JPH02307988A - Sheet-like material and production thereof - Google Patents

Abstract

PURPOSE:To provide a flexible sheet-like material excellent in resistance to hydrolysis, fungi and flexural fatigue, moisture permeability, etc., made up of a fibrous substrate layer containing a specific polyurethane porous layer and a second polyurethane porous layer differing in the composition from the former polyurethane. CONSTITUTION:Firstly, a porous fibrous substrate layer is prepared by impregnating a knitted fabric or nonwoven fabric consisting of natural, regenerated or synthetic fiber with a polyester composition liquid with, as soft segment, a polyester 700-4000 in average molecular weight, i.e., a condensate from a dicarboxylic acid and diol consisting mainly of 1,9-nonanediol and/or 2- methyl-1,3-octanediol, followed by coagulation. Thence, the porous fibrous substrate layer is coated with a polyurethane composition liquid with, as soft segment, a polyether 500-3000 in average molecular weight or a polymer mixture of >=50wt.% of the polyether, followed by coagulation to form a porous layer of the polyurethane, thus obtaining the objective flexible leathery sheet-like material excellent in feeling and durability.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for producing a sheet material suitable for producing a leather-like sheet material that is flexible, has excellent hydrolysis resistance, mold resistance, flexibility, moisture permeability, good appearance, and texture. .

[Conventional technology]

Conventionally, fiber aggregates are impregnated with an elastomeric polymer solution mainly composed of polyurethane, or impregnated and applied, and treated in a non-solvent of the polymer to coagulate to produce a sheet-like leather-like material. When producing a base material, many proposals have been made regarding regulators and coagulation methods for controlling the coagulation properties of polymers and the pore structure of the porous layer to be formed. For example, Japanese Patent Publication No. 7110/1983 describes that sorbitol, sorbitan, or alkylene oxide adducts of carboxylic acid esters of sorbite are mixed with a polyurethane solution and wet-coagulated. Japanese Patent Publication No. 49-8507 discloses that a polyurethane solution blended with a phosphoric acid ester having an alkyl group or an alkylene group is coagulated, and Japanese Patent Publication No. 54-255 discloses that a polyethylene glycol alkyl ether compound is added to polyurethane.
46, and Japanese Patent Publication No. 58-42308 proposes wet coagulation of a polyurethane composition in which a sulfosuccinate compound is added to polyurethane. On the other hand, when coagulating a polyurethane solution in a non-solvent, the applicant uses higher alcohols, higher carboxylic acids, higher hydrocarbons, sorbitan surfactants, and polyoxyethylene surfactants as coagulation regulators in the polyurethane solution. For example, Japanese Patent Publication No. 42-22719 and Japanese Patent Publication No. 42-27269 disclose the addition of nonionic surfactants such as glycerin esters, fatty acid amides or ethylene oxide adducts of higher alkyl amines, and ethylene oxide adducts of fatty acids. Japanese Patent Publication No. 45-39634, Japanese Patent Publication No. 45-39635, Japanese Patent Publication No. 46-2
593 Publication, Special Publication No. 47-3477, Special Publication No. 4
7-5634, Japanese Patent Publication No. 48-4939, Japanese Patent Publication No. 48-4940, Japanese Patent Publication No. 48-4941, Japanese Patent Publication No. 48-5264, Japanese Patent Publication No. 55-470
Publication No. 54, Special Publication No. 55-47055, Special Publication No. 6
Publication No. 2-7220, Japanese Patent Publication No. 62-49899,
Special Publication No. 63-' 66956, Special Publication No. 63-'
It has been proposed in Publication No. 67588, etc. Additionally, the applicant has disclosed that 1,9-nonanediol and/or 2-methyl-
The production of polyurethane using a polyester diol obtained by condensation polymerization of a diol mainly composed of 1,8-octanediol and an aliphatic dicarboxylic acid, and the use of the polyurethane for artificial leather have already been reported in Japanese Patent Application Laid-Open No. 6
This method has been proposed in Japanese Patent Application Laid-open No. 1-185520 and Japanese Patent Application Laid-open No. 62-22817.

