JPH0345144B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to a leather-like sheet material that is flexible and tough, and has excellent heat resistance, solvent resistance, light resistance, hydrolysis resistance, and the like. (Prior Art) Silver-covered artificial leather made by coating a fibrous base material with a polyurethane composition is preferably used because of its flexibility and toughness. However, it has heat resistance that can withstand ironing, solvent resistance that can withstand dry cleaning and washing, and color fastness that can withstand long-term use.
The reality is that it is not possible to obtain products that fully satisfy durability (stability against light, heat, acidity, etc.). Various methods have been proposed to improve these drawbacks, including (a) using polyurethane with a specific structure, (b) adding various stabilizers, and (c) combining (a) and (b). However, it has not been possible to satisfy the above-mentioned characteristics in a well-balanced manner. Generally, the coating layer made of polyurethane is provided by providing an adhesive layer made of polyurethane and an isocyanate crosslinking agent on the fibrous substrate side, and further providing at least one coating layer for surface finishing on the adhesive layer. The polyurethane used for the adhesive layer has a lower molecular weight and is more flexible than the skin layer polyurethane, taking into consideration factors such as adhesion to fibers, texture, and processability.
Perform sufficient crosslinking to provide the necessary strength. In addition, the surface layer polyurethane should have a higher molecular weight and be harder than the adhesive layer polyurethane in consideration of dry touch, abrasion strength, bending strength, etc., and the desired properties can be achieved by appropriately combining the polyurethanes of both layers. That is, it is common practice to use a coating layer on the surface side that has a larger 100% modulus. (Objective of the present invention) The present invention aims to provide the polyurethane used in these coating layers with a high degree of the various properties described above by using a specific polyurethane composition. That is, the object of the present invention is to provide a silver-covered artificial leather particularly suitable for clothing, which satisfies the well-balanced properties of being flexible and strong, with little discoloration or deterioration when worn for a long period of time, and withstands dry cleaning and ironing. Our goal is to provide the following. (Structure of the present invention) The leather-like sheet material of the present invention consists of a fibrous substrate and at least coating layers (A) and (B), and the 100 modulus of (A) is smaller than that of (B), and the leather-like sheet material of the present invention In a leather-like sheet product having a coating layer (A) on the base side, the coating layer (A) includes at least a polyurethane elastomer, a hindered amine compound represented by the following general formula (), and a trifunctional isocyanate represented by the following general formula (). The leather-like sheet material is made of a reaction product of a compound, and the coating layer (B) is made of a reaction product of at least a polyurethane elastomer and a hindered amine compound represented by the following general formula (). General formula () [However, in the formula, R ₁ is a substituent selected from the group consisting of hydrogen, a benzyl group, a halogen, a lower alkyl group, or a benzyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkoxy group. R ₂ is hydrogen, a lower alkyl group, a phenyl group, a halogen, a phenyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkyl group or a lower alkoxy group, a benzyl group, a halogen,
