phosphonium salt of sulfonic acid having a reaction activity with an isocyanate group is used. Addition copolymerization may be performed.

For example, to copolymerize in a polymer diol, a desired amount of tetrabutylphosphonium 3,5-carbomethoxybenzenesulfonate is added to an aliphatic dicarboxylic acid having 2 to 12 carbon atoms such as adipic acid or sebacic acid. When,
A method of adding and copolymerizing an aliphatic diol having 2 to 12 carbon atoms such as tetramethylene glycol, diethylene glycol, and ethylene glycol when polycondensing, or tetrabutylphosphonium 3,5-carbomethoxybenzenesulfonate, and a molecular weight Can be exemplified by a method of polycondensing an alkylene diol or polyoxyalkylene diol having a molecular weight of from 62 to 2,000. In addition, the polymer diol produced by such a method has an average molecular weight of 500 to 40.
The range of 00 is appropriate, the acid value is desirably 1 mgKOH / g or less, and the water content is desirably 0.5% or less.

In order to copolymerize an intermediate diol (or an intermediate diisocyanate), a desired amount of tetrabutylphosphonium 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonate and a polyester diol are used. A polycarbonate diol, a polylactone diol, a polymer diol having an average molecular weight of 500 to 4000 such as polyether diol is reacted with an excess or an insufficient amount of diphenylmethane diisocyanate, an organic diisocyanate compound such as tolylene diisocyanate, and both terminals are hydroxyl groups or A method for forming an intermediate polymer that is an isocyanate group can be exemplified.

Among the above methods, a method of copolymerizing the sulfonic acid quaternary phosphonium salt compound at the stage of producing the intermediate diol (or the intermediate diisocyanate) is as follows:
It is preferable because the obtained polyurethane has excellent mechanical properties and durability.

The copolymerization amount of the quaternary phosphonium salt sulfonic acid compound in the polyurethane resin is 2.0 to 250 mol / 10 ⁶ g, preferably 20 to 200 mol / 10 ⁶ g, based on the weight of the polyurethane resin. When the amount is less than 2.0 mol / 10 ⁶ g, sufficient dyeability cannot be obtained. On the other hand, when the amount exceeds 250 mol / 10 ⁶ g, the strength and the like are undesirably reduced.

When the above-described polyurethane resin of the present invention is combined with a fibrous base material to produce a leather-like sheet, its modulus is preferably adjusted to an appropriate range. To adjust this value, when producing the polyurethane resin, the type and ratio of the polyol, and,
What is necessary is just to adjust the ratio of an organic diisocyanate and a low molecular weight chain extender. Usually, it can be best expressed in terms of the percentage of organic diisocyanate, and a range of about 2.6 to 4.5% by weight is appropriate, given the content of nitrogen atoms based on organic diisocyanate. Alternatively, the adjustment may be made by using another type of polyurethane resin (which may or may not have a quaternary ammonium sulfonate group). The modulus of such a polyurethane resin is 1 when measured on a film.
40~130kg / cm ² at 100% elongation modulus, is suitable particularly from 60~110kg / cm ^2.

For processing into a leather-like sheet, it is preferable to dissolve the polyurethane resin in an organic solvent and impregnate and / or coat a fibrous base material in the solution. For example, dimethylformamide, dimethylacetamide, It may be appropriately selected from organic solvents such as N-methylpyrrolidone, toluene, acetone, methyl ethyl ketone, and tetrahydrofuran.

The fibers constituting the fibrous base material used in the present invention are not necessarily dyed in the case of a silver-coated leather-like sheet having a polyurethane resin coating layer formed on the surface thereof. In order to prevent the color of the cut surface of the leather-like sheet from giving an unusual color sensation, it is preferable to use a fiber which can be dyed with a cationic dye. On the other hand, in the case of a suede-like leather-like sheet having naps of fibers on the surface, a sheet made of fibers dyeable with a cationic dye is preferred. Such cationic dye-dyeable fibers include, for example, polyester fibers containing 3,5-dicarboxybenzenesulfonic acid tetraalkylphosphonium salt or 5-sodium sulfoisophthalic acid as a copolymer component,
Acrylonitrile fibers are preferred.