[Problem to be solved by the invention]

Conventional coagulation control of polyurethane solutions is largely controlled by the chemical structure of the polyurethane, and currently there is no coagulation regulator common to all polyurethanes. Even if polyurethane has the same soft segment, a stable porous structure cannot be formed unless the coagulation regulator is changed depending on the composition ratio of the hard segment and soft segment, the difference in the chemical structure of the hard segment, and the coagulation conditions. In particular, it is not easy to stably obtain a homogeneous porous structure with polyurethane in which a highly hydrophobic polymer is used for the soft segment. In particular, it is not easy to solidify polyurethanes with different chemical structures under the same solidification conditions to form a polyurethane layer with good uniformity and a stable porous structure. The present invention aims to balance the elastic properties of the base layer and the surface coating layer in a silvered leather-like sheet material and to obtain a product with excellent durability. We use two types of polyurethane with different chemical formulas, each with a highly hydrophobic polymer as a soft segment, and coagulate the polyurethane solutions under the same coagulation conditions to create a stable polyurethane layer with a homogeneous porous structure. An object of the present invention is to provide a method for manufacturing a sheet-like article. Furthermore, it is an object of the present invention to provide a sheet material suitable for producing a leather-like sheet material that is flexible, has excellent hydrolysis resistance and mold resistance, and has good bending resistance, moisture permeability, appearance, and texture.

[Means to solve the problem]

The present invention provides a sheet-like article comprising a fibrous base layer containing a polymer mainly composed of polyurethane and a porous layer made of a polymer mainly composed of polyurethane, in which the polyurethane constituting the fibrous base layer contains 1. It is a porous polyurethane material with a soft segment made of polyester with an average molecular weight of 700 to 4,000, which is a condensation product of diol and dicarboxylic acid mainly consisting of 9-nonanediol and/or 2-methyl 1,8-octanediol. , the polyurethane constituting the porous layer has an average molecular weight of 500 to 3,000.
of polyether or at least 50! This sheet-like material is characterized in that it is a polyurethane porous body whose soft segment is a polymer mixture of polyether/polyester in which i amount % is polyether. Furthermore, in the present invention, when a fiber aggregate is impregnated with a polymer solution mainly composed of polyurethane, applied, and then coagulated in a non-solvent of the polymer to produce a sheet-like article, A polyester diol with an average molecular weight of 700 to 4,000 obtained by condensation polymerization of a diol mainly composed of 1.9-nonanediol and/or 2-methyl 1.8-octanediol and a dicarboxylic acid, an organic diisocyanate, and chain elongation. At least one type of additive selected from the group of a polymer mainly composed of polyester polyurethane obtained by reacting with a polymer, alcohol-modified silicone oil, higher alcohol, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene block copolymer. and a polymer composition solution consisting of a polymer solvent;
■The coating polymer solution is a polyether diol with an average molecular weight of 500 to 3,000 or a mixed polymer diol of at least 50% by weight of polyether diol and polyester diol, organic diisocyanate, and carbon number 6.
At least one type of polymer selected from the group of polyurethane-based polymers obtained by reacting with the following low-molecular diols, polyoxyethylene alkyl ethers, higher alcohol sulfate salts, and polyoxyethylene polyoxypropylene block copolymers. A method for producing a sheet-like article characterized by using a polymer composition solution comprising an additive and a polymer solvent. That is, the present invention consists in laminating two types of polyurethane solutions with different compositions and producing a sheet-like material with a good porous structure by a wet coagulation method. The polyurethane used in the present invention is: (1) The polyurethane impregnated into the fiber aggregate is 1,9-nonanediol and/or 2-methyl 1,8-octanediol, or this diol and other diols, such as ethylene glycol.
Propylene glycol, 1,4-butanediol, 1.