A substituent selected from the group consisting of a benzyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkyl group or a lower alkoxy group, and a cyano group. _{and _ _} a substituent selected from the group consisting of groups (where R ₃ is a lower alkyl group, R ₄ is an organic dicarboxylic acid residue, R ₅
is an organic diol residue, n is an integer from 1 to 50, and m is from 1 to
(represents an integer of 15). R ₈ and R ₉ are the same or different alkyl groups having 1 to 3 carbon atoms, or R ₈ and R ₉ combine to form a saturated 5- or 6-membered ring. ] General formula () (R is a divalent hydrocarbon residue having 2 or 3 carbon atoms.) That is, the present invention provides a coating layer comprising at least a polyurethane elastomer, a specific hindered amine compound, and a specific trifunctional isocyanate compound on a fibrous base. (A) and a covering layer (B) consisting of a polyurethane elastomer and a specific hindered compound are sequentially laminated to obtain silver-coated artificial leather with desirable characteristics. In the present invention, it is sufficient that the fibrous substrate, the coating layer (A), and the coating layer (B) are configured in this order, and other coating layers may be interposed between them to the extent that the effects of the present invention are not impaired. Alternatively, it is also possible to provide another layer on the outermost surface. Furthermore, as described above, the 100% modulus of the covering layer (A) needs to be smaller than that of the covering layer (B), but its value can be selected as appropriate. Generally (A) 100
The % modulus is preferably 5 to 150 Kg/cm ² , more preferably 10 to 80 Kg/cm ² . The 100% modulus of (B) is preferably 30 to 300 Kg/cm ² , more preferably 50 to 200 Kg/cm ² . Here, 100% modulus refers to tensile strength at 100% elongation. The polyurethane elastomer used in the present invention is
It is a polymer obtained by reacting a polymeric diol with an organic diisocyanate and a chain extender. Examples of polymeric diols include polyether glycol, polyester glycol, and polyether ester glycol, which have hydroxyl groups at both ends and have a molecular weight of 500 or more, preferably 1,000 to 5,000. These include ethylene oxide) glycol, poly(propylene oxide) glycol, poly(tetramethylene oxide) glycol, polycaprolactone glycol, polyethylene adipate, polybutylene adipate, polytetramethylene adipate, polycarbonate diol, etc. alone or in mixtures. Examples of the organic diisocyanate include diphenylmethane-4,4'-diisocyanate, toluylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and mixtures thereof. The chain extender is a compound having two functional groups that react with the organic diisocyanate as shown in the above example, and the glycol chain extender includes ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, etc. be. Examples of the diamine chain extender include 4,4'-diaminodiphenylmethane, tolylene diamine, 4,4'-diaminodicyclohexylmethane, and mixtures thereof. The object of the present invention is flexibility, high strength, and
In order to satisfy various physical properties such as heat resistance, solvent resistance, and weather resistance in a well-balanced manner, the amount of organic diisocyanate relative to the polymer diol should be 1.5 to 6.0 molar equivalents, and the nitrogen content based on the isocyanate group should be 2 to 8% by weight.
is preferred. It is desirable to use a high molecular weight polyurethane elastomer with an OH value of 20 or less, preferably 10 or less, and it is necessary to select the most suitable one depending on the desired properties. Specific examples of hindered amine compounds used in the present invention include 2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-
Tetramethyl-4-methyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-ethyl-4-hydroxypiperidine, 2,2,6,
6-tetramethyl-4-phenyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-
4-aminopiperidine, 2,2,6-trimethyl-6-ethyl-4-hydroxypiperidine, 2,
2,6-trimethyl-6-ethyl-4-aminopiperidine, 2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine, 2,2-dimethyl-6,6-diethyl-4-aminopiperidine,