As the fibrous base material, a woven fabric, a knitted fabric, a nonwoven fabric and the like are used, and a nonwoven fabric is most suitable from the viewpoints of characteristics of the obtained leather-like sheet material, difficulty in forming nap, and fineness. An ultrafine fiber nonwoven fabric in which fibers having an average single fiber fineness of 0.2 denier or less, particularly 0.005 to 0.1 denier, are three-dimensionally entangled in a bundled state is preferable.

The fibrous base material composed of such an ultrafine fiber bundle is prepared by mixing and spinning the above-described fiber-forming resin capable of dyeing a cationic dye and a thermoplastic resin having a different solvent solubility. It can be produced from ultrafine fiber-forming fibers obtained by spinning into a composite fiber such as a sea-island type or a mutually bonded type.

When the component forming the ultrafine fibers is polyester, the thermoplastic resins having different solvent solubility include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer,
Styrene or the like can be used.

The obtained fiber is made into a fibrous base material (fiber entangled nonwoven fabric) by using a known nonwoven fabric production equipment such as an opener, a card, a cross wrapper, and a needle locker.

Next, the fibrous base material is impregnated and / or coated with the organic solvent solution of the polyurethane resin, and then formed into a leather-like sheet by a wet coagulation method or a dry coagulation method. Note that a coagulation regulator, a light stabilizer, an antioxidant, a colorant, and the like may be added to the polyurethane resin solution as needed.

When the fibers forming the fibrous base material are ultrafine fiber forming fibers, the treatment with the polyurethane resin solution may be performed before or after the ultrafine fiber forming treatment of the fibers. Although it does not matter, by preventing the bonding of the fiber and the polyurethane resin and by preventing the ultrafine fiber bundle from being bundled, a leather-like sheet having a softer feeling can be obtained. It is preferably performed after the treatment.

The proportion of the polyurethane resin in the leather-like sheet composed of the fibrous base material and the polyurethane resin does not need to be particularly limited.
In order to balance the properties such as bending durability, the amount of the polyurethane resin is 20 to 110 with respect to the fiber weight of the fibrous base material and, in the case of the ultrafine fiber forming fiber, the fiber weight after the ultrafine fiber forming treatment is performed. %, Preferably in the range of 40 to 90%.

The leather-like sheet of the present invention may be provided with a coating layer comprising a porous layer obtained from the polyurethane resin or a non-porous layer on the surface, if necessary, to form a leather-like sheet with silver. Is also good. Alternatively, at least one surface may be subjected to a brushing process to obtain a suede-like leather-like sheet.
The obtained leather-like sheet material can be dyed with a cationic dye to give a sheet excellent in color developability, various fastnesses, color transfer properties, hand feeling, and the like.

The dyeability of the cationic dye is almost proportional to the content of the dyed seat when the kind of the polymer is the same, but the polymer forming the fibrous base material such as the leather-like sheet of the present invention is used. In the case of a composite in which the resin and the polyurethane resin impregnated therewith are different, the coloring properties are likely to be different between the fiber and the impregnated polymer. Further, since the impregnated polyurethane resin is more amorphous than the fiber-forming polymer, the dye usually has good exhaustion properties, and the polyurethane resin is more likely to be dyed darker when simultaneously dyeing in the same dyeing bath. However, in the case of a leather-like sheet, particularly a leather sheet having nap, since it is preferable in terms of quality to dye the fibers, especially the nap fibers, in a darker color than the polyurethane resin, it is preferable. It is preferred that the cationic dye-dyeing seat groups occupy in the fibers of the fibrous base material are larger than those in the polyurethane resin so that the fibers are dyed more densely even when dyed simultaneously in the same dyeing bath. When the dyed seats are of the same type of functional group, it is usually preferable that the dyed seating amount of the fiber is 20% or more, preferably 40% or more larger than that of the polyurethane resin.

[0039]

The present invention will be described in more detail with reference to the following examples. In the examples, parts not otherwise specified are parts by weight.