A mixed diol obtained by mixing diols selected from 5-bentanediol, 3-methyl 1.5-bentanediol, 1.6-hexanediol, etc. and an aliphatic dicarboxylic acid,
For example, one selected from aliphatic dicarboxylic acids or aromatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid. 4. At least one type of polyester diol having an average molecular weight of 700 to 4,000 obtained by condensation polymerization of one type or two or more types of dicarboxylic acids, and an organic diisocyanate such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4. 4
Aromatic diisocyanates such as '-diphenylmethane diisocyanate, ■-Isocyanate 3-incyanate methyl-3,5,5-1-limethylcyclohexane, l,6-hexamethylene diisocyanate, 1.4
-dicyclohexylmethane diisocyanate, 4.4'
-dicyclohexylmethane diisocyanate, 3.3'
At least one organic diisocyanate selected from aliphatic diisocyanates or alicyclic diisocyanates such as -dimethyl-424'-dicyclohexylmethane diisocyanate, and the chain extender, for example, ethylene glycol, propylene glycol, 1,4-butanediol. , 1,6-hexanediol, 3-methyl-1
, 5-bentanediol, l,4-cyclohexanediol, diols such as xylene glycol, ethylenediamine, propylenediamine, hexamethylenediamine, hydrazine, adipic acid dihydrazide, isophthalic acid dihydrazide, N-methyl-bis(3-aminopropyl) Amine, bis-N, N'-(3-aminopropyl)
Piperazine, cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3.3″-dimethyl-4
, 4'-diaminodicyclohexylmethane, l-amino-3-aminomethyl-3,5,5-)limethylcyclohexane, etc. , this polyurethane is referred to as PNOA polyurethane). Alternatively, the PNOA polyurethane may be mixed with other polyurethanes in an amount of 40% by weight or less. The preferred polyurethane to be mixed is polyoxyethylene polyurethane or polyoxytetramethylene polyurethane. ■Polyurethane for forming the porous surface layer is polyether diol with an average molecular weight of 500 to 3.000,
For example, at least one polymer diol selected from polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, etc., or less than 50% by weight of polyester diol for polyether diol. Diols, such as polyethylene adipate glycol, polyethylene propylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, 3-methyl-1,5-
A mixed polymer diol prepared by mixing at least one polymer diol selected from pentane adipate glycol, polycaprolactone glycol, etc., and an organic diisocyanate, such as phenylene diisocyanate,
Aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4゜4''-diphenylmethane diisocyanate, l-isocyanate-3
-incyanate methyl-3,5,5-trimethylcyclohexane, 1,6-hexamethylene diisocyanate, 1,4-dicyclohexylmethane diisocyanate,
4.4'-dicyclohexylmethane diisocyanate,
3. At least one selected from aliphatic diisocyanates or alicyclic diisocyanates such as 3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.
types of organic diisocyanates, preferably organic diisocyanates mainly consisting of aromatic diisocyanates;
Chain extenders, such as ethylene glycol, propylene gellicol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-bentanediol,
1. Polyurethane obtained by reacting with at least one diol selected from 4-cyclohexane diol, xylene glycol, etc. (hereinafter, this polyurethane is referred to as P
ET polyurethane). The PNOA polyurethane and PET polyurethane used in the present invention are prepared using the solvent N,N'-dimethylformamide (
Polyushituff 10 dissolved in DMF (hereinafter abbreviated as DMF)
The polyurethane has a solution viscosity of at least 1 poise, preferably in the range of 1.3 to 10 poise, when the wt % DMF solution is measured at a temperature of 30 DEG C. If the viscosity of this polyurethane is low, the strength and bending fatigue resistance of the sponge structure will not be sufficient. In addition, if the viscosity of polyurethane is high, it may not be easy to impregnate it into the fiber aggregate, it may not form a good solution coating layer, it may be difficult to process it into a good sheet-like product, and it may also be difficult to form a good sheet-like product. It becomes difficult to solidify into a sponge structure. In addition, the solution concentration of polyurethane is
The amount for PNOA polyurethane impregnation is in the range of 5 to 30% by weight, preferably 8 to 25% by weight, and the amount for PET polyurethane application is in the range of 10 to 25% by weight, preferably 12 to 23% by weight. If the concentration of polyurethane is low, a sponge structure with sufficient strength cannot be obtained. On the other hand, if the concentration of polyurethane is high, the coagulability will be uneven, making it impossible to obtain a flexible sponge structure with good homogeneity. Next, as the coagulation regulator added to the polyurethane solution, (1) the additive added to the polymer mainly composed of PNOA polyurethane impregnated into the fiber aggregate is -H or -CH,
, R1 is an alkyl group, n is an integer of 10 to 35, average molecular weight 850 to 3,500), alcohol-modified silicone oil, higher alcohol having 8 or more carbon atoms, e.g. Eva,
Octatool, nonanol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, oleyl alcohol, ceryl alcohol, myricyl alcohol, etc., sorbitan fatty acid esters For example, monoester, diester or triester obtained by reacting sorbitan with one, two or three molecules of higher carboxylic acid such as lauric acid, myristic acid, valmitic acid, oleic acid or stearic acid, etc., with the general formula HO (CHzCHzO) -(CHzCH(
CHs)O), average molecular weight represented by H 200-10
,000 polyoxyethylene polyoxypropylene block copolymers and the like. In addition, (1) the additive added to the polymer mainly composed of PET polyurethane that forms the porous surface layer has the general formula RO (C
Polyoxyethylene alkyl ethers represented by H, CH, O), )l, such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, higher alcohol sulfate salts, such as stearyl alcohol Sodium sulfate, sodium oleyl alcohol sulfate, sodium cetyl alcohol sulfate, sodium myristyl alcohol sulfate, sodium lauryl alcohol sulfate, sodium 2-ethylhexyl alcohol sulfate, etc.1. General formula HO(CH,CH20), (CHICH(CH2)O