2,2-dimethyl-4-hydroxy-1-azaspiro[5,5]undecane, and 2,2-dimethyl-4-amino-1-azaspiro[5,5]undecane, or a mixture thereof. 1-benzyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 1-benzyl-2,2,
6,6-tetramethyl-4-ethyl-4-hydroxypiperidine, 1-benzyl-2,2,6,6
-Tetramethyl-4-phenyl-4-hydroxypiperidine, 1-benzyl-2,2,6,6-tetramethyl-4-aminopiperidine, 1-benzyl-2,2,6-trimethyl-6-ethyl-4 −
Hydroxypiperidine, 1-benzyl-2,2,
6-trimethyl-6-ethyl-4-aminopiperidine, -1-benzyl, -2,2-dimethyl-6,
6-diethyl-4-hydroxypiperidine, 1-
Benzyl-2,2-dimethyl-6,6-diethyl-4-aminopiperidine, 1-benzyl-2,2
-dimethyl-4-hydroxy-1-azaspiro[5,5]undecane, and 1-benzyl-2,
2-dimethyl-4-amino-1-azaspiro[5,5]undecane or a mixture thereof. 1-methyl-2,2,6,6-tetramethyl-
4-hydroxypiperidine, 1-methyl-2,
2,6,6-tetramethyl-4-ethyl-4-hydroxypiperidine, 1-methyl-2,2,6,
6-tetramethyl-4-phenyl-4-hydroxypiperidine, 1-methyl-2,2,6,6-tetramethyl-4-aminopiperidine, 1-methyl-2,2,6-trimethyl-6-ethyl- 4-hydroxypiperidine, 1-methyl-2,2,6-
Trimethyl-6-ethyl-4-aminopiperidine, 1-methyl-2,2-dimethyl-6,6-diethyl-4-hydroxypiperidine, 1-methyl-
2,2-dimethyl-6,6-diethyl-4-aminopiperidine, 1-methyl-2,2-dimethyl-
4-hydroxy-1-azaspiro[5,5]undecane, 1-methyl-2,2dimethyl-4-amino-1-azaspiro[5,5]undecane or a mixture thereof. More preferably, 2,
2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-aminopiperidine, 1-benzyl-2,2,6,6
-tetramethyl-4-hydroxypiperidine, 1
-benzyl-2,2,6,6-tetramethyl-4
-Aminopiperidine, 1-methyl-2,2,6,
6-tetramethyl-4-hydroxypiperidine,
1-methyl-2,2,6,6-tetramethyl-4
- aminopiperidine or a mixture thereof. More preferably, 2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,
6,6-tetramethyl-4-aminopiperidine,
1-methyl-2,2,6,6-tetramethyl-4
-Hydroxypiperidine, 1-methyl-2,2,
6,6-tetramethyl-4-aminopiperidine or a mixture thereof. In addition to the above-mentioned compounds, the hindered amine compound of the present invention is characterized in that the hydrogen bonded to the oxygen or nitrogen atom of the amino group, hydroxyl group, or monoalkylamino group of the substituent represented by X is -
(R ₃ O) n-H or -(COR ₄ COOR ₅ O) m-H
It may be substituted by In the former case, R ₃ is a lower alkylene group and n is 1
Represents an integer between ~50. The lower alkylene group has 2 to 14 carbon atoms. The compound is obtained by reacting the original hindered amine compound with R ₃ O (alkylene oxide). Specific examples of R ₃ O (alkylene oxide) include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, and mixtures thereof. In the latter case, R ₄ is an organic dicarboxylic acid residue, R ₅
represents an organic diol residue, and m represents an integer of 1 to 15. The organic dicarboxylic acid preferably has 2 to 12 carbon atoms, and specifically includes succinic acid, adipic acid,
Examples include azelaic acid, sebacic acid, phthalic acid, isophthalic acid, anhydrides thereof, and mixtures thereof. Organic diol has 2 or more carbon atoms
8 is preferred, and specific examples include ethylene glycol, propylene glycol, butylene glycol, hexane glycol, octane glycol, diethylene glycol, triethylene glycol, etc., and mixtures thereof. The above-mentioned hindered amine compounds are, for example,
53-1294 and its cited references. Trifunctional isocyanate compound (C) used in the present invention
is represented by the above general formula, 2,6-diisocyanate caproic acid-β-isocyanate ethyl ester, 2,6-diisocyanate caproic acid-γ-isocyanate propyl ester,