Example 1 1) Synthesis of tetrabutylphosphonium salt of 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonic acid 532 parts of 5-tetrabutylphosphonium sulfo-dimethylisophthalate and 130 parts of ethylene glycol were stirred. After adding 0.5 part of sodium acetate and 0.1 part of titanium tetraisopropoxide, and reacting at 180 ° C. for 3 hours while stirring under a nitrogen stream, the methanol flowing out under reduced pressure in vacuo was removed. After removal, the temperature was further raised to 220 ° C. and the reaction was carried out for 1 hour. Compound (D-1) obtained
Represents a hydroxyl value of 182.82 mgKOH / g and an acid value of 0.08
mgKOH / g, molecular weight 614.

2) Synthesis of Polyurethane Resin Containing Tetraalkylphosphonium Salt of Sulfonic Acid 61.4 parts of the above compound (D-1) and 174 parts of tolylene diisocyanate were mixed with 706.2 parts of dimethylformamide, and the mixture was stirred for 1 hour under a nitrogen stream. Reacted. Then, polytetramethylene glycol (average molecular weight: 1000) 190
0 parts and 5700 parts of dimethylformamide were added, and the mixture was further reacted for 2 hours. Subsequently, diphenylmethane-
1,000 parts of 4,4'-diisocyanate, 186 parts of ethylene glycol, and 3558 parts of dimethylformamide were added thereto, and the mixture was further reacted for 4 hours. The obtained polyurethane resin A has a quaternary phosphonium sulfonic acid base of 31.
The content was 9 mol / 10 ⁶ g.

3) Preparation of leather-like sheet-like material A 5-tetrabutylphosphonium sulfoisophthalic acid component (tetrabutylphosphonium 3,5-dicarboxybenzenesulfonate) was copolymerized by 2.0 mol% with respect to the acid component. Polyethylene terephthalate is an island component (19 islands x
0.10 de: composite ratio 60% by weight), composite spinning was performed using low-density polyethylene as a sea component (40% by weight), treated with an oil agent, and cut into a length of 51 mm to produce ultrafine fiber-forming short fibers.

The obtained short fiber was formed into a laminated web using a card and a cross wrapper, and then subjected to needle punching to obtain an entangled nonwoven fabric. Then, it was heated in a chamber at 145 ° C. for 3 minutes and passed through a calender roll to a thickness of 1.
A 2 mm non-woven fabric having a weight of 480 g / m ² was obtained.

The obtained nonwoven fabric was impregnated with an impregnating solution having the following composition, coagulated in water containing 20% dimethylformamide, and then washed with water to obtain an impregnated base material. Impregnating solution: polyurethane resin A (concentration: 25%) 100 parts Crisbon Assister-SD-8 (manufactured by Dainippon Ink and Chemicals) 1.5 parts Crisbon Assister-NO-10 (manufactured by Dainippon Ink and Chemicals) 0.5 Parts dimethylformamide 66 parts

The obtained impregnated substrate was treated in hot toluene to dissolve and remove the polyethylene component. Next, the front and back surfaces of the obtained base material were raised with an emery buffing machine, and the obtained base material was further sliced and divided into two parts. The obtained sheet was dyed using a cationic dye under the following conditions. The dyed sheet was a suede-like artificial leather having a clear color, excellent in fastness to washing, fastness to dry friction and fastness to wet friction, and also excellent in hydrolysis resistance and light resistance. Dyeing conditions Dye Kayacryl Red GRL-ED (manufactured by Nippon Kayaku) Dye concentration 7 g / liter Acetic acid 0.2 ナ ト リ ウ ム Sodium acetate 0.1 浴 Bath ratio 1:50 Temperature x time 130 ° C x 60 minutes

[Embodiments 2 and 3]
5-bis (2-hydroxyethoxycarbonyl) benzenesulfonic acid tetrabutylphosphonium salt (Compound D-
1) with 186 parts (sulfonic acid 4 in polyurethane resin)
95.7 mol / 10 ⁶ g of secondary phosphonium base:
Example 2) or 372 parts (the same content: 191.5 mol /
10 ⁶ g: Example 3), and the other conditions were the same as in Example 1 to prepare a polyurethane resin.
In the same manner as described above, a non-woven fabric was impregnated to form a sheet and dyed.

As a result, the color clarity was as good as in Example 1, and the washing fastness, dry rub fastness and wet rub fastness were also excellent. In Examples 2 and 3, compared to Example 1, the resin was dyed in a darker color than the fiber and had a slight dichroism, and this tendency was stronger in Example 3. However, all were excellent as suede leather-like sheets.

