JPH04258642A - Durable leatherlike sheet and its production - Google Patents

Abstract

PURPOSE:To produce a leatherlike sheet excellent in fastness to light and washing. CONSTITUTION:A leatherlike sheet comprising a fibrous substrate impregnated or coated with a polyurethane elastomer which contains a polycondensate prepd. from 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpyridine and dimethyl succinate, having an average mol.wt. of 3300, and bonded to an org. isocyanate constituting the elastomer and 0.00005-0.003mmmol of a hindered amine per g of the elastomer.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet material having excellent light resistance and washing fastness, and a method for producing the same.

0002

[Prior Art] A leather-like sheet material made of a fibrous base material and a polyurethane elastic material has a texture similar to natural leather, has excellent flexibility, abrasion resistance, and mechanical strength, and is also easy to process. It is widely used as artificial leather. However, general polyurethane sheet materials obtained using the wet coagulation method have disadvantages such as poor light resistance, discoloration due to sunlight, nitrogen oxide gas, automobile exhaust gas, etc., and a decrease in strength and elongation. Therefore, its use is severely restricted.

Conventionally, in order to prevent the deterioration of polyurethane elastomers, there have been methods to (a) use polyurethane with excellent light resistance, (b) methods to add light resistance improvers to polyurethane, and (c) methods to add light resistance improvers to polyurethane. A method using polyurethane with weather resistance has been proposed. For example, regarding (a), so-called non-yellowing polyurethanes using aliphatic or alicyclic organic diisocyanates have extremely excellent resistance to discoloration, but have poor heat resistance and bending resistance. It is not commonly used because of its poor physical properties such as, poor wet film forming properties, and poor appearance and texture. In addition, polyurethanes in which non-aromatic diisocyanates are mixed with aromatic diisocyanates or are reacted sequentially have been proposed in Japanese Patent Publication No. 4866/1983, but they achieve both yellowing resistance, heat resistance, and wet film formability. is difficult and cannot be put to practical use.

Regarding (b), antioxidants such as hindered phenol type and phosphite type, ultraviolet absorbers such as hindered amine type and benzotriazole type, light stabilizers, hydrazine derivatives, triazine derivatives, etc. are used alone or A method of adding multiple
834, JP 56-107009, JP 53-144957, JP 52-11465
Many proposals have been made, including Publication No. 2. Although the dry method is effective, in the case of the wet method, added ultraviolet absorbers and antioxidants dissolve into the coagulation bath and are difficult to remain on the sheet material, and they may fall off during dry cleaning or washing. However, the reality is that they cannot be used satisfactorily for long periods of time due to loss of effectiveness.

Regarding (c), a method using a hindered amine compound as a part of the chain extender and/or terminal stopper (JP-A-56-43478, JP-B-Sho 61)
-6097 Publication), and a method of using a piperidine compound as part of the polymerization raw material for polyurethane (Japanese Patent Publication No. 63-63).
31490) and a method of introducing a bisphenol monoester compound at the end of polyurethane (Japanese Patent Publication No. 1983-
58851), but when copolymerized in a sufficient amount to produce sufficient effects, it is possible to balance the level of elution/bleed prevention effect and yellowing resistance, sustainability of effect with long-term use, and compatibility with polyurethane. There are these problems, and a stabilizer for polyurethane that can satisfy these requirements has not yet been developed.

[0006]

[Problems to be Solved by the Invention] An object of the present invention is to improve light resistance by using polyurethane chemically bonded with a specific compound that has the effect of improving light resistance as a polyurethane for use in leather-like sheet materials. An object of the present invention is to provide a leather-like sheet material having excellent washing fastness.