2,6-diisocyanate caproic acid-2-methyl-β-isocyanate ethyl ester. All of these can be produced by a known method of phosgenating an ester of lysine and an amino alcohol. Conventionally, as a crosslinking agent used in an adhesive layer, (a) a 3-adduct of trimethylolpropane with tolylene diisocyanate and (b) a 3-adduct of hexamethylene diisocyanate with trimethylolpropane have been frequently used. When (a) is used, a tough but hard film is obtained. If the amount used is increased in order to improve the properties, the material becomes harder and harder, making it impossible to simultaneously satisfy various properties such as flexibility, toughness, heat resistance, and solvent resistance. In the case of (b), it is used as a non-yellowing type crosslinking agent, but although it is relatively flexible, the reaction is slow and the crosslinked structure is rough, so it has disadvantages such as inferior properties. However, the trifunctional isocyanate of the present invention has a fast crosslinking reaction, can obtain a dense crosslinked structure, is excellent in the above-mentioned properties, and is a non-yellowing type, so it has excellent resistance to discoloration and light deterioration. Furthermore, in the present invention, color fastness and light fastness can be significantly improved by bonding a specific hindered amine to a polyurethane molecular chain. Methods for introducing hindered amines include (a) a method of adding and mixing at the time of synthesis of a polyurethane elastomer, a method of adding and mixing at the time of reaction of a polyol and an isocyanate, or a method of adding and mixing at the time of reacting a terminal isocyanate prepolymer and a chain extender; (b) A method of adding and mixing a polyurethane elastomer and a trifunctional isocyanate during a crosslinking reaction,
Alternatively, a method may be used in which a trifunctional isocyanate and a hindered amine are mixed and reacted, and then crosslinked with a polyurethane elastomer, or (c) a method in which a reaction product of a trifunctional isocyanate and a hindered amine is used. In the case of (a), there are drawbacks such as the difficulty in increasing the molecular weight of the polyurethane and the fact that the polyurethane elastomer bound with hindered amine is in a liquid state and easily decomposes when left for a long period of time. In the case of (b), the above-mentioned concerns are avoided and it is preferable because the components are added, mixed, and reacted during the preparation of the paint. In the case of (c), it is easier to obtain a polyurethane with higher molecular weight and better properties, and is particularly preferable for synthesizing the polyurethane of the coating layer (B). An example of a method for obtaining a reaction product between a trifunctional isocyanate compound and a hindered amine compound is to gradually react dropwise a solution of 1 mole of the hindered amine compound dissolved in a solvent such as butyl acetate or toluene to 1 mole of the isocyanate compound. obtained by. The reaction temperature is below 100℃,
Preferably, the reaction temperature is 50° C. or lower, and room temperature is also possible, and the reaction is carried out for a predetermined period of time. The reaction product is a compound having essentially two NCO groups, 1
It consists of a compound with one NCO group and a mixture of compounds with completely reacted NCO groups. For example, as a trifunctional isocyanate, 2,6
The reaction product of -diisocyanate-caproic acid-β-isocyanate ethyl ester (LTI-E) and 1-methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine (MTHP) as a hindered amine (LTI-E) /MTHP)
teeth, Consists of etc. The three NCO groups of the trifunctional isocyanate compound used in the present invention are characterized by different reactivities, and as a result of analysis, the proportion of these compounds is determined to be ≧
'>>>, and the compounds () and (') are the main components and are desirable. There is no particular limit to the amount of hindered amine added, but it is preferably 0.1 parts per 100 parts of the polyurethane elastomer.
-5 parts, particularly preferably 0.1-2 parts.
The hindered amine of the present invention is effective in small amounts;
All of the above methods (a), (b), and (c) have remarkable effects without impairing the original properties of polyurethane, and are not simply mixed.