Example 4 Polyethylene terephthalate obtained by copolymerizing a 5-sodium sulfoisophthalate component with an acid component at 3 mol% was used as an island component (39 islands × 0.05 d).
e, 70% by weight) and low-density polyethylene in the sea component (30%).
(Weight%), and after drawing and oil treatment, cut into a length of 51 mm to prepare ultrafine fiber-forming short fibers having a fineness of 2.8 de.

The obtained short fiber was formed into a laminated web using a card and a cross wrapper, and then subjected to needle punching to obtain an entangled nonwoven fabric. Then, it was heated in a chamber at 150 ° C. for 2 minutes, and passed through a calender roll to a thickness of 1.2 mm.
A 5 mm nonwoven fabric having a weight of 480 g / m ² was obtained.

The obtained nonwoven fabric was impregnated with an impregnating solution having the following composition, coagulated in water containing 10% dimethylformamide, and then washed with water to obtain an impregnated substrate. Impregnating liquid: Polyurethane resin A (concentration: 25%) 100 parts Crisbon Assister-SD-8i (manufactured by Dainippon Ink and Chemicals) 1.5 parts Crisbon Assister-NO-10 (manufactured by Dainippon Ink and Chemicals) 0.5 Parts dimethylformamide 39 parts

The resulting impregnated substrate was treated in hot toluene at 90 ° C. to dissolve and remove the polyethylene component. Next, after drying the obtained base material, the front and back surfaces of the base material are
The hair was raised with a mesh emery paper, the raised surface was shirred, and then dyed with a cationic dye in the same manner as in Example 1. The obtained dyed sheet had a vivid color, was a suede-like artificial leather excellent in washing fastness, dry rub fastness, and wet rub fastness, and also had good hydrolysis resistance and light fastness. .

Comparative Example 1 Dimethyl isophthalate 19
4 parts, 130 parts of ethylene glycol, 0.5 part of sodium acetate, and 0.1 part of titanium tetraisopropoxide were reacted at 180 ° C. for 3 hours while stirring under a nitrogen stream, and then methanol was distilled off under reduced pressure. 2 while removing
The temperature was raised to 20 ° C., and the reaction was further performed for 1 hour.

The obtained reaction product had a hydroxyl value of 458.0 m.
The main component was bis (2-hydroxyethyl) isophthalate having a gKOH / g and a molecular weight of 245.0.

After reacting 24.5 parts of this reaction product with 174 parts of tolylene diisocyanate and 595.5 parts of DMF under a nitrogen stream for 1 hour, 1900 parts of polytetramethylene glycol (average molecular weight: 1000) was dissolved in 5700 parts of DMF. Then, the reaction was further performed for 2 hours. Then
Diphenylmethane-4,4'-diisocyanate 100
0 parts, 186 parts of ethylene glycol and 3558 parts of dimethylformamide were added thereto, and the mixture was further reacted for 4 hours.

The procedure was performed in the same manner as in Example 1 except that the above polyurethane resin was used in place of the polyurethane resin A used in Example 1. In the obtained sheet, the fibers were dyed, but the polyurethane resin was not dyed, and the quality was poor.

Comparative Example 2 1) Synthesis of sodium salt of 3,5-bis (2-hydroxyethoxycarbonyl) benzenesulfonic acid 5-sodium sulfo-dimethylisophthalate 264
And 130 parts of ethylene glycol in a reactor with stirring, 0.5 part of sodium acetate and 0.1 part of titanium tetraisopropoxide are added, and the mixture is stirred under a nitrogen stream.
After reacting at 80 ° C. for 3 hours, the methanol flowing out was removed under reduced pressure under vacuum, and the temperature was further raised to 220 ° C. to react for 1 hour. The obtained compound (D-2) had a hydroxyl value of 32.
5.32 mgKOH / g, acid value 0.10 mgKOH /
g, molecular weight 345.