), H, and polyoxyethylene polyoxypropylene block copolymers having an average molecular weight of 200 to 10,000. The amount of additives added to control the coagulation of polyurethane-based polymers varies depending on their effect; additives that exist as minute solids in the polymer solution or that precipitate as crystals form the nucleus for pore formation. In the case of 0.3 to 20% by weight of the polymer,
Additionally, additives may be present in the polymer solution to control the surface tension of the polymer composition liquid and prevent the coagulation of the polymer during the coagulation process, or additives may be present in the polymer solution to cause phase separation and polymerization. If it is necessary to prevent agglomeration, it is preferable to add it in an amount of 3 to 30% by weight based on the weight of the polymer. If the amount added is small, a good sponge structure cannot be obtained, resulting in a hard texture and poor bending fatigue resistance. on the other hand,
When the amount added is large, it becomes a coarse sponge structure,
This is not preferable because it reduces scratch strength and abrasion strength. In addition, in order to make the coagulation control effect of the additive more effective, water is added to the polymer composition solution at a zero level.
．． Adding the polymer in an amount in the range of 0.05 to 3.0% by weight and within a range in which the polymer does not precipitate is also effective in controlling the coagulation rate of the polymer and can form a good sponge structure. Next, the method of processing the impregnated polymer composition liquid and the coated polymer composition liquid into a sheet-like material is carried out using ordinary fibers, for example, chemical fibers such as polyester, polyamide, polyacrylonitrile, polyolefin, polyvinyl alcohol, regenerated cellulose, natural fibers, etc. Fiber-entangled nonwoven fabrics, fiber-napped knitted fabrics made of fibers or special types of fibers, such as ultrafine fibers such as polyester, polyamide, polyacrylonitrile, ultrafine fiber bundles, porous array special fibers, etc. One type of fabric selected from cloth, a laminated fabric of non-woven fabric and knitted fabric, etc. is impregnated with an impregnated polymer composition solution having a predetermined polymer solution concentration, and then coated with a polymer composition solution having a predetermined polymer solution concentration. The sheet-like material obtained by applying the liquid is
Coagulate in a non-solvent of the polymer. The condition for coagulating the polymer into a good sponge structure is to allow the coagulation regulator to act effectively. One method for this is to heat the polymer composition solution to which the coagulation regulator has been added to a temperature of about 40 to 80°C, and if you want the pores to have a larger sponge structure, you can Methods for rapidly forming a skin layer, such as coagulating in a coagulating liquid at a temperature lower than the temperature of 100 ml, or using a solvent-nonsolvent composition of the polymer as the coagulating liquid and coagulating in a coagulating liquid system containing a large amount of non-solvent. If you want the pores to have a fine sponge structure, you can solidify them in a coagulation solution at a temperature similar to or higher than that of the polymer composition solution, or use a polymer solvent-nonsolvent composition solution as the coagulation solution. Then, the polymer is coagulated by a slow coagulation method such as coagulation with a coagulating liquid system containing a large amount of solvent, and a fibrous base layer containing a polymer mainly composed of polyurethane and a porous layer composed of a polymer mainly composed of polyurethane are formed. A sheet-like material consisting of a solid layer is obtained. In addition, the additives for coagulation control present in the sheet-like material are
It is necessary to remove the additive if it has a negative effect on the sheet material, for example if it degrades the polymer, hardens it, or migrates to the surface and impairs its appearance, but in other cases it is not necessarily removed. There's no need. Since some additives have the effect of softening the sheet material, it is also preferable to use them in combination. The sheet-like material obtained in the present invention is subjected to finishing treatment as a leather-like sheet-like material, such as applying a coloring agent, a gloss modifier, etc. to the surface of the porous layer, embossing, softening treatment, dyeing, etc. It is made into a leather-like sheet-like material with a silver finish. Also,
The surface of the porous layer is buffed to expose internal pores to give it a suede-like surface, and a suede-like, leather-like sheet material is made by softening treatment, dyeing, etc. The leather-like sheet material obtained in the present invention forms a polymer layer with a spongy structure with good homogeneity, and has good shapeability in embossing and processability into secondary products, and is highly flexible. It is possible to obtain a material with a wide range of textures up to a certain level of flexibility, and the composition of the base layer and surface coating layer is well balanced, so it has good sensibility in terms of texture, appearance, etc. It has excellent properties such as hydrolysis resistance, mold resistance, bending fatigue resistance, and moisture permeability. For this reason, it is useful in the field of men's shoes, which require good setting properties and durability, where conventional artificial leather is insufficient, as well as sports shoes, sports equipment, and the like. Furthermore, since the orientation of the soft segment of the polyester polyurethane is small, the temperature dependence of the polyurethane is small, and the influence of texture at low temperatures is small. Therefore, it is suitable for use in shoes, clothing, gloves, and other products used at low temperatures.