[0007]

[Means for Solving the Problems] The present invention provides a compound in which a residue obtained by removing a hydrogen atom from the terminal hydroxyl group of a hindered amino group represented by the following formula 2 is bonded to an organic isocyanate constituting a polyurethane elastomer. The repeating unit of is 0.00005 to 0.0 per gram of polyurethane elastic material.
0.3 mmol of polyurethane elastic material and a fibrous base material,

The present invention also provides a leather-like sheet-like product by impregnating a fibrous base material with a polyurethane solution and/or coating it with porous polyurethane, introducing the base material into a coagulation bath, washing with water, and drying. In the method for producing a product, the impregnating polyurethane and/or the coating polyurethane are composed of a polymeric diol having an average molecular weight of 500 or more, an organic polyisocyanate, and a chain extender, and at least one of the chain extender and/or terminal stopper is used. 1 g of a polyurethane elastomer containing repeating units of the compound of formula 1 as parts
A method for producing a leather-like sheet material, characterized in that a polyurethane elastomer polymerized in an amount of 0.00005 to 0.003 mmol per product is used,

Furthermore, the present invention provides a polymer diol having an average molecular weight of 500 or more, an organic polyisocyanate, a chain extender, and the repeating unit of chemical formula 2 in an amount of 0.00005 to 0.003 mmol per 1 g of the polyurethane elastomer. 2
A fiber aggregate is made of a polyurethane multicomponent fiber whose sea component is a thermoplastic polyurethane obtained by melt polymerizing a compound of and then treated with a solvent that is a solvent for the polyurethane component and a non-solvent for the other components to dissolve some or all of the polyurethane,
This is a method for producing a leather-like sheet material, which comprises introducing the substrate into a coagulation bath to coagulate the polyurethane, followed by washing with water and drying.

0010

[Case 2]

The compound represented by formula 2 in the present invention is:
1-(2-hydroxyethyl)-4-hydroxy-2,
It is obtained by condensation polymerization of 2,6,6-tetramethylpiperidine and divalent carboxylic acid or carboxylic acid dimethyl ester, for example, dimethyl succinate and 1-(
2-hydroxyethyl)-4-hydroxy-2,2,6
, 6-tetramethylpiperidine. In the compound represented by Chemical Formula 2, the average of n is 4 or more and 20 or less, preferably 6 or more and 15 or less. If n is less than 4, the amount of the polyurethane to be blended will be large to obtain the desired effect, resulting in the molecular weight of the polyurethane becoming too small and the compatibility decreasing. On the other hand, if n is larger than 20, the molecular weight of the compound becomes too large, which may affect the polymerization reaction of polyurethane or cause poor physical properties. The polyurethane elastomer of the present invention can be prepared by adding a polymer diol, an organic diisocyanate, a chain extender, and, if necessary, a terminal capping agent at the same time, as is generally done in polyurethane polymerization. It is also possible to use a so-called prepolymer method in which a polymeric diol and an organic diisocyanate are reacted in advance to synthesize a prepolymer and then extended with a chain extender.

The compound represented by formula 2, which is a feature of the present invention, may be added at any stage of the above reaction, but in order to ensure its introduction into the molecule, it is recommended to add it at the initial stage of the reaction. preferable. On the other hand, in the case of melt polymerization, a compound represented by chemical formula 2 is added to the three components of polymer glycol, organic diisocyanate, and a low-molecular compound having two active hydrogen atoms, and the polyurethane chain is formed using the dissociation reaction of polyurethane. It can also be incorporated into. Examples of the polyurethane in the present invention include polyester glycol obtained by condensation polymerization of glycol and aliphatic dicarboxylic acid, polylactone glycol obtained by ring-opening polymerization of lactam, aliphatic or aromatic polycarbonate glycol, or polyether glycol. The average molecular weight selected from at least one species is 500 to 5000, preferably 600 to 3.
It is obtained by reacting raw materials mainly consisting of four components: a polymer glycol in the range of 0.000, an organic diisocyanate, a low molecular weight compound having two active hydrogen atoms, and a compound represented by formula 2.

Typical polyester glycols include ethylene glycol, propylene glycol,
C2-C10 aliphatic diols such as butanediol, hexamethylene glycol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,8-octanediol, nonanediol, polyalkylenes such as diethylene glycol Examples include polyols obtained by condensation polymerization of glycol and aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as succinic acid, adipic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid.