Since it is bonded to polyurethane, it will not bleed out or be extracted and removed by solvent treatment, and its effect is permanent. The compositions of the present invention include other elastomeric polymers, pigments,
Dyes, fillers, stabilizers, etc. can be mixed and used as required. The fibrous substrate may be a non-woven fabric, a woven fabric, a knitted fabric, or a laminated or sandwiched fabric made of ultra-fine fibers and ultra-fine fiber bundles formed from natural and synthetic fibers of normal fineness, sea-island type fibers, peelable and split type fibers, etc. A polymer elastomer solution and/or dispersion liquid is applied as necessary. Moreover, a material provided with a porous layer on the surface may also be used. At least one side of these fibrous substrates may be fluffed by napping, buffing, or the like. It is preferable that such a fibrous substrate is colored, but if it is not colored, it may be colored after imparting a silver surface. It is desirable to form a silver surface on this fluff layer. Furthermore, the finer the denier of the fibers in the fluff layer, or the higher the fluff density, the thinner the grain layer can be, resulting in a product with a softer feel and superior appearance quality. Also,
It is preferable that the surface of the fibrous substrate is made of microfibers and/or bundles thereof densely intertwined, since its smoothness allows the coating layer of the high molecular weight polymer to be made thinner, thereby reducing the rubbery feel. In addition, methods for obtaining grain-faced artificial leather include a method of applying the composition of the present invention to a fibrous substrate using a gravure roll, a reverse roll coater, a knife coater, etc., heating and curing it, adding texture, and finishing the surface. A surface resin is applied to a textured release paper, and after drying and solidifying, the composition of the present invention is applied thereon, a fibrous substrate is bonded to the fibrous substrate while it is dry and still sticky, and both are peeled off after being heated and cured. Possible methods include obtaining the amount by (Effects of the present invention) In the leather-like sheet material of the present invention, the specific trifunctional isocyanate used in the coating layer (A) is a non-yellowing type, highly crosslinkable, provides a dense structure, is flexible and strong, It can satisfy various properties such as color fastness, weather resistance, heat resistance, and solvent resistance in a well-balanced manner. Furthermore, by bonding a specific hindered amine to this, color fastness and light deterioration resistance can be further improved. This hindered amine does not bleed out or is extracted and removed by dry cleaning, providing a long-lasting effect. Usually, a combination of non-yellowing type polyurethane and non-yellowing type crosslinking agent is used, but it is difficult to achieve a high level of both physical properties and color fastness, such as poor physical properties, especially severe repeated deformation and poor heat resistance. By using a specific trifunctional isocyanate and a specific hindered amine in combination as in the present invention, a polyurethane can be selected within a suitable range depending on the desired physical properties. The coating layer (B) further reinforces the properties of the coating layer (A) and adjusts the touch, color, and gloss.
Again, by using a specific hindered amine, a polyurethane with high physical properties can be selected. Therefore, when the leather-like sheet material of the present invention is used for clothing, it has a soft texture, high grain strength, excellent ironing and dry cleaning properties (especially changes in appearance), and is free from discoloration and deterioration due to long-term use. It exhibits characteristics such as low In addition, it exhibits features such as extremely low bleed-out of various additives in the coating during long-term storage under high temperature and high humidity conditions, migration of dye from the dyed base material to the film, and extremely low bleed-out. Further, these features are particularly exhibited when the color of the coating layer is light-colored, especially white. Furthermore, in the production method of silver-covered artificial leather, which involves forming a surface layer on release paper, applying an adhesive layer on top of the surface layer, and laminating the base material, the flexible and highly crosslinking properties of the crosslinking agent of the present invention can be utilized to form an adhesive layer on the adhesive layer. It is also possible to increase solvent resistance by using a large amount and allowing a part of it to migrate to the surface layer. Embodiments of the present invention will be shown below, but the present invention is not limited thereto. Unless otherwise indicated, percentages and parts are by weight. In addition, the following abbreviations are used in the examples. DMF Dimethylformamide TOL Toluene LTI 2,6-diisocyanate caproic acid β-isocyanate ethyl ester MTHP 1-Methyl-2,2,6,6-tetramethyl-4-hydroxypiperidine LTI/MTHP Equimolar reaction product of LTI and MTHP PCL Polycaprolactone glycol MDI Diphenylmethane-4,4'-diisocyanate BG Butylene glycol TMP/TDI Trimethylolpropane tolylene diisocyanate 3 mole adduct IPDI Isophorone diisocyanate EDA Ethylene diamine The evaluation method is as follows. Texture: Sensory evaluation was performed on a five-point scale (5 being the best). Colorfastness: The discoloration after irradiation at 63°C for 50 hours was visually evaluated using a fade meter on a five-point scale (5 being the best). Light resistance: 63°C with a fade meter; 63°C with a flexometer (JIS
K6545-1970), the state of surface cracks after being bent for 500,000 hours was visually evaluated on a five-point scale (5 being the best). Hydrolysis resistance: Samples were left for 5 weeks at a temperature of 70°C and humidity of 90% RH, and then visually evaluated using a flexometer for cracking on the surface after 500,000 hours of bending (5). is the best). Washing resistance: Visually check appearance changes such as wrinkles that occur on the sample surface after dry cleaning with normal Perclean 5 times.