【Example】

Next, embodiments of the present invention will be explained using specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified. (Production of PNOA polyurethane) Reference example 1 Polyester diol with an average molecular weight of 1,900 obtained by condensation polymerization of 1.9-nonanediol and adipic acid,
4.4'-diphenylmethane diisocyanate and ethylene glycol in a molar ratio of 1:4.5:3.5
Then, an amount to give the target solution concentration of 25% was added to the DMF solvent, and the reaction was carried out under heating until the solution viscosity at 75°C was about 1.
When the temperature reached 80 voids, the temperature was lowered to stop the polymerization reaction. The obtained polyurethane had a concentration of 10% and a temperature of 30%.
The solution viscosity at °C is 3.4 poise, and the theoretical ratio of soft segments in polyurethane is 58.6%. This polyurethane is designated as PNOA-1 polyurethane. Reference example 2 1,9-nonanediol 50%, 2-methyl-1,8-
Polyester diol with an average molecular weight of 2.000 obtained by condensation polymerization of a mixed diol containing 50% octanediol and adipic acid, 4.4'-diphenylmethane diisocyanate and 1.4-butanediol in a molar ratio of 1:5:
In step 4, an amount to give a target solution concentration of 25% was charged into a DMF solvent and reacted under heating. When the solution viscosity at 75° C. reached about 190 voids, the temperature was lowered to stop the polymerization reaction. The obtained polyurethane had a concentration of 10% and a temperature of 3
The solution viscosity at 0°0 is 3.5 voids, and the theoretical ratio of soft segments in polyurethane is 55.4%. This polyurethane is designated as PNOA-2 polyurethane. Reference Example 3 1.9-nonanediol and adipic acid were condensed and polymerized to obtain (1) a polyester diol with an average molecular weight of 900, (2) a polyester diol with an average molecular weight of 1,380, and (2) a polyester diol with an average molecular weight of 3,200. . These polyester diols each have a 4.4'-
Diphenylmethane diisocyanate and a mixed diol of 50% ethylene glycol and 50% 3-methyl-1,5-bentanediol were mixed in a molar ratio of 1:2:1 (theoretical ratio of soft segment 60. 8%), molar ratio 1:3.5:2.5 for polyester diol (■) (theoretical ratio of soft segment 56.1%), molar ratio 1:8 near C for polyester diol (■) The theoretical ratio of soft segment is 55.5%), and an amount to give a target solution concentration of 25% is charged into a DMF solvent, and reacted under heating.
When the solution viscosity at °C was in the range of about 180-200 poise, the temperature was lowered to stop the polymerization reaction. The solution viscosity of the obtained polyurethane was measured at a concentration of 10% and a temperature of 30°C. As a result, the solution viscosity of polyurethane from polyester diol (1) was 2.8 voids (referred to as PNOA-3 polyurethane). Solution viscosity of polyurethane from polyester diol (2) is 3.7 poise (referred to as PNOA-4 polyurethane). The solution viscosity of the polyurethane from the polyester diol (1) was 3.1 voids (referred to as PNOA-5 polyurethane). Reference Example 4 Polyester diol with an average molecular weight of 1.650 obtained by condensation polymerization of 2-methyl-1,8-octanediol and sebacic acid, tolylene diisocyanate, and ethylene glycol in a molar ratio of 1:6:5 to achieve the target Solution concentration 25%
An amount of
When the solution viscosity at 75°C reached about 135 voids, the temperature was lowered to stop the polymerization reaction. The obtained polyurethane had a concentration of 10% and a solution viscosity of 2.5% at a temperature of 30°C.