[0014] Polylactone glycols include polyols such as polycaprolactone diol and poly(β-methyl-δvalerolactone) diol, and polycarbonate glycols include 4,4'-dioxydiphenyl-2,2 ´-Aromatic polycarbonates from propane (bisphenol A) and aliphatic 2 such as pentamethylene glycol, hexamethylene glycol, etc.
Examples include aliphatic polycarbonates obtained by reacting alcohols with phosgene, and examples of polyether glycols include polytetramethylene glycol, polypropylene glycol, and polyethylene glycol, each of which may be used alone or in combination of two or more. .

[0015] As the organic diisocyanate, known aliphatic compounds containing two isocyanate groups in the molecule,
Alicyclic, aromatic diisocyanates, especially 4,4'-diphenylmethane diisocyanate, P-phenylene diisocyanate, tolylene diisocyanate, 1,5 naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane Examples include diisocyanate. As a chain extender, a low molecular weight compound having a molecular weight of 400 or less and containing at least two hydrogen atoms capable of reacting with isocyanate, such as ethylene glycol, 1,4 butanediol, hexamethylene glycol, 3-methyl-1,5 pentane, etc. diol, cyclohexanediol, xylylene glycol,
1,4-bis(β-hydroxyethoxy)benzene, diols such as neopentyl glycol, hydrazine, ethylenediamine, hexamethylenediamine, 4,4'-
Examples include diamines such as dicyclohexylmethane diamine and isophorone diamine.

In the present invention, the compound represented by formula 2 is blended in polyurethane in an amount ranging from 0.00005 to 0.00005 repeating units of formula 2 (in parentheses) per 1 g of polyurethane elastomer.
0.003 mmol, more preferably 0.0001-0
．． The amount is such that it becomes 0.001 mmol. If the amount is less than this, the light resistance will be insufficient, and if it is too much, the polymerization reaction will be affected or the physical properties of the polyurethane will be impaired, which is not preferable. The composition of the present invention may further contain known additives such as antioxidants, ultraviolet absorbers, dyes/pigments, fillers, coagulation regulators, etc., if desired.

The fibrous substrate of the present invention can be made of ordinary fibers, such as chemical fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, polyvinyl alcohol, regenerated cellulose, natural fibers, or special fibers such as polyester, polyamide, etc. From fabrics such as fiber-entangled nonwoven fabrics, napped knitted fabrics, laminated fabrics of nonwoven fabrics and knitted woven fabrics, etc., made of fibers selected from ultrafine fibers such as polyacrylonitrile, ultrafine bundled fibers, special fibers with porous arrays, etc. One selected type of fabric is impregnated with an impregnating polyurethane composition solution at a predetermined solution concentration, then coated with a coating polyurethane composition solution at a predetermined solution concentration, and then wet-coagulated in a polyurethane non-solvent. When using ultrafine fiber generation type fibers, peelable and split type fibers, etc.
Before impregnating and applying the polyurethane composition or after solidifying,
Solvent extraction treatment using toluene, trichlene, perchlorene, etc., or division treatment using hot water containing an alkali, an activator, etc., may also be performed.

The fibrous substrate of the present invention may also be a polyurethane multicomponent fiber having a thermoplastic polyurethane obtained by melt polymerization as a sea component and a thermoplastic polymer incompatible with the polyurethane as an island component, or A fiber aggregate is made from the main fibers, and then treated with a solvent that is a solvent for the polyurethane component and a non-solvent for the other components to dissolve part or all of the polyurethane, and the substrate is introduced into a coagulation bath. It can also be obtained by coagulating polyurethane, then washing with water and drying. The surface of the obtained leather-like sheet material may be finished with raised fibers to produce suede-like artificial leather, or the surface may be provided with a coating layer, or simply smoothed and then finished with a colored finishing layer. It may also be made of silver-finished artificial leather.