Evaluation was made in stages (5 indicates the least change in appearance and good condition). Heat resistance: Changes in surface aperture when pressed at 150° C. for 10 seconds under 0.2 Kg/cm ² were visually evaluated on a five-point scale (5 indicates the best with the least change). Color transfer resistance: Layer the colored sample on a white polyurethane sheet (target piece), 70℃ x 70
%RH, 1Kg/cm ² for 24 hours, color transfer was visually evaluated on a 5-grade scale (5
indicates the best color transfer with the least amount of color transfer). Solvent resistance: A cloth was impregnated with toluene and the degree of change in the silver surface when gently wiped was visually evaluated on a five-point scale (5 being the best). Examples 1-2 The island component is 70 parts of polyester, the sea component is 30 parts of polystyrene, number of islands is 36, single yarn denier is 3.5
I made needle punched felt using 51mm denier. Next, this was shrunk in boiling water and dried, then impregnated with a 10% mixed dispersion consisting of 3 parts of non-yellowing type polyurethane and 7 parts of polyvinyl alcohol, and dried. Next, polystyrene was extracted and removed in triclene, dried, impregnated with a 12% polyvinyl alcohol solution, dried, impregnated with a 12% solution of non-yellowing type polyurethane, wet coagulated in water, and then soaked in a solvent in hot water. and polyvinyl alcohol was removed and dried. Slice this into half thickness, #100 on both sides.
Buffed with sandpaper, then finished buffed with #150 sandpaper, dyed white (no dye) with a jet dyeing machine, thickness 0.65mm, basis weight
A white fibrous substrate with naps on both sides having a weight of 210 g/m ² and an apparent density of 0.323 g/cm ³ was obtained. A polyurethane composition liquid for the coating layer (B) and a polyurethane composition liquid for the coating layer (A) were prepared as follows. (1) Polyurethane composition liquid for coating layer (B) A 30% DMF solution of polyurethane consisting of PCL having a molecular weight of 2000, MDI, LTI/MTHP reactant, and BG was obtained. To this, 10 parts of white pigment was added based on the solid content of polyurethane, further diluted with DMF,
% polyurethane composition liquid was obtained. The 100% modulus of the dry film of this composition is 120
Kg/ ^cm2 , and the solid content of polyurethane
MTHP content is 1%. (2) Polyurethane composition liquid for coating layer (A) 45% MEK/TOL of polyurethane consisting of PCL, MDI, MTHP, and BG with a molecular weight of 2000 = 2/1
A solution was obtained. Next, regarding the polyurethane solid content,
Add 10 parts white pigment and 12 parts LTI, and
A 25% polyurethane composition solution was obtained by diluting with DMF and TOL. The 100% modulus of the dry film of this composition is 20
Kg/ ^cm2 , and the solid content of polyurethane
MTHP content is 0.5%. Next, the above-mentioned polyurethane composition for the coating layer (B) is applied to a release paper having a kerf-adjusted drawing using a knife coater so that the dry film has a thickness of 7μ, and after drying, the above-mentioned polyurethane composition for the coating layer (A) is applied. The solution was applied so that the dry film had a thickness of 20 μm, and after removing a portion of the solvent, the above fibrous substrate was laminated, fixed by pressure, dried and cured, and then peeled off after aging to obtain a leather-like sheet. Comparative Example 1 Example 1 except that the polyurethane composition liquid for the coating layer (A) in Example 1 was prepared as follows.