6 voids, the theoretical ratio of soft segments in polyurethane is 54.9%. This polyurethane is designated as PNOA-6 polyurethane. (Manufacture of PET polyurethane) Reference Example 5 Polytetramethylene ether glycol having an average molecular weight of 1.500, 4.4°-diphenylmethane diisocyanate and ethylene glycol were mixed at a molar ratio of 1:4.5:
In step 3.5, an amount to give the target solution concentration of 25% was charged into the DMF solvent, reacted under heating, and when the solution viscosity at 75°C reached about 185 voids, the temperature was lowered to stop the polymerization reaction. Ta. The obtained polyurethane and rethane have a concentration of 10%,
The solution viscosity at a temperature of 30°C is 3.3 poise, and the theoretical ratio of soft segments in polyurethane is 52.8%. This polyurethane is referred to as PET-1 polyurethane. Reference Example 6 Mixed polymer diol of 60 parts of polytetramethylene ether glycol with an average molecular weight of 2,000 and 40 parts of polyethylene adipate glycol with an average molecular weight of 2.000, 4.4'-diphenylmethane diisocyanate and 1.4-butanediol in moles An amount to give a target solution concentration of 25% at a ratio of 1:5:4 was charged into a DMF solvent, reacted under heating, and when the solution viscosity at 75°0 reached approximately 190 boids, the temperature was lowered and polymerization was carried out. The reaction was stopped. The obtained polyurethane had a concentration of 10%, a solution viscosity of 3.5 voids at a temperature of 30°C, and a theoretical soft segment ratio in the polyurethane of 55.4%. This polyurethane is referred to as PET-2 polyurethane. (Manufacture of sheet-like product) Example (Preparation of impregnated polymer composition liquid) Impregnation liquid 1 80 parts of PNOA-1 polyurethane solution, average molecular weight 1.
1 part 850 alcohol denatured silicone oil and DM
A liquid containing 19 parts of F was prepared and kept at a liquid temperature of 50°C. The composition liquid viscosity at 50°C is 56.5 poise.
I. Impregnation solution 2 A composition solution of 72 parts of PNOA-1 polyurethane solution, 1 part of carbon black, 2 parts of stearyl alcohol, 1 part of sorbitan tristearate, and 24 parts of DMF was prepared,
The liquid temperature was kept at 55°C. The composition liquid viscosity at 55°C was 28.5 poise. Impregnation liquid 3: 80 parts of PNOA-1 polyurethane solution, average molecular weight: 1.
A composition liquid containing 3 parts of 500% polyoxyethylene polyoxypropylene block copolymer and 17 parts of DMF was prepared and kept at a liquid temperature of 55°C. The composition liquid viscosity at 55°C was 52 poise. Impregnation Solution 4 A composition solution containing 64 parts of PNOA-2 polyurethane solution, 2 parts of ceryl alcohol, 2 parts of sorbitan monostearate, 1 part of water, and 31 parts of DMF was prepared and kept at a solution temperature of 55°C. Impregnation solution 5 72 parts of PNOA-3 polyurethane solution, average molecular weight 2.
A liquid composition of 1 part of 400% alcohol-denatured silicone oil, 2 parts of cetyl alcohol, and 25 parts of DMF was prepared and kept at a temperature of 50°C. Impregnation liquid 6 72 parts of PNOA-4 polyurethane solution, average molecular weight 2.
A liquid composition containing 1 part of 400-alcohol-modified silicone oil, 2 parts of cetyl alcohol, and 25 parts of DMF was prepared and kept at a liquid temperature of 50°C. Impregnation solution 7 72 parts of PNOA-5 polyurethane solution, average molecular weight 2.
A liquid composition containing 1 part of alcohol-denatured silicone oil 400, 2 parts of cetyl alcohol, and 25 parts of DMF was prepared and kept at a liquid temperature of 50°C. Impregnation liquid 8 (comparative example) 80 parts of PNOA-1 polyurethane solution and 20 DMF
Adjust the polyurethane solution at 500C! Keep it warm. Impregnation solution 9 (comparative example) 80 parts of PNOA-2 polyurethane solution, 1 part of water and D
Adjust the polyurethane solution in the MFlQ part and bring the solution temperature to 50.
It was kept warm at 'C. Impregnation Solution 10 (Comparative Example) A polyurethane solution containing 80 parts of PNOA-2 polyurethane solution, 2 parts of butanol, and 18 parts of DMF was prepared and kept at a liquid temperature of 50°C. (Adjustment of Coating Polymer Composition Liquid) Coating liquid I A composition liquid containing 80 parts of PET-1 polyurethane solution, polyoxyethylene oleyl ether and 17.5 parts of DMF was prepared, and the liquid temperature was 5.