2) Synthesis of Polyurethane Resin Containing Sodium Sulfonate Group 34.5 parts of the above compound (D-2) and 174 parts of tolylene diisocyanate were mixed with 625.5 parts of dimethylformamide and reacted for 1 hour under a nitrogen stream. Was. Then, polytetramethylene glycol (average molecular weight: 1000) 190
0 parts and 5700 parts of dimethylformamide were added, and the mixture was further reacted for 2 hours. Subsequently, diphenylmethane-
1,000 parts of 4,4'-diisocyanate, 186 parts of ethylene glycol, and 3558 parts of dimethylformamide were added thereto, and the mixture was further reacted for 4 hours. The obtained polyurethane resin B contained 30.3 mol /
10 was found to contain ⁶ g.

3) Preparation of a leather-like sheet The same non-woven fabric (1.2 mm thick,
480 g / m ² ) was impregnated with an impregnating solution having the following composition, and then coagulated in water containing 20% dimethylformamide.
Then, it was washed with water to obtain an impregnated substrate. Impregnating solution: polyurethane resin B (concentration: 25%) 100 parts Crisbon Assister SD-8 (manufactured by Dainippon Ink and Chemicals) 1.5 parts Crisbon Assister NO-10 (manufactured by Dainippon Ink and Chemicals) 0.5 part Dimethyl Formamide 66 parts

The resulting impregnated substrate was treated in hot toluene to dissolve and remove the polyethylene component. Next, the front and back surfaces of the obtained base material were raised with an emery buffing machine, and the obtained base material was further sliced and divided into two parts. The obtained sheet was dyed using a cationic dye under the same conditions as in Example 1. The dyed sheet had a vivid color and was a suede-like artificial leather having excellent washing fastness, dry rub fastness, and wet rub fastness. However, compared with Example 1, weathered fastness was as shown in Table 1. Was inferior. The weather fastness was measured using a sunshine carbon arc two-lamp system at 20, 40, and 63 ° C.
The dyed cloth after 60 hours was graded based on the degree of color fading.

[0060]

[Table 1]

[0061]

Since the polyurethane resin of the present invention is copolymerized with a compound having a quaternary phosphonium sulfonic acid base, it not only exhibits excellent dyeing properties for cationic dyes, but also has excellent mechanical properties and properties. Excellent in durability, processing characteristics, etc. Therefore, taking advantage of these characteristics,
It can be used for the production of a leather-like sheet which can be dyed clearly with a cationic dye and has excellent durability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) D06N 3/14 101 D06N 3/14 101 F term (reference) 4F055 AA01 BA12 BA16 EA01 EA04 EA11 EA12 EA24 FA15 4F072 AA04 AA07 AA08 AB04 AB05 AB17 AB28 AB29 AD43 AH02 AH21 AJ04 AK05 AL01 4J002 BB033 BB063 BB073 BB123 BC033 BG102 CF142 CF152 CK031 CK041 CK051 FA042 FA043 FD012 FD013 4J0314 CA03 CA12 CB03 CC03 CC03 DF20 DF22 DG03 DG04 DG06 HA01 HA07 HC03 HC12 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 JA42 JA44 KA01 KB02 KC16 KC17 KD02 KD04 KD11 KE02 MA22 MA24 QC08 RA03

Claims (6)

[Claims] 1. A polyurethane resin, wherein a compound having a quaternary phosphonium sulfonic acid base is copolymerized in the polyurethane resin in an amount of 2.0 to 250 mol / 10 ⁶ g. 2. The polyurethane resin according to claim 1, wherein the compound having a sulfonic acid quaternary phosphonium base is a bis-ester of 5-quaternary phosphonium sulfoisophthalic acid represented by the following general formula. Embedded image 3. The method according to claim 1, wherein a polymer diol having an average molecular weight of 500 to 4000, a compound having a quaternary phosphonium salt of a sulfonic acid represented by the following general formula, a low molecular chain extender and an organic diisocyanate are reacted. Polyurethane resin. Embedded image 4. A leather-like sheet comprising a fibrous base material and a polyurethane resin, wherein at least a part of the polyurethane resin is the polyurethane resin according to any one of claims 1 to 3. Characteristic leather-like sheet material capable of dyeing cationic dyes. 5. The leather-like sheet according to claim 4, wherein the fibers constituting the fibrous base material are cationic dyeable fibers. 6. The dyeing seating amount for the cationic dye in the fibrous base material is such that the fibrous base material is dyed darker than the polyurethane resin when dyed with the cationic dye. A leather-like sheet according to claim 5.