A leather-like sheet material was obtained in the same manner as above. Polyurethane composition liquid for coating layer (B): During polyurethane synthesis in Example 1, LTI/MTHP reactants were not used, and instead, ultraviolet absorber Tinuvin P was used as a stabilizer, and Irganox 1010 was used as an antioxidant. One part of each was added to the polyurethane. Polyurethane composition liquid for coating layer (A): During polyurethane synthesis in Example 1, MTHP was not used, and instead, the same amount of the same stabilizer as for coating layer (B) was added. Furthermore, instead of LTI, 15 parts of TMP/TDI was used based on polyurethane as a crosslinking agent. Comparative Example 2 A leather-like sheet product was obtained in the same manner as in Example 1, except that the following polyurethane compositions were used for the coating layer (B) and the coating layer (A). Polyurethane composition for coating layer (B); instead of the polyurethane of Example 1, PCL with a molecular weight of 2000 was used.
A polyurethane composition liquid was obtained in the same manner as in Example 1 except that polyurethane consisting of IPDI and EDA was used. Polyurethane composition liquid for coating layer (A); instead of the polyurethane in Example 1, PCL with a molecular weight of 2000 was used.
Polyurethane consisting of IPDI and EDA was used, and TMP/HMDI was used instead of LTI as a crosslinking agent.
15 parts of polyurethane was used. The results are shown in Table 1, and it can be seen that the leather-like sheet material of the present invention is excellent in all properties.

[Table] Example 2 A leather-like sheet product was obtained in the same manner as in Example 1, except that the fibrous base material was dyed red and a red pigment was used in the polyurethane composition. Comparative Examples 3 and 4 Leather-like sheets were obtained in the same manner as in Comparative Examples 1 and 2, except that a fibrous substrate dyed red was used and a red pigment was used in the polyurethane composition.

[Table] As shown in Table 2, the results show that the leather-like sheet material of the present invention has excellent color transfer resistance and solvent resistance.

Claims (1)

[Scope of Claims] 1 Consisting of a fibrous base and at least covering layers (A) and (B), the 100% modulus of (A) is smaller than that of (B), and the covering layer (A) is provided on the side of the fibrous base. ), the coating layer (A) is made of at least a reaction product of a polyurethane elastomer, a hindered amine compound represented by the following general formula (), and a trifunctional isocyanate compound represented by the following general formula (). A leather-like sheet material, wherein the coating layer (B) is at least made of a reaction product of a polyurethane elastomer and a hindered amine compound represented by the following general formula (). General formula () [However, in the formula, R ₁ is a substituent selected from the group consisting of hydrogen, a benzyl group, a halogen, a lower alkyl group, or a benzyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkoxy group. R ₂ is hydrogen, a lower alkyl group, a phenyl group, a halogen, a phenyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkyl group or a lower alkoxy group, a benzyl group, a halogen,
A substituent selected from the group consisting of a benzyl group in which the hydrogen of the benzene nucleus is substituted with a lower alkyl group or a lower alkoxy group, and a cyano group. _{and _ _} a substituent selected from the group consisting of groups (where R ₃ is a lower alkyl group, R ₄ is an organic dicarboxylic acid residue, R ₅
is an organic diol residue, n is an integer from 1 to 50, and m is from 1 to
(represents an integer of 15). R ₈ and R ₉ are the same or different alkyl groups having 1 to 3 carbon atoms, or R ₈ and R ₉ combine to form a saturated 5- or 6-membered ring. ] General formula () (R is a divalent hydrocarbon residue having 2 or 3 carbon atoms.)