[0019]

[Action] The leather-like sheet material obtained by the method of the present invention is
It is composed of a polyurethane elastomer containing a compound having a specific hindered amino group as an impregnation polyurethane and/or a coating polyurethane, and a urethane compound obtained by reaction with an organic isocyanate, and a fibrous base material. It has a texture and appearance similar to leather, and compounds with hindered amino groups do not fall out of the system during wet coagulation or extraction, and it exhibits characteristics that reduce discoloration and deterioration due to long-term use. In addition, it does not fall off during dry cleaning or washing, making it particularly suitable for clothing, footwear, interior decoration, etc. For silver-coated materials, there is extremely little bleed-out of various additives in the coating during long-term storage. Has characteristics.

[0020]

[Examples] Next, embodiments of the present invention will be explained with specific examples. Note that parts and percentages in the examples are by weight unless otherwise specified. Reference Example-1 191 parts of polyester diol with an average molecular weight of 2000 obtained from 1,4-butanediol and adipic acid, 286 parts of polytetramethylene glycol (hereinafter abbreviated as PTMG) with an average molecular weight of 1100, and 4,4'- Diphenylmethane diisocyanate (hereinafter abbreviated as MDI) 4
29 parts, ethylene glycol (hereinafter abbreviated as EG) 8
4 part and R1 of chemical formula 2 is CH3 and the average molecular weight is 33
00 dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperazine in 1500 parts of DMF.
The mixture was reacted at 0° C. for 8 hours, and the viscosity was increased to a predetermined viscosity using MDI. Then, a DMF solution containing 1 part of citric acid and 8 parts of methanol as a reaction terminator was added to obtain a polyurethane having a solid content of 25% and a weight of 350 poise.

Analysis of the polyurethane revealed that it contained 0.00027 mmol of the repeating unit of the compound represented by formula 2. This solution was diluted to 15% and the thickness was 0.
A 05mm dry film was prepared and its physical properties were measured using a Tensilon tensile tester, and the tensile strength was 612.
kg/cm2. After irradiating the film with a fade tester (carbon arc, 63°C) for 80 hours, the tensile strength was measured and found to be 563 kg/cm2 (
Strength retention rate: 92%).

Comparative Reference Example-1 The same procedure as Reference Example-1 was carried out except that the compound represented by Chemical Formula 2 was not used, and the strength was maintained after 80 hours of irradiation using a dry film fade tester (carbon arc, 63°C). The light resistance was extremely poor, with a rate of 32%.

Example 1 A multicomponent fiber with a fineness of 4 denier and 51 mm obtained by melt-spinning and drawing 40 parts of highly fluid polyethylene and 60 parts of 6-nylon (6-nylon is an ultrafine fiber component) was used. A fiber-entangled nonwoven fabric with an apparent density of 0.160 g/cm3 was prepared through the steps of , carding, cross-wrapping, and needle punching. The nonwoven fabric was heated to melt and heat set the sea component polyethylene to obtain a fiber-entangled nonwoven fabric with an apparent density of 0.285 g/cm 3 and smoothed on both sides. Using the 25% polyurethane solution obtained in Reference Example-1, polyurethane 12
%, an impregnating solution consisting of 1% stearyl alcohol, 1.5% sorbitan tristearate and 85.5% DMF, and 21% polyurethane, 1.5% titanium oxide, 2
- Ethylhexyl sulfate ester sodium salt 1%, polyoxyethylene oleyl ether 0.5% and DMF
Coating solutions each consisting of 76% were prepared. After impregnating the above fiber-entangled nonwoven fabric with the impregnating liquid and removing the excess impregnating liquid on the surface, the coating liquid was applied in an amount of polyurethane of 120 g/m2.
It was then coagulated in a coagulation bath of 30% DMF aqueous solution and washed with water to obtain a sheet-like material in which the polyurethane was coagulated into a porous structure. This sheet-like material is treated in hot toluene to dissolve and remove the polyethylene component of the multicomponent fibers, and a base material containing porous polyurethane in a 6-nylon ultrafine fiber bundle fiber entangled nonwoven fabric and a porous polyurethane coating layer are formed. A sheet-like product was obtained.