The temperature was kept at 5°C. The composition liquid viscosity at 55°C was 52 poise. - Coating liquid 2 80 parts of PET-1 polyurethane solution, 2 parts of 2-ethylhexyl alcohol sulfate ester sodium salt, 0.5 part of polyoxyethylene lauryl ether, and DMF17
．． 5 parts of the composition solution was prepared and kept at a temperature of 55°C.
The composition liquid viscosity at 55°0 is 5o. 5 points hot
I. Coating liquid 3 A composition liquid containing 64 parts of PET-2 polyurethane solution, 2 parts of 2-ethylhexyl alcohol sulfate sodium salt, 0.5 m of polyoxyethylene lauryl ether, 2 parts of titanium oxide, and 31.5 parts of DMF was adjusted, and the liquid temperature was 55.
The temperature was kept at °C. The composition liquid viscosity at 55°C was 15 poise. Coating liquid 4: 72 parts of PET-2 polyurethane solution, average molecular weight: 2.3
A composition liquid containing 3 parts of polyoxyethylene polyoxypropylene block copolymer No. 00, 1 part of water, and 22 parts of DMF was prepared and kept at a liquid temperature of 55°C. The composition liquid viscosity at 55°C was 25.5 poise. Coating liquid 5 (comparative example) A composition liquid of 72 parts of PET-2 polyurethane solution, 1 part of water, 2 parts of titanium oxide, and 25 parts of DMF was adjusted, and the liquid temperature was 5.
The temperature was kept at 5°C. The composition liquid viscosity at 55°C is 27
It was Poise. (Manufacture of sheet-like product) Multicomponent fiber with a fineness of 6 denier obtained by melt-spinning 40 parts of high-flow polyethylene and 60 parts of 6-nylon and drawing it (
6-Using nylon as a superfine fiber component), a fiber web is made as a staple fiber by a dry method and laminated. After that, needle punching is performed from both sides to obtain an average basis weight of 300 g/+a.
This fiber-entangled nonwoven fabric was impregnated with the previously prepared impregnating liquid, and then the previously prepared coating for forming a coating layer was applied to one side of the fiber-entangled nonwoven fabric impregnated with the impregnating liquid. After applying a coating composition solution in an amount of 100 g/m'' as polyurethane amount, a 30% DMF aqueous solution,
The fibers are immersed in a coagulating solution at a liquid temperature of 35°C to coagulate, washed with hot water, the polyethylene component in the fibers is removed by hot toluene treatment, and then treated with a cationic activator dispersion and dried. , a sheet-like material was obtained. This sheet-like material was finished by applying a finishing composition liquid containing a coloring agent onto the surface of the coating layer, and subsequently embossing the surface to obtain a grain-finished leather-like sheet-like material. The coagulation properties of polyurethane can be determined from the state of the sponge structure of these leather-like sheets.
In addition, Table 1 shows a comparison of performance related to sensitivity such as folding and texture of the coating layer. The evaluation symbols in the table were determined as follows. (1) Regarding the texture, 0: Flexibility with cowhide-like elasticity, ○: Slightly elastic texture, Δ: Texture with a slightly strong rebound, X: Hard texture with strong rubber rebound, (2) Creases. Wrinkle condition: ◎: Many fine, long wrinkles similar to cowhide leather occur, O: Many fine wrinkles occur, △: Wrinkles mixed with loose folds occur, ×: Only rough fold wrinkles occur. , also JIS -65
The moisture permeability measured by the 49 method was 1.150-1,450g/mZ・2.4 for the leather-like sheet material of Example 1-10.
hr, whereas the leather-like sheet materials of Comparative Examples 1 to 5 were 350 to 420 g/m!・It was a low 24 hours. In other words, the polyurethane of the sheet-like material of the example forms a stable spongy structure with good uniformity when coagulated, so it has a stiff flexibility similar to cowhide, and the creases that occur are natural like leather. It is a shape that occurs in Furthermore, it was possible to easily produce a leather-like sheet-like product with a good appearance. On the other hand, in the sheet-like material of the comparative example, not only the pores were formed irregularly, but also the formed sponge structure was unstable. This results in a sheet-like product with a poor appearance and high rubber repulsion, resulting in a structure similar to that of a non-porous structural layer dotted with large pores. Furthermore, it was not possible to produce a leather-like sheet material with a good appearance. Comparative Example 6 Polyester polyurethane obtained by polymerizing polybutylene adipate glycol with an average molecular weight of 2.000, 4.4'-diphenylmethane diisocyanate, and 1.4-butanediol at a molar ratio of 1:6:5 (soft segment in polyurethane). A coating composition liquid 6 containing 18% (theoretical ratio 50.6%), 1% stearyl alcohol, 1% polyoxyethylene oleyl ether, and 78% DMF was prepared and kept at a liquid temperature of 50°C. A fiber-entangled nonwoven fabric made of polyester staple fibers with a fineness of 1.5 denier was impregnated with impregnating liquid 2, and then coating composition liquid 6 was applied on one side in an amount of 100 g/m'' as a polyurethane amount, and a 30% DMF aqueous solution, The polyurethane was coagulated by treatment in a coagulation solution at a temperature of 40°C, washed with water, and dried to obtain a sheet-like material.The sponge structure of this sheet-like material was a slightly fine sponge with good uniformity, and it was A leather-like sheet-like product was prepared in the same manner as in the example.This leather-like sheet-like product had a firm and flexible texture, and had good folds and wrinkles.Next, the leather-like sheet-like product of Comparative Example 6 was prepared. and Example 1-10
A leather-like sheet material was immersed in hot water at 90°C, and when the leather-like sheet material was bent 10 times, the immersion time until the polyurethane of the surface coating layer cracked was compared to determine the hydrolysis resistance. compared. As a result, cracks were observed in the leather-like sheet material of Comparative Example 6 on the 11th day, but no cracks were observed on the 20th day in the leather-like sheet material of Example. In addition, after being left in several types of mold for 10 days, a bending test was performed using a 7 Lexo-ohmeter, and as a result, cracks were observed on the surface of the leather-like sheet material of Comparative Example 6 after 2.380 bends. However, no cracks were observed in the leather-like sheet material of the example even after being bent 100,000 times.

【Effect of the invention】

The leather-like sheet material obtained in the present invention forms a polymer layer with a spongy structure with good homogeneity, and has good embossing properties and processability into secondary products. It is possible to obtain products with a wide range of textures, including certain flexibility, and has good sensitivity in terms of texture and appearance, and has excellent durability such as hydrolysis resistance, mold resistance, bending fatigue resistance, and moisture permeability. It is something that Therefore, it is suitable for use in the field of men's shoes, where conventional artificial leather is insufficient, as well as sports shoes, sports goods, clothing, gloves, and other articles.

Claims (2)

[Claims] (1) In a sheet-like article consisting of a fibrous base layer containing a polymer mainly composed of polyurethane and a porous layer made of a polymer mainly composed of polyurethane, the polyurethane constituting the fibrous base layer contains 1,9 -nonanediol and/or
Or, it is a polyurethane porous body with a soft segment made of polyester with an average molecular weight of 700 to 4,000, which is a condensation product of a diol mainly composed of 2-methyl 1,8-octanediol and a dicarboxylic acid, and constitutes a porous layer. A sheet-like material, characterized in that the polyurethane is a polyurethane porous body whose soft segments are polyether having an average molecular weight of 500 to 3,000 or a polyether/polyester polymer mixture in which at least 50% by weight is polyether. (2) When a fiber aggregate is impregnated with a polymer composition solution mainly composed of polyurethane, applied, and then coagulated in a polymer non-solvent to produce a sheet-like product, [1] Impregnated polymer composition solution. is a polyester diol with an average molecular weight of 700 to 4,000 obtained by condensation polymerization of a diol mainly composed of 1,9-nonanediol and/or 2-methyl 1,8-octanediol and a dicarboxylic acid, an organic diisocyanate, and a chain. At least one selected from the group consisting of a polymer mainly composed of polyester polyurethane obtained by reacting with an extender, alcohol-modified silicone oil, higher alcohol, sorbitan fatty acid ester, and polyoxyethylene polyoxypropylene block copolymer.
[2] The coating polymer composition liquid has an average molecular weight of 500 to 3,000.
0 polyether diol or a mixed polymer diol of at least 50% by weight of polyether diol and polyester diol, a polymer mainly composed of polyurethane obtained by reacting an organic diisocyanate and a low molecular weight diol having 6 or less carbon atoms. , polyoxyethylene alkyl ether, higher alcohol sulfate ester salt, polyoxyethylene polyoxypropylene block copolymer, and a polymer solvent. Characteristic sheet-like product manufacturing method.