[0024] On the surface of the sheet-like material, a finishing ink made of PTMG/polycarbonate-based polyurethane with titanium oxide added is applied in an amount to an average thickness of 6 μm using a gravure roll. After drying, embossing of the rough texture pattern of the leather is performed. conduct,
Further, a softening treatment was performed to obtain a grain-finished leather-like sheet material (1). This leather-like sheet material had extremely good appearance, creases, and texture, and was also excellent in surface strength, bending fatigue resistance, etc., and was suitable for sports shoes, sports equipment, and the like. In addition, the surface of the sheet-like material is buffed with sandpaper to expose the air bubbles inside the coating layer to give it a suede-like appearance, and then the suede-like leather-like sheet material (2) obtained by finishing is had a good tactile feel. A fade tester (Carbon Arc, 63
Table 1 shows the results of evaluating the light resistance of the front and back surfaces after irradiation for 80 hours.

[0025]

[Table 1]

Comparative Example-1 In addition to using the polyurethane solution of Comparative Reference Example-1, silver-finished leather-like sheet material (3) and suede-like leather-like sheet material (4) were prepared in exactly the same manner as in Example-1. ) was created. Table 1 shows the results of evaluating light resistance.

Comparative Example-2 Example-1 except that the polyurethane solution of Comparative Reference Example-1 was used and one part of the compound of chemical formula 2 used in Reference Example-1 was added as a light stabilizer to the impregnating liquid and coating liquid. A grain-finished leather-like sheet material (5) and a suede-like leather-like sheet material (6) were produced in exactly the same manner as described above. Table 1 shows the results of evaluating light resistance. The results of the above evaluation are as shown in Table 1. The leather-like sheet material using the polyurethane of the present invention has a soft texture due to the extraction method, and the compound of chemical formula 2 is bonded to the polyurethane chain. However, in the leather-like sheet material of Comparative Example-2, the compound of chemical formula 2 has fallen off during toluene extraction, and the light resistance remains the same as in Comparative Example-1. The quality was poor.

Reference example-2
495 parts by weight of PTMG with an average molecular weight of 2000, 164 parts by weight of polycaprolactone glycol with an average molecular weight of 2000, 26 parts by weight of EG, 15 parts of the compound of formula 2 used in Reference Example-1 and 250 parts by weight of MDI were added to DMF.
After reacting in 1500 parts to obtain a prepolymer, 4,
A DMF solution containing 4'-diaminodiphenylmethane was added in an amount of 0.99 molar equivalent to the remaining isocyanate groups of the prepolymer, and the solid content concentration was set to 25%, and the reaction was carried out at 30°C for 8 hours to adjust the viscosity to 350 poise. After making adjustments, add 1 part of citric acid and 8 parts of methanol as a reaction terminator.
332 poise of polyurethane was obtained. Dilute this solution to 15% and make it 0.05mm thick.
A dry film was prepared and its physical properties were measured using a Tensilon tensile tester, and the tensile strength was 233 kg/c.
It was m2. The film was irradiated with a fade tester (carbon arc, 63° C.) for 80 hours, and then its tensile strength was measured to be 212 kg/cm 2 (strength retention rate: 91%).

Comparative Reference Example 2 The same procedure as Reference Example 2 was carried out except that the compound shown by Chemical Formula 2 was not used, and the strength was maintained after 80 hours of irradiation with a dry film fade tester (carbon arc, 63°C). The light resistance was extremely poor, with a rate of 18%.

Example 2 An apparent density of 0.150 g/cm3 consisting of sea-island fibers consisting of 75 parts of polyethylene terephthalate and 25 parts of low-density polyethylene, with a number of islands of 50 (polyethylene terephthalate is the island component) and a fineness of 4.5 denier. The three-dimensionally entangled nonwoven fabric was shrunk in warm water to an area shrinkage rate of 30%, impregnated with a 10% aqueous solution of polyvinyl alcohol, dried, and immersed in percrene to dissolve the polyethylene and form ultrafine fibers. A nonwoven fabric was obtained in which bundles of .

Using the 25% polyurethane solution obtained in Reference Example-2, an impregnating solution consisting of 13% polyurethane, 1% alcohol-modified silicone, and 86% DMF was prepared and impregnated into the nonwoven fabric to remove excess impregnation on the surface. After removing the liquid, it is coagulated in a coagulation bath of 30% DMF aqueous solution, and washed in warm water to elute and remove the polyvinyl alcohol, thereby producing a sheet-like material containing porous polyurethane in a polyethylene terephthalate ultrafine fiber bundle entangled nonwoven fabric. Obtained. This sheet-like substrate is sliced into two parts, the back (sliced) side is buffed to match the thickness, and the front (non-sliced) side is
Buff the surface with sandpaper to a thickness of 0.7
A fiber napped sheet of mm was obtained. The sheet was coated with 0.2% OWF of Sumikalon Blue E-RPD (disperse dye).
After processing with a circular dyeing machine at 130° C. for 1 hour, alkali reduction cleaning was performed to obtain a pale blue colored sheet. After drying, brush the raised hair on the surface,
When the hair was styled with a nylon brush, a suede-like sheet material with vivid color development, an appearance with an elegant lighting effect, and a soft texture was obtained.

[0032] The sheet-like material was dry-cleaned five times using perclean, and then irradiated with a fade tester (carbon arc, 63°C) for 80 hours. There is no difference in the discoloration of the irradiated surface of the sheet before and after dry cleaning, and both are No. 4, and when the weight loss after 100,000 times of abrasion was measured according to the JISL1096 Martindale method, the abrasion loss of the irradiated surface of the sheet before dry cleaning was is 35
mg, and after dry cleaning it was 38 mg, which showed almost no deterioration and had excellent light resistance.

Comparative Example 3 The same procedure as Example 2 was used except that the polyurethane solution of Comparative Reference Example 2 was used and 1 part of the compound of formula 2 used in Reference Example 1 was added as a light stabilizer when preparing the impregnating solution. Similarly, a suede-like leather-like sheet material was prepared and its light resistance was evaluated. The sheet-like material was dry-cleaned five times using perclean, and then irradiated with a fade tester (carbon arc, 63° C.) for 80 hours. The difference in discoloration of the irradiated surface of the sheet before and after dry cleaning was large; it was No. 3 before dry cleaning, but No. 1 after dry cleaning. On the other hand, when the weight loss after 100,000 wears was measured according to the JISL1096 Martindale method,
The abrasion loss of the irradiated surface of the sheet before dry cleaning is 4
The amount was 2 mg, but it was 58 mg after dry cleaning, and the light resistance was significantly decreased.

Example-3 533 parts of polyester diol with an average molecular weight of 1500 obtained from 3-methyl-1,5-pentanediol and adipic acid, 104 parts of 1,4-butanediol, Reference Example-1
By reacting 6 parts of the compound of formula 2 used in the above with 357 parts of MDI, the nitrogen content based on isocyanate groups was 4.
Pellets of 0% thermoplastic polyurethane were obtained. The thermoplastic polyurethane and the terminal amino group concentration are 1.5 x 10-
Using 5 eq/g of 6-nylon as a spinning raw material, the polymer streams extruded from separate extruders were combined to become 40 parts of polyurethane stream and 60 parts of 6-nylon stream.
A polyurethane multicomponent fiber having a fiber count of 50 (6-nylon is the island component) and a fineness of 10 denier was obtained by melt spinning using a splitting and integrating method. The obtained multicomponent fiber was
Stretched three times in hot water at ℃ and heat-set to a fineness of 3.5 dr.
fibers were obtained. After applying an oil agent to this fiber, it was mechanically crimped and cut into fiber lengths of 51 mm to obtain staple fibers.

[0035] Next, each staple fiber is passed through a card and a random web and laminated by a cross-lap method to form a fiber web with an average weight of 500 g/m2, and then needle punched from both sides of the fiber web at a total punch density of 980 punches/cm2. The fiber-entangled nonwoven fabric was obtained by impregnating it with a 7.5% aqueous solution of polyvinyl alcohol, squeezing at a target squeezing rate of 150%, and drying to obtain a nonwoven fabric with a stable form. After that, a DMF solution containing water-soluble silicone was added. The fibers were impregnated at an impregnation rate of 200% to dissolve the polyurethane in the fiber in an atmosphere at a temperature of approximately 45°C, and then immersed in a 30% DMF aqueous solution to coagulate the polyurethane, followed by hot water washing to remove polyvinyl alcohol. One side of the obtained fibrous sheet has a thickness of 1.
It was sliced into 0 mm pieces, and the surface side upon coagulation was subjected to a napping treatment to create a suede-like sheet, which was then dyed and rubbed to produce a product. The product of the example had a firm and flexible texture with little shedding of fuzz, and was excellent as a suede-like sheet for clothing.

[0036] The sheet-like material was dry-cleaned five times using perclean, and then irradiated with a fade tester (carbon arc, 63°C) for 80 hours. There is no difference in the discoloration of the irradiated surface of the sheet before and after dry cleaning, and both are No. 4, and when the weight loss after 100,000 times of abrasion was measured according to the JISL1096 Martindale method, the abrasion loss of the irradiated surface of the sheet before dry cleaning was is 43
mg, and after dry cleaning it was 46 mg, and excellent light resistance was maintained before and after dry cleaning.

[0037]

[Effects of the Invention] As explained above, the leather-like sheet material of the present invention is produced by using polyurethane reacted with a compound having a specific hindered amino group. The compound with hindered amino groups is less likely to fall off from the polyurethane.
When used for clothing, shoes, interior decoration, etc., it is less likely to fall off from the product during dry cleaning or washing, so it can maintain high light resistance over a long period of time.
It exhibits characteristics such as minimal discoloration, deterioration, migration, and bleed-out.

Claims (4)

[Claims] Claim 1: A residue obtained by removing a hydrogen atom from the terminal hydroxyl group of a hindered amino group represented by the following formula 1 is bonded to the organic isocyanate constituting the polyurethane elastic body, and the repeating unit of the compound is 1 g of the polyurethane elastic body. A leather-like sheet-like material comprising a polyurethane elastic material having a content of 0.00005 to 0.003 mmol per unit and a fibrous base material. [Chemical formula 1] 2. After impregnating a fibrous base material with a polyurethane solution and/or coating it with porous polyurethane,
In the method for producing a leather-like sheet material by introducing the substrate into a coagulation bath, then washing with water and drying, the impregnating polyurethane and/or the coating polyurethane include a polymeric diol having an average molecular weight of 500 or more, an organic It consists of a polyisocyanate and a chain extender, and the compound of formula 1 is used as at least a part of the chain extender and/or end stopper in an amount of 0.00005 to 0 per 1 g of the polyurethane elastomer.
．． 1. A method for producing a leather-like sheet material, characterized in that a polyurethane elastomer polymerized in an amount of 0.003 mmol is used. 3. A polymeric diol having an average molecular weight of 500 or more, an organic polyisocyanate, a chain extender, and a repeating unit of formula 1 in an amount of 0.0 per gram of polyurethane elastomer.
A polyurethane multicomponent fiber comprising a thermoplastic polyurethane obtained by melt polymerizing the compound of formula 1 in an amount of 0005 to 0.003 mmol as a sea component, and a thermoplastic polymer incompatible with the polyurethane as an island component. . 4. A fiber aggregate is made from the fiber of claim 3 or a fiber mainly composed of the same, and then treated with a solvent that is a solvent for the polyurethane component and a non-solvent for the other components to form a part or all of the polyurethane. 1. A method for producing a leather-like sheet material, which comprises dissolving the polyurethane, introducing the substrate into a coagulation bath to coagulate the polyurethane, followed by washing with water and drying.